Jurnal Internasional

INTERNATIONAL JOURNAL OF
SCIENTIFIC RESEARCH
EDITOR-IN-CHIEF
MANAGING EDITOR
ASSISTANT MANAGING EDITOR
Hamid M.K. Al-Naimiy

Brian Murphy
Khaled Abbas El-Tarabily
EDITORIAL BOARD OF CONSULTANTS

Joseph F. Becker
Department of Physics, San Jose State University, U.S.A.
John E. Dyson
Department of Physics and Astronomy, University of Leeds, U.K.
Veronique Gouverneur
Department of Chemistry, University of Oxford, U.K.
Kevin B. Nolan
Department of Pharmaceutical and Medicinal Chemistry, Royal College of Surgeons, Republic of Ireland.
Ramesh D. Gulati
Centre of Limnology, Netherlands Institute of Ecology, The Netherlands.
Krishnapillai Sivasithamparam
School of Earth and Geographical Sciences, The University of Western Australia, Australia.
Billy E. Rhoades
Department of Mathematics, Indiana University, Bloomington, Indiana, U.S.A.
Robin E. Harte
Department of Pure and Applied Mathematics, University of Dublin, Trinity College, Republic of Ireland.
David R. Gray
Department of Earth Sciences, Monash University, Melbourne, Australia.
Robert J. Stern
Department of Geosciences, University of Texas at Dallas, U.S.A.
___________________________________________________________________________
EXECUTIVE COMMITTEE
ADMINISTRATIVE STAFF
Hamid M.K. Al-Naimiy

Brian Murphy
Khaled Abbas El-Tarabily
Basem Attili
Abdel Rahman Fowler
Girija Bhaskaran
Contact Information:
International Journal of Scientific Research,
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Tel: 00971-3-7134230
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Email: GirijaB@uaeu.ac.ae
___________________________________________________________________________
N.B.
The views expressed in this issue are those of the authors and do not necessarily reflect the views of the Editorial
Board of Consultants, the Executive Committee or the policies of the United Arab Emirates University.
2005 by the UAE University
All rights reserved. No part of this publication may be reproduced or copied in any form or by any means without
prior written permission from the Editor-in-Chief of the Journal.
i
International Journal of Scientific Research, Vol. 14, 2005
Editorial Preface
It is our pleasure to present to you this latest, and in many senses inaugural, issue, Volume 14, of the
International Journal of Scientific Research (IJSR). This issue, published by the College of Science
at UAE University, carries the title IJSR for the first time, replacing the previous title, Journal of the
Faculty of Science, UAEU. The reason for this change of name is understandable if one looks at the
nature and diversity of the research papers currently being submitted to the Journal. The scope and
reach of the Journal has widened, and the ultimate aim is to achieve a wider international
participation.
In this issue, you will see a number of new features. For example, the Journal includes a
Perspective article for the first time. This issue features an excellent perspective written by Professor
John Dyson from the University of Leeds in the UK, on Interstellar Bubbles. The Journal also
includes full research papers which encompass a wide variety of topics and has a new section on
Book Reviews.
Journal articles are now abstracted/indexed in CAS (Chemical Abstracts), Zentralblatt MATH
and BIOSIS UK (Zoological Records) and the Editorial Board continues to be strengthened by
members with expertise across the entire spectrum of science. Furthermore, all future editions of the
Journal will be printed in both hard-copy and electronic format.
The refereeing process has also been stream-lined and the Journal continues in its effort to
provide top-class peer-reviewed evaluations to all contributing authors.
If you have any suggestions for further improving this Journal, please do not hesitate to contact
the IJSR Office.
Professor Joseph Hill

Dean of the College of Science, UAEU
Professor Hamid M.K. Al-Naimiy

Editor-in-Chief, IJSR
ii
VOLUME 14, 2005
ISSN 1021-0806
CONTENTS
IJSR PERSPECTIVE
1-9
Interstellar Bubbles (Front cover graphic)
J. E. Dyson
IJSR FULL PAPERS
11-91
Determination of Radiological Doses of Radon and Natural Radionuclides

in the Open Environment of the Lahore and Kasur Districts, Pakistan
11
R. Najeeb, E. Hussain and U. Masood
Synthesis and Characterization of Some Composite Mesoporous Organosilicas

by a Co-condensation Route
19
J.E.G. Mdoe and D.J. Macquarrie
Corals as Bio-indicators to Trace Metal Pollution on the Kuwaiti Coral Islands,

Off the Arabian Gulf
27
A.H. Bu-Olayan, B.V. Thomas and A.H. Shaker
High Level Expression and Single-step Purification of in vivo Biotinylated

Green Fluorescent Protein
37
S. Salman Ashraf
iii
Assessment Study on Selective Physical Characteristics of Lubricating Oils
45
M.A. Rauf, S. Khaliq and S. Manzoor
Effect of Alkali Salts on the Viscosity of KAHU Grass Black Liquor
51
M. A. Rauf, M. J. Iqbal and Q. M. Malik
Design, Synthesis and Biological Evaluation of Novel Carbapenems
59
G.H. Hakimelahi, A.A. Moosavi-Movahedi, A.A. Saboury, V. Osetrov,

G.A. Khodarahmi and K.-S. Shia
Synthesis and Characterization of Some New Heterocyclic Tellurium(IV)Dithiocarbamate Complexes
71
A. Z. Al-Rubaie and M. Y. Al-Luaibi
Jordan Laid Bare
79
Robin Harte and Cora Stack
Convex Random Integral Functionals and Epiconvergence
83
K. Messaoudi, M. L. Leghmizi and M. Zerguine
IJSR BOOK REVIEWS
93-99
iv
Int. J. Sci. Res., Vol. 14 (2005), pp. 1-9
INTERSTELLAR BUBBLES
J.E. Dyson
Department of Physics and Astronomy, University of Leeds, Leeds LS2 9JT, UK
E-mail: jed@ast.leeds.ac.uk
Keywords: Stars, stellar winds, supernova remnants, mass-loading, linear structures.
ABSTRACT
Stars blow bubbles in the interstellar gas in galaxies. The bubbles can be produced by stellar UV
radiation fields, by stellar winds or mass-loss and by supernova explosions. A review of the
underlying basic theoretical descriptions is given followed by a discussion of some of the
modifications that have to be made to these necessitated by ever increasing high quality
observational data.
INTRODUCTION
Stars form from the cool interstellar medium
in galaxies. During their lifetimes, more or less
from their birth, most stars go through periods
of often violent prolonged mass-loss
collectively known as stellar winds. These
winds are driven by a wide variety of physical
processes including atmospheric wavemomentum deposition and radiation pressure.
The most catastrophic mass-loss process is the
almost instantaneous loss of about half the
mass of a star which is the final end-point of
evolution of the most massive (M > 8 M~)
stars; these are the Type II supernovae.
The various mass-loss events not only greatly

affect stellar evolution (since stellar evolution
is largely determined by stellar mass), but the
mass-loss represents an input of mass,
momentum and energy into any material in the
stellar environs. Massive stars also have
extremely powerful radiation fields that heat
the surrounding gas via photoionization. The
result is that the physical state of the
interstellar medium (ISM) in galaxies is
largely (though not entirely) determined by its
interaction with stars.
__________________________________________________________________________________
John Dyson was born in
Meltham in Yorkshire in the
UK in 1941, and received his
BSc. from Kings College at
the University of London
(Special Honours Physics) in
1962. This was followed by a
PhD in Astrophysics at the
University of Manchester
which he obtained in 1966
and a DSc. which he obtained in 1978. He has held
several positions throughout his career, which include
Research Fellow at the University of Wisconsin, USA
(1966-1967), Lecturer, Senior Lecturer, Reader in
Astronomy then Professor of Astronomy at the University
of Manchester (1967-1993). In 1996, he joined the
University of Leeds in the UK and was appointed
Professor of Astronomy there, a post which he still holds.

In 2003, he became President Division VI (Interstellar
Matter) of the International Astronomical Union.
In addition to these posts, Professor Dyson has held
several visiting fellowships in the Netherlands, Germany,
Australia and Chile. He has research interests in
interstellar and circumstellar gas dynamics, planetary
nebulae, active galactic nuclei and physical processes.
Professor Dyson has authored or co-authored over 150
refereed papers in these areas of research and has edited
3 books. He is co-author (with Professor D. A. Williams)
of Physics of the Interstellar Medium, which is a leading
undergraduate/postgraduate textbook, already in its
second edition (1997). In addition, he is co-author (with
Professor T. W. Hartquist and Dr. D. Ruffle) of a semipopular book, Blowing Bubbles in the Cosmos (2004).
The mass, energy and momentum deposition is

impulsive in the case of supernova sources and
continuous in the case of winds or radiation
fields. These are not mutually exclusive since,
for example, clusters of massive stars are
common and the different rates of evolution of
stars of differing masses can result in
combined wind and supernova activity.
Moreover, a sequence of individual supernova
explosions can often be reasonably
approximated as a continuous wind with a
mean power of the typical supernova energy
divided by the characteristic time between
explosions.
The literature on the interstellar gas flows
produced by winds and explosions is vast
indeed. Classic pioneering papers include [1]
flows driven by the radiation fields of massive
stars [2] supernova driven flows [3] flows
driven by fast winds from massive stars.
Although relatively simple models for the
complex flows produced have enabled much
progress to be made, the wealth of multiwavelength data now available have shown
that considerable modifications to the simple
models need be made. Indeed, badly
understood physical processes need to be
added to the models as best one can. One of
the driving forces behind these modifications

has been the recognition that the ISM reacting
to the stellar influences is multi-phase, usually
consisting of cool clouds embedded in a hotter
substrate as opposed to the single phase
medium assumed in the simple models. This
multi-phase nature leads to the process of
mass-loading of flows that has the most
profound consequences for flow structure and
evolution [4]. In this article I will briefly note
the classical models of star-ISM dynamical
interactions and review some of the most
recent work on modifications to them.
FLOW DYNAMICS IN SINGLE PHASE
MEDIA
Radiation driven bubbles (HII regions)
Radiation fields can inject momentum into
surrounding gas because of the absorption or
scattering of photons (e.g. by embedded dust
grains) or the radiation can heat the gas and
the increased pressure produces a hot
expanding bubble into which ISM is
assimilated during the expansion. The most
important case is when the hard radiation of a
massive star of high (several 104K) surface
temperature photoionizes the ISM, producing
an HII region (or ionized nebula). An example
is shown in Figure 1.
Fig. 1. The Orion Nebula (M42).
The heated gas has a temperature of about

104 K and an ionization front (IF) over-runs
the surrounding neutral gas that has a
temperature of 100 K or less. Neutral gas
crosses this front and exits fully ionized. These
IFs separating ionized and neutral gas are thin
(thickness about equal to a typical ionizing
photon mean-free-path in the neutral gas).
Initially a very fast IF over-runs the neutral
gas and sets up quickly an essentially
stationary bubble of hot gas. This bubble starts
to expand at the sound speed (about 10
km/sec) in the hot gas and drives a shock wave
ahead of the IF into the neutral ISM. The
bubble radius R (1+at)4/7, where a is a
constant, is dependent on the (assumed
constant) ISM density and the ionizing photon
output rate from the star, and its expansion
velocity V (1+at)-3/7.
As the bubble
expands, its interior density drops because to
maintain the gas in the state of total ionization
it must have, the electron-proton recombination
rate in the whole ionized volume equal to the
(constant) stellar ionizing photon output. The
interior pressure in the hot bubble then
decreases with time and depending on
circumstances, there can be a final state of
pressure equilibrium between a hot stationary
bubble and the neutral ISM. Note that many
(though not all) of the stars with hard radiation
fields have dynamically significant fast winds
and in reality, the bubble really is a combined
radiation and wind driven bubble (see below).
Wind-driven bubbles
The winds from stars can often be extremely
fast (velocities 100-1000 km/sec typically)
and are hypersonic both with respect to the
surrounding interstellar gas and to their
internal sound speeds. When these impinge on
the ISM, two shock waves are generated.
A very strong inwards facing shock slows
down the wind; an outwards facing shock
accelerates and sweeps up the ISM. Because
the mass-loss is continuous, the reverse shock
(in the stellar wind) never collapses onto the

star and a two-shock flow pattern moves
outwards in the stellar frame. The thermal
behaviour of the shocked wind determines the
flow dynamics. If this gas behaves
adiabatically, the outer shock is driven by the
pressure of the shocked wind; the flow is
called energy-driven and the outer shock
evolves with R t3/5 and V t-2/5. This
situation obtains for wind speeds greater than
100-200 km/sec, which apply to the winds of
massive stars. On the other hand, if the
shocked gas cools very quickly (wind speeds
less than the limits above), the outer shock is
driven by wind momentum and unsurprisingly
is called momentum-driven. This situation
obtains with winds from young stars with
masses not much more than that of the Sun.
Then the outer shock evolves as R t1/2, V
t-1/2. The quoted exponents above apply when
the ISM has a uniform density and where the
wind mass-loss rate and velocity are constant
in time. A special and important case of the
bubble
dynamics
obtains
when
the
exceptionally fast ( 2000-4000 km/sec) winds
from the stellar cores left behind after the
ejection of slow moving shells of cool gas in
the red-giant or asymptotic-giant-branch
phases of stars of a few solar masses interact
with these shells. To a first approximation,
these envelopes have densities that vary
inversely with the square of the radial distance
from the cores. This interaction produces
energy driven bubbles that have constant
velocities and these are the very well-known
planetary nebulae, an example of which is
shown in Figure 2. Flows can change from one
type to another depending on spatial variations
in the ISM density and/or time variations in
the wind properties; these changes are
discussed by [5] and [6a,b]. Bubbles in the
general ISM can eventually merge with their
surroundings and so lose their identities.
Fig. 2. The planetary nebula Abell 49 (HST).
Supernova driven bubbles-supernova remnants

The ejection of several solar masses of
material at velocities of 1000 s of km/sec into
the ISM corresponds to the sudden injection of
energy ( 1044 J). A forward shock is driven
into the ISM and a reverse shock into the
ejected stellar gas. In the initial free
expansion phase, the forward shock has a
roughly constant velocity and thus a radius
proportional to time; the reverse shock
accelerates towards the stellar remnant driven
by the pressure of shocked ejecta. When the
mass of ISM swept up by the forward shock is
about 10 times the mass of ejected gas, the
reverse shock vanishes into the stellar remnant
and the remnant enters the Sedov-Taylor
stage of evolution where only the forward
shock exists. The flow pattern is just an
expanding bubble headed by a single shock.
Radiation losses from the shocked gas are
negligible (though it does radiate) and the
supernova remnant evolves with radius

R t2/5 and velocity V t-3/5. Eventually,
radiation losses which begin in the shocked
ISM behind the shock, remove thermal energy
from all except the very hot rarefied interior of
the expanding bubble and the remnant enters
the pressure-driven snowplough phase where
R t2/7 and V t-5/7. An expanding supernova
remnant in this radiative phase is shown in
Figure 3. Depending on circumstances, the hot
interior may eventually cool and the resulting
momentum-driven snowplough evolves as
R t1/4, V t-3/4. Eventually, the remnant
merges into the ISM when the shock
degenerates into a sound wave or when the
expansion velocity matches the typical random
velocity in the local ISM. As previously,
the exponents quoted apply only to the case
where the ISM has a uniform density.
A comprehensive overview of remnant
evolution is given by [7].
Fig. 3. The radiative supernova remnant N49 (HST).
Mass injection into bubbles

Although spatial density variations can be
accommodated within the models above, the
effects of bubble generation in multi-phase
(or clumpy) gas need further consideration.
Clumps of material can inject gas into various
parts of the global flow. So, for example, the
interior bubble of a supernova remnant can
have a mass greater than just that of the ISM
over-run by the forward shock. This has
consequences for both the radiation rates from
this region and, of course, the dynamics. There
are several ways of injecting material into
flows. Neutral clumps can be photoionized by
stellar radiation fields; conduction fronts can
cause mass transfer from cool clumps to hot
gas (or vice-versa); hydrodynamic ablation of
clumps because of pressure differences
between a flow moving relative to a clump
(the Bernouilli effect) can likewise cause
mass transfer.
Mass transfer between clumps and flows

eventually results in mass addition to the flow.
There is a distinct hierarchy of spatial scales
associated with this. On the smallest scales,
mass is accelerated in boundary layers towards
full integration with the main or global flow.
Because the global flows are directional, there
is a tendency for the accelerated material to be
stretched in the flow direction producing
elongated intermediate scale tail features.
The integration of the transferred mass into the
global flow takes place on these scales. The
largest scale is, of course, that of the flow
itself. Provided there is suitable diagnostic
emission or absorption, these various
structures can be investigated in astronomical
objects and this gives information on
structures and processes (such as hypersonic
compressible boundary layers with mass
injection) that are either difficult or impossible
to study under terrestrial laboratory conditions.
It follows also that these diagnostics must be

used in tandem with the flow models to
determine the correctness of the models for
these structures and processes.
MODIFIED MODELS OF BUBBLES
Radiation driven bubbles
Mass injection into radiation driven bubbles
(or HII regions) is particularly important since
massive stars form in cool molecular clouds
whose structures are extremely clumpy on a
wide range of spatial scales. What happens is
that the material injected into the HII region
by clump photoevaporation increases the gas
density and effectively soaks up ionizing
photons to such an extent that the process selflimits. The HII region has to be kept fully
ionized and for this to occur the amount of
ionized gas cannot exceed a certain amount.
Physically, the bubble becomes surrounded by
a recombination front across which ionized
gas flows and becomes neutral (the inverse of
an ionization front). One defining characteristic
of such bubbles is that they can remain
essentially of constant size as long as mass
injection takes place as opposed to having an
ever-increasing size if bounded by an
ionization front. This property is one means of
accounting for a longstanding problem with
the anomalously long lifetimes of a class of
small HII regions known as ultracompact
HII regions-UCHIIR [8, 9].
Surprisingly perhaps, one of the main
ingredients in the study of such bubbles-the
IFs- still hold considerable interest even half a
century after the pioneering study of [1].
Unlike shock fronts in the ISM where the
simple ideal gas equation of state allows only
compressive shock waves, there are four
different IFs allowed by the jump conditions
analogous to the well-known RankineHugoniot shock transitions. This physically
occurs because the gas passing through the IFs
is externally heated and cools by radiation and
therefore the condition of entropy increase that
must hold across shock fronts no longer
applies. There are two classes of fronts, R-type
and D-type; the ionized density is greater than
the neutral density in R-types and vice-versa in
D-types. Each has two sub-classes. Gas flows
supersonically into R-type fronts and exits
supersonically in weak-R fronts and
subsonically in (the essentially never-found)
strong-R fronts. Gas flows subsonically into
D-type fronts and exits supersonically in

strong-D fronts and subsonically in weak-D
fronts (all velocities are in the front frame).
Which type of front is found depends on the
initial and boundary conditions in the system.
However, these are purely hydrodynamic IFs.
Recent studies though have shown that the
clumps in cool molecular clouds can have
pressures dominated by magnetic field
pressure rather than by gas pressure. Indeed
some measurements of the magnetic-to-gas
pressure ratios in the clumps of some star
forming regions show this ratio may be as
large as about 100. A first study of
magnetohydrodynamic IFs was given by [10]
but this was restricted to rather low values of
magnetic-to-gas pressure ratios. More recent
studies [11] show that even in the simplest
case where the magnetic field is parallel to the
IF the jump conditions change dramatically.
The situation is far more complex when the
magnetic field is oblique to the IF [12]. Front
structures change dramatically and there are
complex situations since any shock heading an
IF is also hydromagnetic. Very little work has
been done on the photoionization of
magnetized clouds IFs. Unpublished calculations
by [13] show that their photoionization can
produce intriguing dynamical phenomena such
as the production of elongated structures from
initially spherical clouds.
Supernova remnants
Mass injection into supernova remnants is
important in a wide variety of astrophysical
contexts. A supernova remnant propagating
inside a molecular cloud propagates through a
multiphase medium with a structure partly
determined by the interaction of the progenitor
star or neighbouring stars with the cloud. The
range of the remnant in the cloud is a
significant factor in the importance of the
remnant for inducing star formation in the
cloud. [14] has argued that although the
global dynamics of supernovae shells in
clouds may be largely determined by the
interaction of the remnant with the diffuse
substrate, the interaction of the remnant with
embedded clouds may greatly contribute to the
remnants observed properties.
On larger scales, the collective effects of
supernova can drive galactic superwinds in
galaxies (starburst galaxies) that have
experienced an extensive burst of massive star
formation [15]. Recent work [16], has shown

that the superwind in the starburst galaxy M82
must possess added mass in order to account
for the observed X-ray emission. The effects
of mass addition on supernova remnants have
been investigated by a variety of means
including numerical [17] and by the rather
specialized similarity solutions [18,19]. These
latter solutions demand restrictive assumptions
regarding the global energetics of the
remnants. What is needed for the generation of
self-consistent superwind solutions is a set of
reasonably accurate approximations to
describe supernova dynamics with mass
addition similar to the very well explored
approximations available for supernova
dynamics in homogeneous media [20,7].
Recent work by [21] and [22] have obtained
approximations for the cases where mass
addition is by hydrodynamic ablation and
conductive evaporation respectively. Perhaps
the most notable conclusion is the dramatic
effect mass addition has on the ranges of
supernovae remnants since mass addition
greatly increases their radiation losses. One
interesting associated effect of radiation losses
is that conductive mass-loading self-limits
since it depends on temperature differences
and radiation losses decrease these. The results
have implications for the conditions necessary
to drive superwind activity; in particular it
may be necessary to clear out the molecular
gas from the regions of star formation in order
to cut down remnant radiation losses.
Wind driven bubbles
Mass injection into stellar wind driven bubbles
has received some attention in connection with
the radiation driven bubbles above,
particularly in connection with the models for
ultra-compact HII regions. This is for the
obvious reason that the massive stars have
both winds and radiation fields. [23,24] have
constructed similarity solutions to describe
adiabatic wind-blown bubble evolution with
mass-loading and for both hydrodynamic and
conductive mass-loading. The mass-loading
has many interesting consequences. For
example, without mass-loading the shock in
the stellar wind is always very strong whereas
with mass-loading, this shock may be very
weak or even non-existent. This weakening of
the shock has been proposed by [13] to
account for the lack of non-thermal emission
from wind blown bubbles. The wind
termination shock is supposed to be too weak

to accelerate any significant population of
relativistic electrons.
Particularly interesting features associated
with wind-blown bubbles are the tail
features mentioned above that are particularly
prominent features of planetary nebulae such
as the Helix nebula, NGC 7293, [25] and the
structures collectively known as PROPLYDs
[26] visible in the Orion Nebula (M42).
We concentrate on the former here since they
have stimulated a considerable amount of
work. It has always been assumed that the tail
structures are produced behind clumps of
material and there have been two basic models
put forward. The earliest ideas postulated that
tails were simply radiation shadows behind
clumps [27]. Shadow here should be
interpreted as a change in ionization (and thus
radiation emission) structure produced by the
blocking of the direct stellar radiation field;
the shadow is ionized by a scattered radiation
field with different characteristics to the direct
field. This model has been widely elaborated
in recent years [28]. However, recent
numerical studies [29] have cast doubts on this
picture, primarily due to the fact that the
shadow region tends to get destroyed.
Dyson et al., [30], have taken the view that the
tail features are produced hydrodynamically
by the effects of a mass-source placed in a
flow, as described earlier. They concentrated
on the tails in the Helix nebula; these have the
notable feature that the tails are very long and
thin (Figure 4). Their length-to-width ratio is
of order 10. There are several distinct
interaction possibilities since the massaddition may occur through either subsonic or
supersonic flow off a clump into a global flow
moving subsonically or supersonically with
respect to the clump. Dyson et al., [30], have
used simple but robust arguments to conclude
that long thin tails can be produced only when
a subsonic global flow interacts with subsonic
flow off a clump. These conclusions were
confirmed by later numerical simulations,
[31]. However there do remain many
unresolved questions. For example, the
calculations so far assume very simple thermal
behaviour of injected and global flow gas and
viscous dissipation in tails may cause local
heating and broadening, [32].
Fig. 4. The tails in the Helix nebula, NGC 7293 (HST).

There are also possible phase changes
involved, particularly in connection with tails
seen in some hydrogen poor planetary nebulae,
[33]. Last, but by no means least, is the
question as to whether the interaction of a
wind with a collection of clumps leads to a
global shock or a collection of individual
shocks around individual clumps. This has
many consequences for clump destruction and
tail production. Perhaps even more
importantly, this is a general question for
shocks in a clumpy ISM and strongly bears on
the absolutely crucial area of star formation.
Pittard et al. (in preparation) have made a
numerical study of this problem when the
clumps are long-lived. Poludnenko et al.,
[34], have published numerical studies of the
interaction of shock waves with very shortlived clumps. Although of considerable
interest, the latter calculations are probably not
relevant to planetary nebula or star formation
studies.
CONCLUSIONS
Although enormous progress in the study of
interstellar bubbles has been made, there
remains much to be done. As has been
demonstrated, there are many areas of the
physics which need further elaboration. More
detailed models of individual objects need to
be made, particularly as the wealth of
observational data increases. One area that
has not been discussed above relates to the
question of X-ray emission from interstellar

super-bubbles driven by combined wind and
supernova activity. This emission is produced
by gas cooling behind the fast shocks. There
are bubbles that are X-ray bright and others
that are X-ray dim. The morphology of the
X-ray emitting gas can vary; it is sometimes
distributed through the bubbles and sometimes
concentrated round their edges. This emission
can be profoundly affected by mass-injection
since the mixing in of cool gas with hot gas
greatly affects emission, as indeed would
shocks be they local or global. Bubbles are
going to remain of prime important to theorists
and observers alike for some considerable
time.
Abbreviations:
A & SS
Ap. Lett
AJ
ApJ
ApJS
A&A
BAIN
MNRAS
QJRAS
Rev. MexAASo. Ast
Astrophysics and Space Science

Astrophysics Letters
Astronomical Journal
Astrophysical Journal
Astrophysical Journal Supplement
Astronomy and Astrophysics
Bulletin of the Astronomical
Institute of the Netherlands
Monthly Notices of the Royal
Astronomical Society
Quarterly Journal of the Royal
Astronomical Society
Revista Mexicana de Astronomia y
Astrofisica
Soviet Astronomy
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DETERMINATION OF RADIOLOGICAL DOSES

OF RADON AND NATURAL RADIONUCLIDES IN THE
OPEN ENVIRONMENT OF THE LAHORE AND KASUR
DISTRICTS, PAKISTAN
R. Najeeb1, E. Hussain2 and U. Masood3
1
COMSATS Institute of Information Technology, Raiwind Road Lahore, Pakistan

E-mail: rashidnajeeb@yahoo.com
2,3
Department of Physics, G.C. University, Lahore, Pakistan
Keywords: SSNTD, CN-85, nuclear tracks, radon concentration.
ABSTRACT
It is well known that the presence of radioactivity in the environment is hazardous to mankind and
to other living creatures. Radon (222Rn) and Thoron (220Rn) gases as well as their daughter products
are present everywhere in the environment. Radium is the precursor of radon/thoron and is present
in trace amounts in all types of rocks and soil. The soil and the bedrock, is the major source of
radon/thoron. If the soil above the bedrock has an enhanced content of uranium-238, the soil is a
potential source of the radon gas present in the soil gas. Radon/Thoron flux measurement has been
carried out in the open environment of the Lahore and Kasur districts, Pakistan. The measurement
was based upon passive detection of Radon/Thoron using CN-85 Solid State Nuclear Track
Detectors in the flux measurement devices, namely SSNTD tubes. The average values of
Radon/Thoron flux, concentration and annual dose were found to be: In Lahore; 12.172 tracks cm-2
hr-1, 135.24 Bqm-3 and 1.549 mSv respectively, In Kasur; 12.457 tracks cm-2 hr-1, 138.248 Bqm-3
and 1.6 mSv respectively; these values are well below the limits described in the International
Commission for Radiological Protection report -65 (ICRP-65).
INTRODUCTION
Radon, an inert, tasteless, odourless, colourless
radioactive gas with atomic number 86,
belongs to the group 18 of chemically inert
(noble) gases. Radon is known to have several
isotopes with the mass number (A) ranging
from A = 200 to A = 226. Three radioactive
series are the primary sources of radon in soil:
222
Rn originates from the 238U series, 220Rn
from the 238Th series and 219Rn from the 235U
series. 219Rn (actinon) with its short half-life of
3.96 s usually does not contribute to the signal
measured with alpha-particle detectors since it
decays before reaching the detecting device.
The dominant contribution to the air activity in
soil originates from 222Rn (radon) and 220Rn
(thoron).
At least 80% of the radon emitted into the

atmosphere comes from the top few meters of
the ground [1]. The main contribution of alpha
activity comes from 222Rn and its daughters
since the half life of thoron (t = 55 s) is too
short to allow for a significant diffusion into
the atmosphere [2].
Experimental Method
The Solid State Nuclear Track Detectors
(SSNTDs) have become an important tool in
the investigation of the presence of radon gas
[3]. Therefore, in this project SSNTDs, namely
CN-85, are used to detect and measure the
concentration of radon. The SSNTDs flux
measurement devices, namely SSNTD tubes,
11
were installed at various locations in the area

of interest in the city (Table 1 and 2). The
detectors in the SSNTD tubes were exposed
for 50 days. After the exposure period, the
tubes were brought back from the locations
and the detectors were removed from SSNTD

tubes and etched at the Radiation Physics
Laboratory (R.P. Lab) at the Government
College University, Lahore.
Fig. 1. This figure shows the geometry of the SSNTD tube.
12
Table (1). Detailed information about the installed SSNTDs.

Sr. No.
01.
02.
03.
04.
05.
06.
07.
08.
09.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
Place
Detector no.
Date of
placement
Date of
detachment
Total days of
exposure
L-1
L-2
L-3
L-4
L-5
L-6
L-7
L-8
L-9
L-10
L-11
L-12
L-13
L-14
L-15
L-16
L-17
L-18
L-19
L-20
L-21
L-22
L-23
L-24
L-25
L-26
L-27
L-28
L-29
L-30
L-31
L-32
L-33
L-34
L-35
L-36
L-37
L-38
L-39
L-40
L-41
L-42
L-43
L-44
L-45
19-jan-02
19-jan-02
19-jan-02
19-jan-02
19-jan-02
19-jan-02
19-jan-02
19-jan-02
19-jan-02
19-jan-02
19-jan-02
20-jan-02
20-jan-02
20-jan-02
20-jan-02
20-jan-02
20-jan-02
20-jan-02
20-jan-02
04-feb-02
04-feb-02
04-feb-02
04-feb-02
04-feb-02
04-feb-02
04-feb-02
16-mar-02
16-mar-02
16-mar-02
16-mar-02
16-mar-02
16-mar-02
16-mar-02
16-mar-02
16-mar-02
16-mar-02
17-mar-02
17-mar-02
17-mar-02
17-mar-02
17-mar-02
17-mar-02
17-mar-02
17-mar-02
17-mar-02
10-mar-02
10-mar-02
10-mar-02
10-mar-02
10-mar-02
10-mar-02
10-mar-02
10-mar-02
10-mar-02
10-mar-02
10-mar-02
11-mar-02
11-mar-02
11-mar-02
11-mar-02
11-mar-02
11-mar-02
11-mar-02
11-mar-02
26-mar-02
26-mar-02
26-mar-02
26-mar-02
26-mar-02
26-mar-02
26-mar-02
05-may-02
05-may-02
05-may-02
05-may-02
05-may-02
05-may-02
05-may-02
05-may-02
05-may-02
05-may-02
06-may-02
06-may-02
06-may-02
06-may-02
06-may-02
06-may-02
06-may-02
06-may-02
06-may-02
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
Gulberg-III
Model Town
Township
Amar Sidhu
Sitara Colony
NESPAK H. S.
Industrial Area sect. D-I
Kot Lakpath
Campus View Town
PIA Colony
Wapda Town
Defence-XX
Cantt.
Cantt.
G.O.R. III
Al-faisal Town
Ayyub Stadium
Hussain Town
Bakr Mandi
Gulshan-e- Ravi
Sanat Nagar
Shad Bagh
UET
Usmanpura
Beghampura
Gadianwala
Govt. College
Minar-e-Pakistan
Iqbal Town (Khabar Block)
Iqbal Town (Nazam Block)
Baghbapura
Mozang
Gulberg-II
GOR-I
Thekri Pir
Defence-L
New Muslim Town
Sadar Bazar
Shalamar Link Road
Defence-GG
Model Town
PCSIR
Mansora
Johar Town
Engineer Cooperative H. S.
13
Table (2). Detailed Information about the Installed SSNTDs.

Sr. No.
01.
02.
03.
04.
05.
06.
07.
08.
09.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
Place
Kot Fateh Din Khan
Kot Azam Khan
Kot Usman Khan
Kot Badar Din Khan
Kot Undron Khan
Kot Gulam Muhammad Khan
Kot Molvi Abdul Qadir
Kot Ali Ghar
Kot Bhudha
Kot Peeran
Kot Murad Khan
Mustafa Abad
Khara
Rangpura
Kheerghar
Bhadurpura
Noorpur
Fatehpur
Khadiyan
Sherkot
Raja Jhang
Kot Akbar Khan
Kot Radha Kishan
Detector
no.
Date of
placement
Date of
detachment
Total days of
exposure
K-1
K-2
K-3
K-4
K-5
K-6
K-7
K-8
K-9
K-10
K-11
K-12
K-13
K-14
K-15
K-16
K-17
K-18
K-19
K-20
K-21
K-22
K-23
25-jan-02
25-jan-02
25-jan-02
25-jan-02
25-jan-02
25-jan-02
25-jan-02
25-jan-02
25-jan-02
27-jan-02
27-jan-02
27-jan-02
27-jan-02
27-jan-02
27-jan-02
27-jan-02
27-jan-02
30-jan-02
30-jan-02
30-jan-02
30-jan-02
30-jan-02
30-jan-02
16-mar-02
16-mar-02
16-mar-02
16-mar-02
16-mar-02
16-mar-02
16-mar-02
16-mar-02
16-mar-02
18-mar-02
18-mar-02
18-mar-02
18-mar-02
18-mar-02
18-mar-02
18-mar-02
18-mar-02
21-mar-02
21-mar-02
21-mar-02
21-mar-02
21-mar-02
21-mar-02
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
50 days
Lahore is the second biggest city of Pakistan

and provincial capital of Punjab. The area of
the city of Lahore (440 km2) was divided
evenly into 50 sectors and in each sector a flux
measurement device, namely an SSNTD tube,
containing CN-85 plastic detector, was
installed. The SSNTD tubes are hollow
cylindrical tubes made of steel, provided with
a handle for handling and installation purposes
(Figure 1). These are 16+0.3 cm long (with an
extra height of 11+2 cm for the handle), with
an opening diameter at one end of the tube of
3+0.3 cm. The detectors were attached at the
middle of the tube with the help of a clip.
A hole was dug about 18 inches deep and the
SSNTD tube containing CN-85 was inserted
vertically in the hole and the hole was covered.
Radon/Thoron diffused from the soil and
gathered in the vicinity of the hollow SSNTD
tubes through the opening present at one end
of the tube. The alpha tracks from
disintegrating Radon/Thoron atoms were
registered. After an exposure time of 50 days
(1200 hours) the detectors CN-85 were
detached from the tubes and were etched
chemically. Chemical etching is the most
14
widely used method for fixing and enlarging

the latent damaged tracks. These enlarged
tracks can be observed and scanned easily
under an optical microscope. The detectors
were etched using etchant 6 N NaOH at 50C
for 70 minutes in the etching bath; afterwards
they were washed in the ultrasonic bath and
carefully scanned under an optical microscope
at a magnification of 400x.
To calculate the background effect, an
unexposed detector was etched using the same
etching conditions, which were observed while
etching the exposed detectors. It was scanned
and the track density [number of tracks per
Field Of View (FOV)] was calculated i.e.
Average number of tracks per FOV = 0.5
Track density = average number of tracks/area
of FOV = 2913.583 tracks cm-2
The simplified relation between the tracked
density and radon flux is given below:
Flux = = Track density/Exposure time
Flux to Concentration
0.09 tracks cm-2 hr-1 = 1 Bqm-3
The track density for etched detectors was

found and hence the radon flux, concentration
and annual dose were calculated for each
location (Table 3 and 4).
Concentration to Annual Dose

1 Bqm-3 = 0.01146 mSv
The conversion factors [4] are as follows:

Table (3). Radon Flux, concentration and the annual dose in the Lahore District.
Detector
no.
L-1
L-2
L-3
L-4
L-5
L-6
L-7
L-8
L-9
L-10
L-11
L-12
L-13
L-14
L-15
L-16
L-17
L-18
L-19
L-20
L-21
L-22
L-23
L-24
L-25
L-26
L-27
L-28
L-29
L-30
L-31
L-32
L-33
L-34
L-35
L-36
L-37
L-38
L-39
L-40
L-41
L-42
L-43
L-44
L-45
Track
density
Average no.
of tracks/FOV cm-2 x 103
2.8
2.9
3.1
3.0
2.8
2.5
3.2
2.9
2.9
2.6
3.3
3.2
3.7
3.4
3.0
2.7
3.1
3.1
2.3
3.3
2.9
2.8
3.4
3.2
3.1
2.7
2.5
3.7
2.8
3.2
2.8
2.9
3.0
2.5
2.7
2.8
3.4
2.9
3.3
3.3
3.4
3.0
3.4
3.0
2.8
16.320
16.900
18.060
17.480
16.320
14.570
18.650
16.900
16.900
15.150
19.230
18.650
21.560
19.810
17.480
15.730
18.060
18.060
13.400
19.230
16.900
16.320
19.810
18.650
18.650
15.730
14.570
21.560
16.320
18.650
16.320
16.900
17.480
14.570
15.730
16.320
19.810
16.900
19.230
19.230
19.810
17.480
19.810
17.480
16.320
Corrected
track density
Tracks cm-2 x 103
Flux
tracks
cm-2 hr-1
Radon
concentration
Bqm-3
Annual
dose
mSv
13.400
13.990
15.150
14.570
13.400
11.650
15.730
13.990
13.990
12.240
16.30
15.730
18.650
19.900
14.570
12.820
15.150
15.150
10.490
16.320
13.990
13.400
16.900
15.730
15.150
12.820
11.650
18.650
13.400
15.730
13.400
13.990
14.570
11.650
12.820
13.400
16.900
13.990
16.320
16.320
16.900
14.570
16.900
14.570
13.400
11.167
11.658
12.625
12.142
11.167
9.708
13.108
11.658
11.658
10.200
13.58
13.108
15.542
16.583
12.142
10.683
12.625
12.625
8.742
13.600
11.658
11.167
14.083
13.108
12.625
10.683
9.708
15.542
11.167
13.108
11.167
11.658
12.142
9.708
10.683
11.167
14.083
11.658
13.600
13.600
14.083
12.142
14.083
12.142
11.167
124.074
129.537
140.278
134.907
124.074
107.870
145.648
129.537
129.537
113.333
150.93
145.648
172.685
184.259
134.907
118.704
140.278
140.278
97.130
151.111
129.537
124.074
156.481
145.648
140.278
118.704
107.870
172.685
124.074
145.648
124.074
129.537
134.907
107.870
118.704
124.074
156.481
129.537
151.111
151.111
156.481
134.907
156.481
134.907
124.074
1.422
1.484
1.608
1.546
1.422
1.236
1.669
1.484
1.484
1.299
1.730
1.669
1.979
2.112
1.546
1.360
1.608
1.608
1.113
1.732
1.484
1.422
1.793
1.669
1.608
1.360
1.236
1.979
1.422
1.669
1.422
1.484
1.546
1.236
1.360
1.422
1.793
1.484
1.732
1.732
1.793
1.546
1.793
1.546
1.422
15
Table (4). Radon Flux, concentration and the annual dose in the Kasur District.
Detector no.
Flux tracks
cm-2 hr-1
Radon concentration
Bqm-3
Annual dose
mSv
K-1
K-2
K-3
K-4
K-5
K-6
K-7
K-8
K-9
K-10
K-11
K-12
K-13
K-14
K-15
K-16
K-17
K-18
K-19
K-20
K-21
K-22
K-23
14.082
10683
12.139
11.654
12.626
11.654
11.654
15.539
14.082
13.11
11.654
11.168
14.082
11.168
11.654
11.169
14.082
12.139
13.111
11.168
11.654
12.626
13.597
156.47
118.702
134.888
129.493
140.283
129.493
129.493
172.657
156.47
145.679
129.493
124.097
156.47
124.097
129.493
124.097
156.47
134.888
145.679
124.097
129.493
140.283
151.075
1.793
1.36
1.546
1.484
1.607
1.484
1.484
1.977
1.793
1.669
1.484
1.422
1.793
1.422
1.484
1.422
1.793
1.546
1.669
1.422
1.484
1.607
1.731
RESULTS AND DISCUSSION

The flux and hence the concentration of Radon
at different locations in the Lahore and the
Kasur districts are summarized in Table 3 and
4. The average values of flux and the Radon
concentration calculated are 12.179 tracks
cm-2hr-1 (ranging from 8.741 to 15.539 tracks
cm-2hr-1) and 135.32 Bqm-3 (ranging from
97.119 to 172.657 Bqm-3) respectively. The
annual dose of Radon concentration has the
average value of 1.55 mSv (ranging from
1.113 to 1.731 mSv). These results show that
the concentration of radon in the open
atmosphere of Lahore and Kasur is well below
the limits 148 Bqm-3 as given in ICRP-65[5].
In general, the high levels of radon are
associated with granite rocks, phosphate
deposits and some beach sands which may
contain a high level of radon progenitors i.e.
uranium or thorium [6]. Therefore it may be
16
thought that the area under study does not

contain such contents. It can be seen that the
values of the radon concentration in the two
districts fall in the same range. This can be
attributed to the same climatic and geological
factors in the respective area under
investigation.
The SSNTD technique, which is cheaper than
any other method used for the measurement of
radon can be applied successfully for this
purpose. In order to keep the environment safe
from the harmful effect of radioactive nuclear
radiations, it is desirable to know about such
types of radiations and their respective levels
in the environment. Hence, predicting the
environmental radiation levels from basic
characteristics of the work place is an area of
interest.
CONCLUSIONS
1. The concentration of Radon in the open
atmosphere in Lahore and Kasur is below
the limits described by the International
Commission on radiological protection.
2. The area under study does not contain
radon progenitors i.e. uranium or thorium.
3. The SSNTD technique, the cheapest one,
can be used to determine the radon levels.
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Measurement 31, 295-300 (1999).
17
SYNTHESIS AND CHARACTERIZATION OF SOME

COMPOSITE MESOPOROUS ORGANOSILICAS BY
A CO-CONDENSATION ROUTE
J.E.G. Mdoe1 and D.J. Macquarrie2
1
Department of Chemistry, University of Dar Es Salaam, P.O. Box 35061

Dar Es Salaam, Tanzania
E-mail: mdoe@chem.udsm.ac.tz
2
Department of Chemistry, University of York, Heslington, York, YO10 5DD, U.K.
Keywords: Organic-silica composites, pore size distribution, sol-gel method,

templating route.
ABSTRACT
Organic-silica composites were prepared by an in situ co-condensation of tetraethyl orthosilicate
and various amine containing organoalkoxysilanes at various ratios over a structure-directing
neutral n-dodecyamine. Characterization of the composites confirmed covalent attachment of the
organic groups onto the silica surface. Their surface areas range from 100 to ca. 800 m 2 g -1,
depending on the organic group loading. Loadings as high as 3.4 mmol g-1 were obtained, although
higher loadings (above 2.4 mmol g-1 and 1.2 mmol g-1 for the monoamines and polyamines based
composites, respectively) resulted in materials that are mostly amorphous. Below these loadings
the composites displayed narrow and monodispersed pore size distribution with typical average
pore diameters of 3.6 nm. In addition, the large sized-polyamine based composites showed
relatively lower surface areas as compared to their monoamine counterparts that have the same
organic group loading.
INTRODUCTION
The discovery of a family of silicate/
aluminosilicate mesoporous molecular sieves
(denoted as M41S) by the Mobil Company in
1992 [1] has attracted a lot of attention in the
last decade. The interest centres on the fact
that these materials have attractive features
ideal for applications as catalysts and/or
catalyst supports. The features in question are
high surface areas (typically 1000 m2g-1),
tuneable pore sizes and good mechanical
stability. The original materials were prepared
by
using
quaternary
alkylammonium
surfactant as a template around which
inorganic precursor polymerises.
The template is normally extracted by a

thermal method. Tanev and Pinnavaia [2] later
developed a neutral templating route in which
alkylamines were used instead of ionic
surfactants. The materials they produced were
known as hexagonal mesoporous silica
(HMS). Since the surfactant-inorganic
precursor interaction was through hydrogen
bonds, which is weaker than electrostatic
interactions, the template could be removed by
washing with hot ethanol.
Indeed, a great deal of work has been carried
out on the preparation, characterisation and
applications of the M41S class of materials.
19
However, tailoring of the materials for specific

applications has always required both
structural
and
compositional
control.
Compositional control is achievable through
chemical modification of the material surface
via
either
post-synthesis
modification
(grafting) or direct modification during the
synthesis process. The majority of publications
[3] on organic-silica composites of the M41Stype
have
involved
post-synthesis
modification of the pre-formed silicas.
However, the post-synthesis modification
technique necessitates the use of excess
organosilane during the grafting process,
which yields materials that sometimes lack
stability due to partial cross-linking of the
organosilane coupling agent to the silica
surface and sometimes there is a possibility of
ending up with materials containing a variety
of surface bound species [4].
A convenient route to organic-silica
composites of the M41S-type materials that
circumvents the above setbacks has been
developed [5,6,7,8]. The route involves a onepot co-condensation of a silica precursor
(tetraethyl orthosilicate, TEOS) and an
organo-alkoxysilane in the presence of a
templating agent. This method generates the
composites in one step, where the organic
group is incorporated during the condensation
of the silica framework, and is therefore likely
to be more fully integrated into the composite,
as indeed observed previously [6]. The
porosity properties as well as the organic
group loading can always be tailored. The
technique for direct synthesis of organic-silica
composites has also been accomplished using
a variety
of basic and non-basic
organoalkoxysilanes [9,5,6,10]. However, the
basic organoalkoxysilanes produced composites
that consistently had lower surface areas
compared to non-basic organic ones, although
the reason is still contentious. The pore size
distribution, however, did not vary among the
two groups of silanes.
Organic-silica composites containing amino
groups have been used successfully as
catalysts in the Knoevenagel reactions [11,6]
and epoxidation of electron deficient olefins
[12,10]. Their structural properties were
however, not studied fully in relation to the
organic group size as well as loading. As part
of a programme of synthesizing organic-silica
composites for applications in catalysis, we
20
hereby report our results on the effect of the

size of the organic group and loading on
structural properties (namely, surface area,
pore volume, pore size and pore size
distribution) of organoamine containing
composites.
METHODS
Chemicals and Reagents
Chemicals such as tetraethyl orthosilicate
(TEOS), -aminopropyl(trimethoxy)silane,
(-trimethoxysilylpropyl)ethylenediamine and
(-trimethoxysilylpropyl)-diethylenetriamine
were purchased from Fluorochem Ltd. Other
standard laboratory grade reagents were
purchased from Aldrich. All chemicals and
reagents were used as received.
Preparation of Materials
The procedure developed by [11] was
followed. In a typical experiment, 18.8 g TEOS
and 1.79 g -amino-propyl(trimethoxy)silane
were added separately, but simultaneously and
rapidly to a stirred mixture of 5.08 g
n-dodecylamine in aqueous ethanol (46 cm3 of
absolute ethanol and 53 cm3 of distilled water)
at room temperature. The mixture was stirred
for 18 h after which it turned to a thick white
paste. After 18 h, the thick solution was
filtered, and the white solid washed with
ethanol. The damp solid product was then
refluxed in ten times its own weight of ethanol
for 3 h and filtered again to remove the
template. The solvent reflux was repeated
twice to completely remove the template from
the material. The final solid was then dried in
an oven at 100 C to give composite 1.
Materials of higher loading were prepared by
changing
the
ratios
of
-aminopropyl(trimethoxy)silane to TEOS. The ratios
used were 1:2 and 1:4 which gave composite 2
and 3, respectively. In each case the templates
were recovered and reused in fresh
experiments as explained elsewhere [5]. Other
composites were prepared in a similar manner
and the ingredients and their respective ratios
are summarized in Table 1. In each case,
precipitation started between 5 and 15 min and
was continued for 18 h. However, in the case
of (-trimethoxysilylpropyl)diethylenetriamine
at a mole ratio of 1:2, the process was
surprisingly very slow. It took 24 h to show
signs of precipitation, and ageing had to be
carried out for 7 days.
Table (1). Identities and ratios of the ingredients used in the preparation of composites.
Organoalkoxysilane
Organosilane to
TEOS ratio
Composite
identity
-aminopropyl(trimethoxy)silane
1:9
1:4
1:2
(-trimethoxysilylpropyl)ethylenediamine
1:9
1:4
1:2
1:9
1:4
1:2
Characterisation
The composites prepared were characterized
by a variety of techniques. The physical
structure of the materials was studied by
nitrogen physisorption on a Coulter SA3100
porosimeter at 77.4 K. Scanning electron
microscopy (SEM) images were obtained from
an Hitach SEM S2400 instrument, using an
electron gun energy of 8 keV. Infrared (IR)
spectra were measured on a Bruker Equinox
55 FTIR spectrometer fitted with an
environmental chamber diffuse reflectance
unit. The samples were dried in air at 110 C
prior to analysis and then run at room
temperature as mixtures with KBr. On the
other hand, solid state 13C Nuclear Magnetic
Resonance (NMR) spectra were obtained on a
Bruker MSL300 spectrometer operating at 75
MHz at a rotor spinning rate of 5 kHz.
The co-condensation of the organoalkoxysilanes and TEOS at various ratios on a
template resulted into solid composite
materials that were whitish in colour (with
very few exceptions). Extraction of the
template with hot ethanol, followed by
complete evaporation of the extracted solution
afforded a 98% recovery of the template and
hence a possibility for template reuse.
Generally, the technique was simple, clean and

versatile.
Analysis of the resultant organic-silica
composites by diffuse reflectance FTIR and
solid state 13C NMR showed that the expected
organic functionalities were present on the
composite surfaces as reported earlier [12,6].
Thermogravimetric studies showed that the
organic groups were robustly bound to the
silicate structure and usually started to
combust at temperatures above 300 C as
observed also in a different study elsewhere
[10].
Table 2 gives a summary of the BET surface
areas, pore volumes and average pore
diameters of the prepared organicsilica
composites. As mentioned previously, M41Srelated materials possess very large surface
areas compared to those of amorphous silica.
From the table it can be seen that the surface
areas
of
the
composites
containing
monoamines are above 700 m2 g-1, a value that
is less than the typical values for such
materials. For composites developed from
large-sized polyamines the surface areas
are even lower, ranging between 360 and 650
m2g-1 (Table 2).
21
Table (2). Physical-chemical properties of the synthesized composites.

Composite
1
2
3
4
5
6
7
8
9
Organic group attached

-(CH2)3NH2
-(CH2)3NH2
-(CH2)3NH2
-(CH2)3NH(CH2)2NH2
-(CH2)3NH(CH2)2NH2
-(CH2)3NH(CH2)2NH2
-(CH2)3NH(CH2)2NH(CH2)2NH2
The reason for the lower surface areas is

probably due to the possibility that the organic
groups protruding into the interior of the pores
occupy a significant amount of space thereby
reducing the area available for nitrogen
physisorption. In all composites the surface
area decreases as the organic group loading
increases. Again, the later reason could explain
this observation. Table 2 also shows that the
pore volumes decrease systematically with the
increase in size of the organotrialkoxysilane.
SBET
(m2/g)
756
745
715
575
530
120
366
460
97
Mean pore
diameter
(nm)
3.6
3.7
8 (broad)
3.5
7.0(broad)
13.5(broad)
3.7
9.9(broad)
14.8(broad)
Total pore
Organic
volume
Loading
(cm3g-1)
(mmol g-1)
0.68
1.1
0.69
2.4
3.4
0.51
1.2
0.70
1.9
0.40
2.5
0.34
1.1
1.14
1.8
0.36
2.4
The materials under study also exhibit narrow

and monodisperse pore size distributions
especially at lower organic group loadings as
exemplified by monoamine-silica composites
in Figure 1. At loadings above 2.4 mmol g-1
for the monoamine-based composite, the pore
size distribution starts to broaden and it is not
predictable. The average pore diameter is 3.6
nm which closely matches the length of
n-dodecylamine [10]. In the case of the
polyamine-based composites, the pore size
distribution starts to broaden beyond the
1 mmol g-1 loading.
Fig. 1. A typical pore size distribution for composites 1 at different organic group loadings.
22
The adsorption-desorption isotherms for the

monoamine-based composites are given in
Figure 2. It can be seen that the isotherms of
the composites with a loading of 1.1 and 2.4
mmol g-1 show a characteristic inflection point
at a relative pressure of about 0.2, consistent
with the adsorption isotherms for MCM-41
type of materials [1]. This is an indication of
capillary condensation in framework confined
pores. Beyond the loading of 2.4 mmol g-1, for
these composites, the isotherm shows a
pronounced hysteresis loop at high relative
pressures implying that most of the pores are
textural. In the case of polyamine-based
composites, only the loading of around
1 mmol g-1 produces materials with framework
confined pores.
Fig. 2.
Generally, the loading of the organic groups

can be varied over a wide range by adjusting
the ratios of organoalkoxysilane to TEOS in
the system. Loadings as high as 3.4 mmol g-1
were obtained for the small sized
organoalkoxysilane (i.e., -aminopropyltrimethoxysilane to TEOS ratio of 1:2).
However, at higher loadings (usually > 1.2
mmol g-1) the resultant materials are mostly
amorphous [5]. In the case of the large sized
organoalkoxysilanes the maximum loading
obtained was 2.4 mmol g-1 at a similar moleratio.
Adsorption-desorption isotherms for composite 1 at different

organic group loadings.
23
Fig. 3. An electron micrograph of composite 1.

Scanning electron microscopy studies of the
composites showed that the shapes and sizes
of the primary particles vary depending on the
organic group loading. At an organosilane to
TEOS ratio of 1:9 the shapes of the primary
particles are roughly spherical or ellipsoidal,
with a roughly regular shape though some
appear in aggregates (see example in
Figure 3). This is seen in all composites at that
mole-ratio. In the case of -aminopropyltrimethoxysilane-based composites the majority
of the particles have a diameter of ca. 0.3 m,
and slightly higher for other composites.
However, when the ratio of the organosilane to
TEOS is increased the particles become less
distinct and their sizes enlarge. The particles
assume an angular morphology and a more
solid texture similar to that of amorphous
silica. Spherical structures present are often
seen in a range of mesostructured materials.
24
CONCLUSION
The organic-silica composites prepared by the
in situ sol-gel method possess surface areas
ranging from 100 to 750 m2 g-1 and organic
group loading above 3 mmol g-1 silica. Their
pore sizes, pore size distributions and pore
volumes change depending on the organic
group loading and the size of the organic
group.
However, it is possible to tailor the structural
and compositional properties to suit particular
applications. Generally, the loading and the
size of the organic groups in composites of
this type do influence the structural and the
compositional properties of the resultant
composites significantly.
ACKNOWLEDGEMENT
JEG Mdoe would like to thank NORADchemistry project for financial support.
REFERENCES
1. C. T. Kresge, M. E. Leonowicz, W. J.
Roth, J. C. Vartuli and J. S. Beck, Nature
359, 710-712 (1992).
2. P. T. Tanev and T. J. Pinnavaia, Science
267, 865-867 (1995).
3. P. M. Price, J. H. Clark and D. J.
Macquarrie, J. Chem. Soc., Dalton Trans.
101-110 (2000).
4. E. F. Vansant, P. van Der Voort and
K. C. Vrancken, Surface Sci. Catal. 93,
195 (1995).
5. D. J. Macquarrie, Green Chem.195-198
(1999).
6. D. J. Macquarrie, D. B. Jackson, J. E. G.
Mdoe and J. H. Clark, New J. Chem. 23,
539-544 (1999).
8. C. E. Fowler, S. L. Burkett and S. Mann,

Chem. Commun. 1769-1770 (1997).
9. J. E. G. Mdoe, J. H. Clark and D. J.
Macquarrie, Synlett, 625-627 (1998).
10. J. E. G. Mdoe, D. J. Macquarrie and J. H.
Clark, J. Mol. Catal. A: Chemical 198,
241-247 (2003).
11. D. J. Macquarrie, J. H. Clark, D. B.
Jackson, A. Lambert, J. E. G. Mdoe and
A. Priest, New Solid Bases and Their Use
in The Knoevenagel Reaction. In: B. K.
Hodnett, A. P. Kybett, J. H. Clark and K.
Smith, eds. Supported Reagents and
Catalysts in Chemistry. Cambridge: Royal
Society of Chemistry, 174-187 (1998).
12. J. E. G. Mdoe, Bull. Chem. Soc. Ethiop.
16(1), 103-112 (2002).
7. S. L. Burkett, S. D. Sims and S. Mann,

Chem. Commun. 1367-1368 (1996).
25
CORALS AS BIO-INDICATORS TO TRACE METAL

POLLUTION ON THE KUWAITI CORAL ISLANDS,
OFF THE ARABIAN GULF
A.H. Bu-Olayan1, B.V. Thomas2 and A.H. Shaker3
1,2
Department of Chemistry, P.O.Box 5969, Kuwait University, Safat-13060, Kuwait

E-mail: buolayan@yahoo.com; bivint@yahoo.com
3
Mari Culture and Fisheries Division, P.O.Box 1638, Kuwait Institute for Scientific
Research (KISR), Ras-Salmiya, Kuwait
Keywords: Corals, trace metals, bio-indicator, pollution.
ABSTRACT
Three predominant corals, Acropora clathrata, Porites compressa and Favia pallida collected from
the three Southern Kuwaiti coral islands exhibited differential trace metals accumulation in their
anterior and posterior body parts. Except for Fe and Cd, the overall trace metal levels in the three
corals were higher during winter than in summer but the sequence of Cu>Ni>Zn>Pb>V remained
unaltered with the seasons. Observation revealed higher levels of metals in the posterior part than in
the anterior part irrespective of the species, at different seasons and sampling sites. Site III
exhibited high levels of metals (1.73 g.g-1) followed by Site II (1.13 g.g-1) and Site I (1.02
g.g-1). Metal levels were higher in P. compressa followed by F. pallida and A. clathrata (0.8
g.g-1, 0.52 g.g-1and 0.34 g.g-1 respectively) during the summer, but the reverse occurred in
winter (0.24 g.g-1, 0.51 g.g-1and 0.96 g.g-1 respectively). Significant variation of trace metals
levels to seasonal analysis could therefore validate corals as a bio-indicator to trace metal pollution.
INTRODUCTION
Corals are apparent by sensitivity to physical
and chemical changes in the marine
environment and therefore can be used as
environmental indicators [1]. Recent studies of
[2,3,4,5,6,7,8,9] showed significant links
between corals and trace metal levels to the
anthropogenic source of contaminants. The
Acroporids, Favids and Porites commonly

used in these studies were abundant in the
Great Barrier Reef and in the tropical Asian
and Middle East regions. Howard and Brown
[10,11,7] reported high levels of metals (Cu,
Fe, Mn, Zn) ranging from 0.01 to 210 g.l-1,
which is an indication of the extent of
pollution to which reefs and coastal regions
are subjected in many parts of the world.
27
The Southern Kuwaiti coral islands such as

Kubbar, Umm Al-Maradeem and Quaro (I-III)
provide habitats for commercially important
species of fishes. These reefs also find a place
in the light of the economy of the country
through recreation, value added products,
scuba diving and fishing activities [12].
Hodgson and Carpenter [13] have described
28 hermatypic and six-ahermatypic corals out
of 500 species of corals worldwide. Downing
[14] observed the influence of marine
pollution in the Kuwaiti coral reefs surveyed
after the Gulf War-I. Several investigations on
poly-aromatic hydrocarbons, climatic factors
and hydrological features determined the
altercations of coral growth before and after
the Gulf War [15,14]. The observations of [16]
on trace metals in the northern Arabian Gulf
region sediments in Kuwait and the
environmental sensitive index for the shoreline
of Kuwait by [17] led [18] to determine the
physiological and hydrological features of the
Kubbar, Quaro and Umm-Al-Maradeem
islands. In addition, Al-Ghadban [18] observed
the morphology, sedimentology (textural) and
mineralogical properties of these islands and
related (1) the impact of the hydrodynamic
regime (high energy zone) and (2) polygenetic
origin characterizing autochthonous materials
derived from the degradation of a variety of
invertebrates especially from the coral
communities and coral debris derived from the
surrounding coral communities by wave
action. He also suggested the potential sources
of the islands sediments arranged in the
sequence of autochthonous shells, dust fallouts
and coastal ridges. However, no publications
to date have dealt with the predominant corals
as a bio-indicator to trace metals pollution in
the Coast of Kuwait and hence the reason for
this study.
MATERIALS AND METHODS
Three coral islands (I-III) of Southern Kuwait,
Kubbar (2904.072N/4829.596E), Umm AlMaradeem (2840.863N/4838.855E) and
Quaro (2049.001N/4846.437E) were chosen
for the present study (Figure 1).
The
predominant
coral
species,
Acropora
clathrata, Porites compressa and Favia
28
pallida were collected (10 replicates each) on

a monthly basis from three fixed transects of
each island (Figure 1). The corals brought
onshore were cleaned with saline and
de-ionized water and identified to species
level. Using a sterile cutter, the cleaned
branched anterior region of the corals
comprising the juvenile polyp were
enzymatically digested (12-36 hours) to
separate the soft tissues (henceforth termed the
anterior part) from that of their skeletal
tissues, at 30C using 1% Proteinase K (USB)
in 0.1 M tris-HCl buffer (pH 7.2) and verified
under the microscope. The skeleton pieces and
polyp (10 g) were collected separately [19].
The basal stalk region (posterior part) of the
three coral species were separated from that of
the anterior region. Thus, the anterior part and
the remnant skeletal tissues of the anterior
region as well as the stalk region (posterior
part) were stored in sterile plastic containers
and later analyzed for trace metals.
The replicate samples were separately labeled
and dried in a hot air oven (GallenKamp II) at
60C for 72 h. They were ground in a mortar
and pestle and sieved to <250 m size to
ensure homogeneity of the samples. These
samples were packed in sterile polyethylene
vials. Samples (2 g) pre-digested in 4% Aristar
grade (Nitric acid (v/v) and 2% Aristar grade
HCl (v/v)) in a 50 ml Fischer brand disposable
sterile centrifuge tube were left for 48 h [20].
Diluted samples (50 ml) in de-ionized water
were digested in an automatic microwave
digester (Spectro-prep CEM) and trace metal
levels measured in an atomic absorption
spectrophotometer (AAS-Perkin Elmer-5100).
Pb, Ni, V and Fe, Cu, Zn, Cd were analyzed
using a HGA-600 graphite furnace equipped
with a deuterium background and flame in
AAS, respectively. A Standard Reference
Material, dogfish muscle (DORM-2) from the
National Research Council, Canada, at 96%
0.05 recoveries of trace metals (Table 1),
determined the precision of the instrument and
the data was statistically treated using the
SPSS programme.
Table (1). Recovery values of the concentrations of trace metals measured standard
reference materials (SRM), dog muscle (DORM-2).
Metals
SRM values
g.g-1
Present study
g.g-1
Recovery
%
Cu
Fe
Zn
Cd
Pb
Ni
V
2.34 0.16
142.00 10
25.60 2.3
0.04 0.008
0.06 0.007
19.40 3.1
1.65 0.25
2.25
137.10
24.80
0.038
0.058
18.60
1.59
96.15
96.54
96.87
95.00
96.66
95.87
96.36

Observations from the three Kuwaiti Southern
islands (Figure 1) revealed A. clathrata, P.
compressa and F. pallida to be more
predominant than any other corals and
supported the observations on the abundance
of species by [13,12]. The mean trace metal
levels of replicates were determined for each
island. The overall observations showed
higher levels of trace metals in winter than in
summer (Figures 2-3). However, metals wise
and species wise studies revealed variations as
discussed below. The sequence of trace metal
levels (Cu>Ni>Zn>Pb>V) in all the samples
remained the same in both seasons (summer
and winter) in each of the three Southern
Kuwaiti islands. However, the sequence for Fe
and Cd varied with the seasons. High levels of
Cu (0.40-2.44 g.g-1) in all the samples
probably occur due to the existence of an algal
layer beneath the coral surface. The absorption
of trace metals such as Cu, Ni and Zn from
algal deposition on the corals as well as the
accumulation of such metals on the rough
surfaces between grooves (Favids) and in the
outermost porous layer (Porites and
Acroporids) were found to be partially
absorbed despite cleaning and preliminary
enzymatic digestion. This supports the
observations of [3,5,8,9]. In the case of Fe, the
sequence not only exhibited alteration with Cd
in coral samples during summer and winter
(Figures 2-3), but also was found to be at
lower levels than the other analyzed metals.
This phenomenon may be due to the
absorption of Fe for the metabolic activity of
corals polyps during the summer.
Relatively speaking, the levels of trace metals

analyzed in this study showed no significant
variation between the skeletal tissues and their
soft polyp tissues (anterior part) of the anterior
region. Hence, this study presents the mean
levels of metals of skeletal and the soft polyp
tissues of corals and designated the anterior
part throughout the manuscript. Comparative
analyses revealed higher levels of trace metals
in the posterior part (3.41 g.g-1) than in the
anterior part of the corals (2.58 g.g-1)
irrespective of the three species, seasons and
sampling islands (Figures 4-5). The species
mean levels of metals were observed highest
in P. compressa (0.8 g.g-1) followed by F.
pallida (0.52 g.g-1) and A. clathrata (0.34
g.g-1) during the summer, but the reverse
occurred in winter (0.24 g.g-1, 0.51 g.g-1and
0.96 g.g-1respectively). Higher levels of
metals in P. compressa during the summer
may be due to (a) their interaction with algal
enrichment causing the accumulation of metals
and (b) the accumulation of metals in the
exposed aragonite lattice skeleton corals due
to the shallowness of the depth of water in
these islands. This supports the observations of
[10,9]. Whereas, during winter, low algal
blooms may result in low levels of trace
metals in P. compressa compared to F. pallida
and A. clathrata. Observations showed the
mean levels of metals to be higher in Site-III
(1.73 g.g-1) in all three species followed by
Site II (1.13 g.g-1) and Site I (1.02 g.g-1)
respectively. The reasons for the high levels of
metals observed in Site III may be caused by
(a) the impact of rapid human activities, (b)
upwelling of the water current that
accumulates trace metals from the surrounding
29
waters and (c) the relative increase in the

depth of water compared to the other two
Islands. Site II was located farthest from the
Kuwaiti Coastline. Trace levels of metals were
relatively higher in the coral samples after the
Gulf War-II and due to human recreational
activities. Evidently, Site-I showed low levels
of trace metals in corals due to (a) shallowness
of the Island, (b) rapid flushing of the nutrients
and the silt, (c) the effect of a relatively strong
water current due to this islands proximity to
the Kuwait Coastline, (d) least land and ocean
bed area when compared to the other two
islands, (e) low abundance of corals species
due to human activities, low nutrients and high
grazing activities of sea urchins. A significant

correlation (>95%) of the mean trace metals
level was observed between the winter and
summer corals samples. This is due to: (1)
upwelling of the water current and low
temperature during the winter causing an
accumulation of trace metals in the corals, (2)
low coral leaching during winter time due to
the low wave action during this period and
supports the views of [18,11,7]. Thus, the
abundance of these predominant corals to
seasonal variation and levels of trace metals in
the anterior and posterior parts suggests that
they can be considered as bio-indicators of
pollution of the trace metals.
Fig. 1. Sampling locations of the southern Islands of Kuwait.

Inset: Sampling loci in Kubbar Island. Similar sampling carried out
in the Qaru and Umm-Al-Maradem Islands.
30
AI
2.44
3
AII
AIII
2.00
g.g-1
1.00
0.00
1.26
3
1.10
3
0.74
3
0.10
3
0.50
3
0.13 0.12
3
3
0.08
3
0.74
3
0.46
3
0.06
3
0.56
3
0.22
0.11
3
3
0.07
3
0.21
0.14
3
3
0.10
3
0.08
3
FI
I
FI
1.25
3
FIII
2.00
g.g-1
1.08
3
1.00
0.72
3
0.36
3
0.00
0.04
3
0.02
3
0.66
3
0.29
0.08 0.07 3
3
3
0.05
3
0.48
3
0.04
3
PI
0.29
0.16 0.09 3
3
3
0.94
3
0.50
3
0.07
3
0.10 0.08
3
3
0.04
3
PIII
PII
2.00
g.g-1
1.00
0.00
0.92
3
0.68
3
0.25
0.07 0.05 0.12
0.02 3
3
3
3
3
0.04
3
c
d
0.58
3
cu
fe
ni
pb
zn
0.02
3
cd
Metals
cu
0.26
0.22
0.03 0.02 3
0.02 3
3
3
3
fe
ni
pb
zn
0.40
3
0.06
3
cd
0.0
4
3
cu
Metals
fe
ni
0.24
0.08 0.02 3
3
3
pb
zn
Metals
A: Acroporid, F: Favid, P: Porites,

I: Kubbar Is., II: Maradeem Is., III: Quaro Is
Error Bars show 95.0% Cl of Mean
Bars show Means
Fig. 2. Mean metal levels in corals during winter.
31
AI
2.00
AII
AIII
1.50
g.g-1
0.90
1.00
0.81
0.50
0.40
0.50
0.06
0.00
0.06
0.08 0.07
0.11
G
0.05
0.03
0.07 0.06
G
FI
2.00
0.31
0.24
0.12
G
0.06
0.08
0.02
FII
0.02
G
0.10
G
FIII
1.60
G
1.50
g.g-1
0.52
G
0.50
0.60
G
0.51
G
0.31
0.09 0.1
0G
0.07
0.12 0.09
0.07
0.18
G
0.02
0.25
0.24
0.10
0.02
1.96
PII
PI
2.00
0.74
0.07
0.00
0.94
0.86
1.00
PIII
1.79
1.42
1.50
g.g-1
1.22
1.04
0.97
1.00
1.08
1.01
0.70
0.55
0.09
0.28
0.19
0.18
0.57
0.57
0.50
0.14
0.14
0.18
0.12
0.15
0.00
Cd
Cu
Fe
Ni
Pb
Zn
Metals
Cd
Cu
Fe
Ni
Pb
Metals
Z
n
Cd
Cu
Fe
Ni
Pb
Zn
Metals
A: Acroporid, F: Favid, P: Porites,

I: Kubbar Is., II: Maradeem Is., III: Quaro Is
Bars show Means
Fig. 3. Mean metal levels in corals during summer.
32
Aa
Ap
Fa
0.40
0.30
g.g-1
D
0.20
0.22
D
D
0.10
0.14
0.17
0.16
0.12
0.09
0.08
0.10
0.08
Fp
Pa
Pp
D
0.40
0.42
D
0.30
D
g.g-1
0.20
0.23
0.22
D
0.22
D
0.15
0.14
0.10
0.29
0.28
0.33
II
III
Sites
II
III
Sites
II
III
Sites
I: Kubbar Is., II: Maradeem Is., III: Quaro Is.,

A: Acroporid, F: Favid, P: Porites, a: anterior, p: posterior
Dot/Lines show Means
Fig. 4. Parts wise trace metals level in corals during winter.
33
Aa
Ap
Fa
0.30
g.g-1
0.20
D
D
0.10
0.11
0.06
0.12
0.10
0.0
9
0.14
0.13
0.09
0.07
Fp
Pa
Pp
D
0.30
0.31
g.g-1
0.26
0.25
0.20
0.19
0.1
8
0.10
0.34
0.18
D
0.11
0.10
I
II
III
Sites
II
III
Sites
II
III
Sites
I: Kubbar Is., II: Maradeem Is., III: Quaro Is.,

A: Acroporid, F: Favid, P: Porites, a: anterior, p: posterior
Dot/Lines show Means
Fig. 5. Parts wise trace metals level in corals during summer.
34
ACKNOWLEDGEMENT
The Environmental Public Authority of
Kuwait (EPA) are acknowledged for their
financial support for this project-EXC-002.
Mr. Shakri, EPA is also thanked for sample
collection and AAS analysis.
REFERENCES
1. G. T. Shen, Rapid changes in the tropical
ocean and the use of corals as monitoring
systems. In: Berger A (Ed.), geo
indicators:Assessing Rapid Environmental
Changes in Earth Systems. Brokfield,
Roterdam (1996).
2. G. T. Shen and E. A. Boyle, Earth Planet
Sci. Lett. 82, 289-304 (1987).
3. P. J. Scott, J. of Expt. Mar. Biol. Ecol. 13,
51-64 (1990).
4. H. M. Guzman and C. E. Jimenez,
Mar. Pollut. Bull. 24, 554-561 (1992).
5. D. McConchie and V. J. Harriot, Proc. of
the 7th Int. Coral Reef Symp. 1, 97-103
(1992).
6. G. Esslemont, Mar. Pollut. Bull. 38(11),
1051-1054 (1999).
7. C. Bastidas and E. Gracia, Mar. Pollut.
Bull. 38, 899-907 (1999).
8. S. J. Fallon, J. C. White and M.
McCulloch, Geochim. et Cosmochim.
Acta. 66, 45-62 (2002).
9. C. P. David, Mar. Pollut. Bull. 46,
187-196 (2003).
10. L. S. Howard and B. E. Brown, Ocean.

and Mar. Biol. Ann. Rev. 22, 195-210
(1984).
11. P. J. Scott and M. Davies, Mar. Pollut.
Bull. 34, 975-980 (1997).
12. E. C. Kent, P. L. Harrison, G. Hodgson,
A.H. Al-saffar and H.A. Shaker, KISR and
EPA publications, Kuwait, 166 (1997).
13. G. Hodgson and K. Carpenter, Pac. Sci.
49, 227-246 (1995).
14. N. Downing, Proc 7th Int. Coral Reef
Symp. Guam. 2, 959-968 (1992).
15. N. Downing, Coral Reefs 9, 231-237
(1985).
16. D. Al-Bakri, F. Khalaf and A. N.
Al-Ghadban, J. Sed. Petrol. 54, 1266-1279
(1984).
17. M. A. Al-Sarawi, E. Gundlack and
B. Baca, Environmental sensitivity index
for the shoreline of Kuwait. Final Report,
Kuwait Foundation for the Advancement
of Sciences, Kuwait, 49 (1985).
18. A. N. Al-Ghadban, M. Abdul Rahaman
and A. Salman, Kuwait Institute for
Scientific Research, Report No. KISR
3419, Kuwait (1990).
19. D. G. Crossby, Environmental toxicology
and chemistry. In: Bricks (Ed.), Topics in
environmental
chemistry,
Oxford
University Press, New York, 366 (1998).
20. E. G. Arnold, S. C. Lenore and A. E.
Eaton, Standard method for the
examination of water and wastewater,
American Public Health Association,
Washington, USA., 4-75 (1992).
35
HIGH LEVEL EXPRESSION AND SINGLE-STEP

PURIFICATION OF IN VIVO BIOTINYLATED GREEN
FLUORESCENT PROTEIN
S. Salman Ashraf
Department of Chemistry, UAE University,
P.O.Box 17551, Al-Ain, UAE
E-mail: salman.ashraf@uaeu.ac.ae
Keywords: E. coli, Escherichia coli, GFP, green fluorescent protein, His6, hexahistidine
tag, AviTagTM, 15 amino acid biotinylation tag, NEB, New England Biolabs,
IMAC, immobilized metal affinity chromatography, NTA, nitrilotriacetic
acid, IPTG, isopropyl-beta-D-thiogalactopyranoside, LB, Luria Broth.
ABSTRACT
Green Fluorescent Protein (GFP) is a unique protein that was initially identified and isolated from
the jellyfish Aequorea Victoria. The unusual stability of this protein combined with its strong
autofluorescence makes this a protein of choice for many biotechnological and cell biology
applications. We describe here a recombinant system that can be used to produce high levels of in
vivo biotinylated GFP-fusion proteins in E. coli. This system combines the versatility of the
hexahistidine tag (His6) with the site-specific in vivo biotinylation of a 15-amino acid tag
(AviTagTM) to produce in vivo biotinylated GFP. We have used this system to express and purify
(in high yields) His-tagged and biotinylated GFP. The multi-affinity tagged GFP protein was
readily purified using a single Ni2+- affinity chromatographic step. Streptavidin-beads pull-down
assays were performed to demonstrate that the purified GFP protein was fully-biotinylated. Lastly,
fluorescent spectroscopic analyses showed that His-tagged and biotinylated GFP had the same
excitation and absorbance spectra as those published for the wild-type GFP. The vector system
presented here is a versatile tool that can be used to produce high levels of biotinylated GFP,
as well as multiple-tagged GFP-fusion of any protein of interest.
INTRODUCTION
The green fluorescent protein (GFP) from the
jellyfish Aequorea Victoria is widely used as a
reporter protein in cell biology and molecular
biology applications [1,2,3,4,5]. Mutant forms
of this protein that allow efficient in vivo
folding, high levels of expression in E. coli,
and increased fluorescence are increasingly
used as fusion proteins for protein engineering
and expression studies [6,7]. For example,
Waldo et al. have reported a technique to

screen for properly folded recombinant
proteins in E. coli, using a GFP fusion tag [8].
In addition to being versatile fluorescent tags,
there are recent reports indicating that GFP
may be used to increase the expression and
solubility of foreign proteins in E. coli.
Perhaps, GFP like Glutathione S-Transferase,
Maltose Binding Protein, thioredoxin, and
NusA may be an efficient solubility enhancing
fusion partner.
37
We have previously reported on the design and

construction of a multi-affinity tag vector that
combined the solubility enhancing property of
MBP, the versatility of the His6-tag, and the
site specific biotinylation of the 15-amino acid
AviTag [9]. In this report, we report the
construction of a novel GFP-fusion vector that
allows for the production of triply-tagged
proteins-GFP, His6 and AviTag. We have used
this vector to produce His6 and AviTag
containing GFP, which was purified using
Ni2+-NTA and was shown to be sitespecifically in vivo biotinylated. In addition to
being a versatile vector, the work presented
here can be used to easily produce large
amounts of biotinylated GFP which can be
employed for proteomics and biotechnologyrelated investigations.
MATERIALS AND METHODS
Materials
The bacterial strain used in this study is based
on the BL21 (DE3) strain (Stratagene),
genotype E. coli B F ompT hsdS(rB mB)
dcm+ Tetr gal (DE3) endA. BL21 (DE3)
expresses T7 RNA polymerase (due to the T7
phage -lysogen) when induced by IPTG. As
described earlier [9], plasmid pBirAcm
(Avidity) was introduced into the strain, which
produces E. coli biotin ligase. pGFP-His-AT
described here was built from the vector pET15b (Novagen), which allows for the
expression of protein from a T7 promoter.
The bacterial growth medium was LB,
supplemented with 30 g/ml chloramphenicol
to maintain the pBirAcm plasmid, 50 g/ml
ampicillin to maintain pGFP-His-AT, and 50
M biotin for in vivo biotinylation of the overexpressed proteins containing the AviTag. All
the restriction enzymes as well as T4 DNA
ligase were from NEB. Ni2+-NTA and
streptavidin agarose resins were from the
Sigma Chemical Company. Site-directed
mutagenesis was carried out using the
QuikChange Site-Directed Mutagenesis Kit
(Stratagene).
Construction of pGFP-HisAT
Plasmid pQBI T7-GFP (Qbiogene) was used
as a template to PCR amplify the GFP gene.
The GFP gene had the following mutations to
allow for enhanced fluorescence and solubility
in E. coli: Phe64 Leu, Ser65 Cys,
38
Ile167 Thr. Before the PCR amplification,

the internal NdeI in the GFP gene (in pQBI
T7-GFP) was eliminated using site-directed
mutagenesis(229CATATG234229CACATG234)
using the QuikChange Site-Directed
Mutagenesis Kit (Stratagene). For PCR
amplification of GFP, the primers were
designed such that the resultant PCR product
had an NdeI restriction site at the 5' end, and a
BamHI site at the 3' end. This PCR product
was digested with NdeI and BamHI after
which it was ligated into the pET-N-AT [9]
vector which had been also digested with NdeI
and BamHI. DNA sequencing was used to
confirm the sequence of the resultant GFPfusion vector, pGFP-HisAT.
For the expression and purification of GFP,
the pGFP-HisAT plasmid was transformed
into the BL21-DE3, pBirA strain, which has
been described earlier [9]. This strain allows
for the high-level expression of recombinant
proteins from a T7 promoter, as well as
allowing in vivo biotinylation of fusion
proteins carrying the AviTag sequence [9].
Expression conditions
Overnight cultures were grown at 25C in LB
with ampicillin (50 g/ml) to select for pGFPHisAT and chloramphenicol (25 g/ml) to
select for the pBirA plasmid. The cultures
were diluted 1:20 into LB containing the
antibiotics and 50 M biotin, and then allowed
to grow at 25C for 3 hours, when the OD600
reached a value between 0.6 and 1. Cultures
were then induced with 0.3 mM IPTG for
16-18 hours at 25C, harvested by
centrifugation, and the pellets stored at -20C.
Purification of His6-avitag-GFP
GFP, containing His6 and AviTag affinity tags,
was purified as described for the E. coli
elongation factor Tu (TufB) and Gyrase
(GyrA) [9]. Briefly, the bacterial pellet was
lysed by 2 cycles of freeze-thaw in 50 mM tris
buffer pH 8.0, and containing 0.1 mg/ml
lysozyme. The lysates were cleared by
centrifugation (30 min at 25,000 x g) and
applied in a batch-mode to a Ni2+-NTA resin
(Sigma). After allowing 30 minutes (at room
temperature) for binding, the resin/lysate
mixture was briefly centrifuged, washed
extensively with 50 mM tris buffer containing
500 mM NaCl, and then with successive wash
of the same buffer containing 5 and 10 mM

imidazole respectively. Bound GFP was eluted
with 50 mM tris buffer pH 8.0 containing 250
mM imidazole.
Fluorescence Spectrophotometer using a 3 ml

quartz fluorescence cell in 50 mM tris buffer
pH 8.5.
Streptavidin-beads pull-down assay

Approximately 10-20 g (in 40 l buffer) of
biotinylated GFP was incubated with 0.5 ml of
streptavidin-coated agarose (Sigma) and
allowed to bind for 30-60 min at 25C. The
agarose beads were then pelleted by brief
centrifugation and washed 2 times with trisbuffered saline wash buffer. The beads were
then re-suspended in 40L of 1% SDS, boiled
for 2 minutes, and analyzed by SDS-PAGE.
Protein analysis
SDS-PAGE was performed with 12% tris gels
and with a tris/Glycine/SDS running buffer.
The protein content was determined by
colorimetric protein assay (BioRad) using
BSA as a standard.
Fluorescence Analysis
Construction of pGFP-HisAT Vector

The pGFP-HisAT plasmid is based on the T7
expression system of pET vectors (Novagen)
and was modified as described in the Materials
and Methods section and schematically shown
in Figures 1 and 2. In the vector, the AviTag
and the His6 tags are at the N-terminus of the
expressed protein, and right before the GFP
gene. Therefore, this vector would express
proteins that will have AviTag and His6 tags at
the N-terminus. In the current version of the
vector, there is a unique NdeI restriction that
can be used for cloning of other proteins of
interest after the GFP, to make GFP-fusion
proteins. This could be made into a multiplecloning site by inserting an NdeI-cassette with
NdeI sites at both ends and a series of
restriction sites of interest.
Emission and excitation spectra of GFP were

determined using the Cary Eclipse
Fig. 1. Plasmid map for pGFP-HisAT expression vector.
39
Fig. 2.
Nucleotide sequence of the affinity tags as well as the location of the

NdeI cloning site in pGFP-HisAT expression vector.
Expression and Purification GFP

Since GFP is highly fluorescent even under
normal light, we were able to visually follow
the expression as well as the purification of the
protein (data not shown). SDS-PAGE analysis
of the induced culture shows that GFP was
expressed at very high levels, accounting for
approximately 70-80% of the soluble cytosolic
proteins (Figure 3). This was consistent with
earlier reports that GFP can be expressed at
high-levels in E. coli, even though there are
some reports that some GFP constructs do not
express well in E. coli [10].
The IMAC-purification of GFP using Ni2+NTA was very efficient and straightforward.
This single step resulted in more than 95%
pure GFP, as judged by SDS-PAGE, followed
by Coomassie Blue (no other contaminants
could be seen). One of the useful features of
this vector is the 15-amino acid biotinylation
tag (AviTag), which is biotinylated in vivo by
40
E. coli biotin ligase. We have shown earlier

how this AviTag could be used to produce in
vivo biotinylated fusion proteins [9] . Figure 3
also shows the results from a streptavidin pulldown assay, in which biotinylated proteins are
allowed to bind to streptavidin-coated beads
(see the Materials and Methods section), and
the subsequent analysis of the beads on SDSPAGE allows for the testing of the
biotinylation of the proteins. As can be seen
from the gel, GFP appears fully biotinylated.
In vivo and site-specific biotinylation of
proteins has been shown to be useful in
analyzing protein-protein interactions and in
other proteomics-based studies [11,12,13,14].
We have previously reported the use of this
biotinylation tag on proteins to format robust
assays and carry out high-throughput
screening to identify inhibitory compounds for
a therapeutically important target [11].
Fig. 3. Soluble expression and purification of GFP and demonstration of biotinylation of

GFP as described in the Materials and Methods section. Lane 1: Uninduced lysate
(soluble proteins); Lane 2: Induced lysate (soluble proteins); Lane 3: Ni2+-NTA
eluate (using 250 mM imidazole); and Lane 4: Protein (GFP) eluted from
streptavidin-agarose beads.
Lastly, to make sure that the N-terminal tags

on GFP from the vector did not change the
fluorescence of GFP, we examined the
excitation and emission spectra of the
recombinant GFP (Figure 4). These excitation
and emission maxima of our GFP are in
agreement with those reported previously in
the literature; hence the His6 and the AviTag
did not significantly alter the fluorescence or
structural properties of GFP.
Site-specific, in vivo biotinylated proteins have

numerous potential in proteomics and
biotechnology [11,12,13,14].
Furthermore,
use of GFP in proteomics and biotechnology
has been steadily increasing.
The work
described here to produce biotinylated GFP or
biotinylated GFP-fusions with other proteins
will lead to further exploitation of GFP for
novel applications.
ACKNOWLEDGEMENT
CONCLUSION
In summary, we report here the construction of
a vector that allows for the high level
expression and single-step purification of
GFP. We have used this vector to express in
vivo biotinylated GFP at very high levels in E.
coli. The biotinylated protein was efficiently
purified by a single step of Ni2+ IMAC
chromatography.
The author thanks the UAE University

Research Affairs Department for financial
support of the work, and Dr. Ahmed Mirza
Almehdi (UAE University, Chemistry
Department) for generous use of his laboratory
resources. Cloning work described here was
done at Karo Bio USA in NC, USA.
41
Fig. 4: Excitation and emission spectra of His6- and biotinylated-GFP. The excitation
spectrum was obtained with the emission set at 500 nm, and the emission
spectrum was obtained with the excitation set at 474 nm. The spectra were
recorded by using Ni2+-NTA-purified GFP in 3 ml 50 mM tris buffer pH 8.5.
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1. R. Y. Tsien, Annu. Rev. Biochem. 67,
509-44 (1998).
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and T. C. Terwilliger, Nat.Biotechnol. 17,
691-5 (1999).
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Y. Koyama, Anal Biochem. 243, 176-80
(1996).
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C. M. Halbleib and H. Gron, Protein Expr.
Purif. 33, 238-45 (2004).
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J. Krijgsveld, E. Katsantoni, A. Heck, F.
Grosveld and J. Strouboulis, Proc. Natl.
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Ejima and T. Arakawa, Biochem. Biophys.
Res. Commun. 312, 1383-6 (2003).
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Ashraf and D. J. Christensen, J. Biomol
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Anal. Biochem. 306, 314-22 (2002).
43
ASSESSMENT STUDY ON SELECTIVE PHYSICAL

CHARACTERISTICS OF LUBRICATING OILS
M.A. Rauf1, S. Khaliq2 and S. Manzoor3
1
Department of Chemistry, UAE University, P.O.Box 17551, Al-Ain, UAE

E-mail: raufmapk@yahoo.com
2,3
Department of Chemistry, Quaid-i-Azam University, Islamabad, Pakistan
ABSTRACT
Viscosity measurements on unused and used lubricating oil samples have been carried out at four
different temperatures, i.e. 25, 40, 70 and 100C using a thermostated U-tube viscometer. The data
was used to calculate the activation energies of flow in such samples. An attempt was also made to
carry out composition analysis of lubricating oils in terms of sulfated ash, aniline point and total
acid number (TAN).
INTRODUCTION
EXPERIMENTAL
The most important property of lubricating oil
is its viscosity. For most of the applications
where boundary lubrication conditions are
prevalent, it is the viscosity of lubricating oil,
which determines to a large extent the uses to
which the oil can be put. Kinematic viscosity
is more significant than other viscosity
parameters in problems of hydrodynamics
because the flow properties of a liquid depend
on inertia as well as internal friction [1].
Although there are a lot of different physical
and chemical tests suggested for lubricating
oils, the important chemical tests include
values usually referred to as sulfated ash, total
acid number (TAN) and aniline point
respectively besides the trace metal content in
oils. The variation of these values will dictate
to a large extent the quality of oils.
The objectives of the present study are twofold. Firstly, to evaluate the physical
parameters of various oils such as activation
energy etc. and secondly, to find out the values
of oil related parameters such as the TAN
value, aniline point etc. This data will be used
to evaluate the quality of both used and unused
oils of different categories.
The viscosity measurements were made by

using Technico BS/U G and B viscometers,
which were pre-calibrated with ASTM oil
standard number S-120 and S-200. The
viscometer was immersed in a thermostated oil
bath with a temperature control of 0.01C.
The flow time was observed with a timing
device with a precision of 0.1 s. For each
sample, at least triplicate runs were performed.
Additionally, the following three important
values in lubricating oils were estimated by
using the standard methods as described in
ASTM D 874-IP 163, ASTM D 1012-FTM
791-3601.5 and ASTM D 611.
Sulfated Ash: The oil sample was ignited and
burned until only ash and carbon remained.
After cooling, the residue was treated with
concentrated sulfuric acid and heated at 775C
until there was complete oxidation of the
carbon. The ash was then cooled, re-treated
with sulfuric acid and heated at 775C. This
procedure was repeated several times until a
constant weight of the contents was obtained.
45
B = Volume (in mL), corresponding to A for

the blank titration.
Aniline Point: A specified volume of aniline

and lubricating oil (usually 10 mL each) were
placed in a tube fitted with a stirrer and
thermometer. The mixture was heated at a
controlled rate, usually 1-3C/min. until the
two phases became miscible. The solution was
then cooled slowly and the temperature at
which the two phases separated out was noted,
as indicated by the first appearance of
turbidity.
N = Normality of the alcoholic KOH solution.

w = Weight of the sample in g.
Oil samples used in this work along with their
grading are listed in Table 1. The oil samples
used in this work are divided into three
categories. First, there are the sealed oil
samples, which are available in the market and
are products of different oil companies. These
have been labeled as S/1-S/8 respectively. The
second batch of oil samples consists of open
oil samples labeled as O/1-O/5. These are oil
samples available in the open form in the
market and do not bear any brand name. These
are in most cases the reclaimed oils. The third
batch, U/1-U/7 are the used oil samples. In this
category, the U/1-U/6 oils are basically the
same ones as S/1-S/6 except that they have
been recovered from the engines after their
usage. All like grade samples are also of a
different make. It was ensured that the oils
recovered were at the same intervals of their
service life (normally 3000 km run for
engines).
Total Acid Number (TAN): The sample was

dissolved in a mixture of toluene and isopropyl
alcohol which also contained a small amount
of water. This was titrated potentiometrically
with alcoholic potassium hydroxide using the
glass electrode as an indicator electrode and a
calomel electrode as a reference electrode. The
potential change on the pH meter was plotted
against the respective volumes of the titer
solution and the end point was taken at a welldefined inflection on the resultant curve.
The total acid number (TAN) was calculated
using the following equation [2]:
TAN = {(AB) x N x 56.1}/w
(1)
A = Volume of alcoholic KOH solution

(in mL) used to titrate the sample to the end
point that occurs at the meter reading of the
inflection point.
Table (1). Sample code and grading of oil samples.
Sample
Grading
Sample
Grading
Sample
Grading
S/1
SAE 30/40
O/1
SAE
U/1
SAE 30/40
S/2
SAE 30/40
O/2
20/40
U/2
SAE 30/40
S/3
SAE 20W-50
O/3
SAE
U/3
SAE 20W-50
S/4
SAE 20W-50
O/4
20/40
U/4
SAE 20W-50
S/5
SAE 20W-50
O/5
U/5
SAE 20W-50
S/6
SAE 20W-50
------
U/6
SAE 20W-50
S/7
---------------
------
U/7
SAE 20/40
S/8
SAE-40
All like grade samples are of a different make.
46
The viscosity values of all the abovementioned oil samples were obtained on a
U-tube viscometer at four different
temperatures, i.e. 25, 40, 70 and 100C. Since
it is known that the viscosity of the lubricating
oils decreases with increasing temperature, a
similar trend was observed for all the oil
samples as shown in Table 2. From the
observed data it can be inferred that the used
oil samples have lower viscosity values as
compared to the respective unused oil samples.
This can be interpreted simply on the basis
that since lubricating oils are complex
mixtures of long and tangled hydrocarbon
chain molecules, breakage or untangling of
these chain molecules takes place at high
temperatures resulting in the decrease of the
viscosity values. This is why the used oil
samples which have gone through rigorous

mechanical and thermal stress, are less viscous
than the unused oils. From the data, it is clear
that the open oil samples are of a low viscosity
value and can be classified as of low quality.
The viscosity temperature characteristics of
the oils can be represented by various values
such as viscosity index (VI), viscosity
temperature coefficient (VTC), viscosity
temperature slope (VTS) and the activation
energy for viscous flow. In this work the data
was analyzed in the light of the last two
values. Firstly, the VTS, was calculated using
the Walther equation [2] given by the
expression:
Log log (V+0.6) = c + m log (T+460)
(2)
Table (2). Viscosity of lubricating oil samples at different temperatures.

Viscosity (cSt)
Sample Code
S/1
S/2
S/3
S/4
S/5
S/6
S/7
S/8
O/1
O/2
O/3
O/4
O/5
U/1
U/2
U/3
U/4
U/5
U/6
U/7
25C
351 1.00
411 0.70
423 1.27
369 0.79
432 1.00
435 1.11
114 1.27
321 1.11
289 1.04
138 0.73
366 1.01
60 0.51
372 1.11
315 1.58
285 0.52
312 0.73
281 1.11
252 0.71
387 1.27
219 0.51
40C
190.6 1.27
186 1.58
189 1.25
172 0.70
210 0.79
221 1.24
51 0.50
128 1.24
116 0.79
66 3.24
159 1.27
33 0.47
162 0.31
138 1.00
110 0.81
135 1.04
148 1.24
100 0.75
174 0.51
73 0.51
70C
36 1.58
45 1.00
57 0.50
42 1.27
60 0.50
66 0.71
14 1.27
24 0.79
21 0.71
18 2.01
39 1.24
11 1.24
42 0.69
30 1.21
21 1.81
27 1.00
25 0.79
20 1.05
45 1.56
11 1.24
100C
6.10.05
8.20.10
12.20.15
7.30.10
110.20
12.90.20
3.00.10
2.90.15
3.30.05
3.70.03
5.50.05
2.70.02
8.20.05
5.50.03
2.70.02
3.70.02
4.50.03
3.00.01
100.10
1.40.01
Results of triplicate measurements.
47
Table (3).
Parameters A and B of the Walther

equation and activation energy, Ev,
from the Andrade equation.
Sample
code
Ev (kcal/mole)
S/1
S/2
S/3
S/4
S/5
S/6
S/7
S/8
O/1
O/2
O/3
O/4
O/5
U/1
U/2
U/3
U/4
U/5
U/6
U/7
9.92
9.34
8.23
9.29
8.02
7.66
11.41
11.97
12.44
10.56
14.46
10.36
9.28
10.56
12.35
11.21
11.45
12.27
9.12
15.85
-3.48
-3.27
-2.86
-3.25
-2.78
-2.65
-4.06
-4.24
-4.41
-3.75
-5.14
-3.77
-3.25
-3.72
-4.38
-3.96
-4.04
-4.33
-3.19
-5.67
10.30
10.00
9.00
9.83
8.91
9.34
9.44
11.73
11.87
9.20
10.11
7.68
9.82
10.65
11.79
11.09
12.06
11.44
9.70
13.50
The viscosity temperature data was also

analyzed using the Andrade equation [3]:
V = A exp Ev /RT
(3)
V is the viscosity in centistokes, R is the gas

constant and T is the temperature in Kelvin.
A plot of viscosity versus temperature gives a
straight line with a pre-exponential value of A
and a slope of Ev, which is the activation
energy for viscous flow. Ev values calculated
for various oil samples are listed in Table 3
and shown graphically in Figure 1 for sample
no. S/1. Generally speaking, a low value of Ev
suggests that the oil is of poor quality as it
requires only a very small temperature change
48
to undergo deformation in its complex

molecular structure. This deformation in oil
structure causes the oil to loose its lubrication
property and slip off from the desired
mechanical parts of the engine thus causing
more frictional motion.
ln Viscosity (cst)
V is the kinematic viscosity in centistokes and

T is the temperature in degrees Fahrenheit.
A plot of log (V+0.6) versus log (T+460) gives a
straight line with an intercept value of c, and a
slope value of m. Both these values for oils in
the present studies are given in Table 3. From
this table one can see that the c value is
smaller in sealed oil samples compared to their
used counterpart. Similarly, the m value is
greater in the sealed oil samples compared to
their used counterpart.
1/T x 1000 (K)
Fig. 1. Temperature dependence of oil

viscosity in sample number S/1.
The second part of the present work involves
the composition analysis in oil samples. Three
parameters, i.e. the %-sulfated ash, aniline
point and the total acid number (TAN) were
determined. The data is given in Table 4. The
sulfated ash may be used to indicate the
concentration of known metal containing
additives in new oil. These additives usually
contain one or more of the following metals:
Ba, Ca, Mg, Zn, K, Na and Sn [4]. When
phosphorous is absent, Ba, Ca, Mg, Na and K
are converted to their sulfates, while Sn is
converted to stannic and Zn to oxide. The %
sulfated ash data obtained for various oil
samples in this study ranges from 0.10-1.04%
respectively.
Another important parameter is the aniline
point. It is generally a measure of the aromatic
and naphthenic compounds present in the
sample. The aniline point is of practical
importance to lubricants. In practically every
oil system, there are seals to prevent leakage,
and oil can have a measurable effect on the life
of the seals depending upon the aniline point.
Rubber is widely used as a sealant. Hence it is
important to know its effect on oil. Generally,
for a fixed rubber formulation, the lower the
aniline point of the oil, the greater the effect
upon the sealing material. The effect is one of
mutual solubility or more specifically, a tendency
CONCLUSION
Table (4).
Results of composition analysis of

lubricating oil samples.
Aniline
%
Sulfated Point (oC)
Ash
S/1
0.69
90
S/2
0.33
92
S/3
0.74
93
S/4
1.02
91
S/5
0.91
94
S/6
1.04
95
S/7
0.10
87
S/8
0.79
89
O/1
0.10
85
O/2
0.13
84
O/3
0.35
83
O/4
0.40
84
O/5
0.61
82
U/1
U/2
U/3
U/4
U/5
U/6
U/7
* TAN = Total acid number
Sample
Code
*TAN
(mgKOH/g)
0.03
0.05
0.03
0.10
0.03
0.02
0.09
0.05
2.02
1.23
2.13
2.23
1.70
2.02
1.90
2.24
2.13
2.24
1.90
2.13
Potential (mV)
to swell rubber. Thus, a low aniline point for

oil is undesirable and is indicative of poor
quality. It was observed that almost all the oil
samples which were obtained in an open form
from the market had low aniline points, and
hence are of poor quality. Another important
parameter, which dictates the quality of oil, is
the total acid number (TAN). Acidity in oil is
due to acidic ingredients present in the oil such
as carboxylic acids, esters and phenolic
compounds etc. For every grade of oil, a
specific value of TAN is a measure of the total
acidic ingredients present in the unused oil
samples. The acid number of new
uncompounded oil is normally in the range of
0.02 to 0.10. Such values indicate that acidic
materials such as process acids have been
adequately removed. In this study all sealed oil
samples fall within this range, which shows
they are of good quality. However, all open oil
and used samples have a high TAN value,
which is an indication of their high acidic
character. It is a fundamental requirement for
lubricating oil to have a specific acidic value
(0.02-0.1) in order to function properly. When
oil comes in contact with air in the presence of
certain metals at high temperature, oxidation
takes place. The oxidation process leads to the
formation of varnish, sludge and more acids.
The acid formed in the oxidation process leads
to the corrosion of metals and alloys in contact
with the lubricant. The TAN value for used oil
is an indicator of its degree of oxidation.
A representative potentiometric titration curve
for oil sample no. S/1 used for the estimation
of TAN values is shown in Figure 2, where the
potential value is plotted vs. the volume of
KOH.
0.5
1.5
Volume of KOH (mL)
A comparative composition analysis of three

types of oil samples (sealed, open and used)
have shown that sealed oils have higher aniline
points compared to open oil samples. In
addition, the TAN values in sealed oils are
much lower compared to open and used oils.
Fig. 2. Potentiometric titration curve for the

estimation of the aniline point in
sample S/1.
49
REFERENCES
1. H. F. Mark, J. J. Meketta and D. F.
Othmer (Ed.), Encyclopedia of Chemical
Technology, John Wiley and Sons, 12, 365
(1967).
2. S. K. Jain, J. V. Parikh and R. P. Gupta,
Industrial Lubricants, Greases and Related
Products, S.B. Publication, New Delhi, 15
(1981).
50
3. P. Atkins, The Elements of Physical

Chemistry, 2nd ed., W.H. Freeman and
Co., New York, 384 (1988).
4. M. W. Ranney, Lubricant Additives:
Recent Developments, Noyes Data
Corporation, Park Ridge, N. J. (1978).
EFFECT OF ALKALI SALTS ON THE VISCOSITY

OF KAHU GRASS BLACK LIQUOR
M. A. Rauf1, M. J. Iqbal2 and Q. M. Malik3
E-mail: raufmapk@yahoo.com
1,
Department of Chemistry, P.O.Box 17551, UAE University, Al-Ain, UAE

Department of Chemistry, Quaid-i-Azam University, Islamabad, Pakistan
2,3
ABSTRACT
A kahu grass thick black liquor (TBL) produced in the paper manufacturing process causes serious
handling problems due to its high viscosity. In the present study, the viscosity of this black liquor
(having 50% solid content) has been decreased significantly in acidic medium by the addition of
small concentrations (<0.1 M) of various alkali salts such as potassium bromide, potassium
thiocyanate, potassium dichromate and potassium permanganate respectively. Parameters related
to viscous flow, like temperature and salt concentration were evaluated and the activation energy of
the viscous flow was calculated. It is believed that the protonated phenolic hydroxyl groups of the
lignin macromolecule, responsible for the elevated viscosity of the black liquor, are prevented from
association by the alkali salts that result in reduction of its viscosity.
INTRODUCTION
The spent liquor (thick black liquor, TBL)
produced in the pulping process for onward
recovery in the paper and pulp manufacturing
process is a complex aqueous mixture of
several components including polysaccharides,
lignin and inorganic materials such as sodium
sulfate and sodium carbonate [1]. The lignin,
polysaccharides and inorganic materials may
be the cause of an extremely elevated viscosity
of the black liquor [2-4]. Handling of such
highly viscous liquor poses serious practical
problems and therefore requires a lowering of
its viscosity [5]. The strong dependence of the
viscosity of the black liquor on temperature
and its solid content is well known and has
also received considerable attention from
rheologists [6,7]. The viscosity of the black
liquor is reduced on addition of caustic alkali
and is thought to be due to oxidation of the
black liquor [7]. A process in which the sulfide
in the black liquor is oxidized to thiosulfate
accompanied by a lowering of the viscosity
has also been reported [8,9]. A method where
carbon monoxide gas is dissolved in the black
liquor to cause reduction in its viscosity has

also been suggested [10]. Another method in
which a few parts per million of a soluble
polymer is used in black liquor has also been
reported in the literature [11]. In many cases, a
thermal depolymerization technique for
decreasing the viscosity of black liquor has
also been suggested and has also come to full
mill-scale operations [12]. All the above
methods are either costly or require special
additional techniques to lower the viscosity of
the black liquor.
Additionally, thiocyanate salts of guanidine,
ammonium, sodium, potassium and lithium
have been tested for the viscosity reduction of
wood black liquor [13]. The advantage of
using these salts is the simplicity of the
process, as it merely requires the addition of
these salts to the black liquor. The addition of
salts reduces the viscosity of the black liquor
thus making it easier to handle during the
subsequent stages. In the present paper, the
effect of alkali salts such as KBr, K2Cr2O7,
KMnO4 and KSCN on the reduction of the
viscosity of the black liquor produced from
51
Kahu grass is reported. Kahu grass is a locally

produced grass in Pakistan, and has shown
promising results for the local paper
manufacturing industry. It also has the
potential to be used on a large scale, instead of
the conventional pulp obtained from various
sources for the manufacture of paper. The
grass is very easily and locally cultivated and
is much cheaper to use as a raw material than
the wooden pulp. This grass, like any other
pulp
raw
material
contains
lignin,
polyscharides and other inorganic materials,
but its composition is quite different from
other raw materials. Although most of the
paper manufacturing units use the well known
"Kraft process" to prepare their products, the
nature of the raw material poses a challenge at
every stage. Kahu grass when used as a
starting material also results in the production
of a thick black liquor (TBL) just like in the
cases of other raw material. However, since
the composition of each raw material is
different, one would anticipate a different
viscosity for this liquid. No attempt was made
to determine the exact composition of the
Kahu grass at this stage. Its usage in the paper
manufacturing process however, demands the
optimization of many variables such as salt
contents which can be used to reduce the
viscosity of the thick black liquor in this case.
In this work, optimized concentrations of such
salts were determined. The effect of
temperature and thereby the activation energy
of viscous flow was also determined.
EXPERIMENTAL
Samples of thick black liquor (TBL) of various
solid contents was procured from the local
manufacturer in Pakistan. No attempt was
made to analyze the samples in terms of its
composition at this stage. The samples were
used as such for further studies in this work.
Density measurement was performed using a
densitometer calibrated with mercury. The
viscosity of the sample was measured in a
thermostated bath using an Ubbelhode
viscometer. Efflux times were noted by a
digital counter of 0.01 s resolution. A temperature
stability of 0.1C was recorded using a
platinum resistance thermometer. Absolute
viscosity (in cps) was calculated by
multiplying the time of flow with the capillary
constant of the viscometer and the density of
52
the sample. The effect of alkali salts, namely

KBr, KSCN, KMnO4 and K2Cr2O7, on the
viscosity of the thick black liquor (50% solid
content) at 80C was also investigated. These
salts were added to the black liquor in the
presence of 0.05 M H2SO4. The salt
concentration was varied over a range of 00.15 M respectively. Samples containing
potassium salts were prepared by adding
appropriate amounts of salt on a molar basis to
the pre-concentrated black liquor. The
mixtures were then stirred vigorously and
heated at about 40C for at least thirty minutes
to dissolve the salt. Each sample was covered
to avoid evaporation losses. The black liquor
(solid content of 50%) was also subjected to
viscosity measurements at five different
temperatures, namely 40, 50, 60, 70 and 80C.
The viscosity measurement of the TBL in the
presence of added salts was also done at
different temperatures. The values of viscosity
obtained as a result of this temperature study
were used to calculate the activation energy of
viscous flow, Ev from the Arrhenius equation.
Initially, the black liquor of varying solid
content
was
subjected
to
viscosity
measurements. The results are given in
Table 1 and also shown in Figure 1. The black
liquor (solid content of 50%) was also
subjected to viscosity measurements at five
different temperatures, namely 40, 50, 60, 70
and 80C. The results are given in Table 2.
The viscosity of the liquor was found to
decrease with increasing temperature. This
behavior may be explained on the basis that at
high temperature, the lignin polymer is
depolymerized, thus decreasing the internal
stress to ease the flow [14]. The viscositytemperature relationship was plotted using the
Arrhenius equation, = o exp (Ev/RT), where
Ev is the activation energy of viscous flow and
o is the pre-exponential parameter. A plot of
1
ln versus
results in a straight line with a
T
slope which corresponds to the activation
energy for viscous flow, Ev . The value of Ev
for a representative case for the black liquor
was found to be 43.60 kJ with an estimated
error of 2 kJ. Figure 2 shows the dependence
of viscosity on temperature for one such case.
Table (2). The coefficient of viscosity of the

black liquor (50% solid content)
containing various salts (0.009 M)
versus different temperatures.
Table (1). The variation of the coefficient of

viscosity of the black liquor at
353 K with the percentage solid
content.
% solid
contents
(Black
liquor)
(Black liquor/
0.05M KMNO4/
0.05 H2SO4
10
4.725
2.9939
20
13.1235
5.9627
30
33.0253
11.1251
40
61.2091
17.8557
50
91.926
23.639
Black
KSCN K2Cr2O7 KBr KMnO4
liquor
313 66.417 28.4914 29.4831 30.0121 29.9121
T(K)
323 39.3221 18.9045 19.5277 21.9031 21.3531

333 23.671 12.8995 13.3621 14.3623 14.1789
343 15.734 9.5753
9.3975
9.1423
10.5171
353 10.4183 6.4356
6.3542
7.0213
7.0882
100
90
80
70
Viscosity(cp)
60
Viscosity
50
With addition of KmnO4& H2SO4
40
30
20
10
0
0
10
20
30
40
50
60
%age of solid contents
Fig. 1. The variation of the coefficient of viscosity of the black liquor at 353 K
with the percentage solid content.
53
70
60
50
Viscosity(cp)
TBL
40
Series2
K2Cr2O7
KSCN
KBR
30
K2Cr2O7
KSCN
KMnO4
20
10
0
30
40
50
60
70
80
90
100
Temperature(C)
Fig. 2. Plot of the coefficient of viscosity of the black liquor (50% solid content)
containing various salts versus different temperatures. TBL = thick black
liquor and Series 2 = black liquor solution containing 20% solid content.
Viscosity measurements were also carried out

under similar conditions by adding different
concentrations of various alkali salts to the
black liquor. The observed changes in its
viscosity at 80C (a suitable temperature for
viscosity measurement of black liquor by an
Ubblehode viscometer) are given in Table 3
and also in Figure 3. In all such cases, it was
observed that the viscosity of black liquor
reduced drastically with an average decrease in
viscosity by more than 75%. In aqueous
systems, such as black liquor, there are several
complicated interactions between the water,
lignin and salt. These play an important role

in the development of changes observed in the
mixture at the end. The solubility of salt,
which is related to viscosity, will depend on
solute-water interactions, ionic interactions
with the salts in solution and repulsive
electrostatic forces when the solute molecules
are charged [15]. The viscosity of the black
liquor at different temperatures was also
measured in the presence of a fixed amount of
the alkali salts (0.009 mol.L-1) used in this
study. The results are shown in Table 4.
Table (3). The coefficient of viscosity of black liquor (50% solid content) at 353 K versus
different salt concentrations.
KBr
Conc./M
0.005
0.01
0.015
0.035
0.045
0.055
0.065
0.075
54
KMnO4
(cP)
8.5245
6.9521
5.9241
4.4151
3.5674
2.938
2.5129
6.3251
Conc./M
0.005
0.01
0.015
0.025
0.05
0.075
0.1
0.125
0.15
(cP)
8.2346
6.4396
5.6789
4.5706
3.9086
3.1968
2.7446
2.3484
10.5661
KSCN
Conc./M
0.0091
0.0197
0.0231
0.0286
0.0333
0.0417
(cP)
6.4356
5.2738
4.106
3.1309
2.4914
7.4455
K2Cr 2O7
Conc./M
0.005
0.006
0.007
0.008
0.009
0.01
0.02
(cP)
7.0379
6.7356
6.0204
4.7773
6.3348
8.2346
8.7092
Table (4).
Log of the coefficient of the viscosity of black liquor (50% solid content)
containing different salts (0.009 M) versus 1/T
1/T(K-1)
TBL
K2Cr2O7
KMnO4
KSCN
KBr
0.003195
0.003096
4.196
3.6718
3.3838
2.9718
3.3981
3.0612
3.3497
2.9394
3.4053
3.0866
0.003003
3.1643
2.5924
2.6518
2.5571
2.6646
0.002915
2.7558
2.2404
2.353
2.2592
2.2129
0.002833
2.3436
1.8491
1.9584
1.8618
1.9489
12
KMnO4
10
K2Cr2O7
Viscosity/cP
KSCN
KBr
0
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
0.16
Salt Concentration/M
Fig. 3. Plot of the coefficient of the viscosity of black liqour (50% solid content)
at 353 K versus different concentrations of salt.
The effect of salt concentration on the

viscosity value of the black liquor was also
investigated. In this context, some commonly
used salts such as KBr, KSCN, K2Cr2O7 and
KMnO4 were selected. These salts have been
tried for reducing the viscosities of the black
liquor obtained from other sources [13]. In this
study it was shown that the viscosity of the
black liquor generally decreased with the
addition of these salts when added upto a
certain concentration. The trend is depicted in
Figure 4. It can be seen from this figure that
the viscosity decreases to a minimum value
(around 70-80% change), with increasing
amounts of different alkali salts. The lowest

viscosity was observed for ~0.011 mol.L-1 of
KBr, 0.008 mol.L-1 of K2Cr2O7, 0.003 mol.L-1
of KSCN and 0.120 mol.L-1 of KMnO4
respectively. This behavior can be explained
using the rationale that addition of ions in the
form of salts to an aqueous solution tends to
change
the
number
of
water-lignin
interactions. Some large and weakly polarized
ions e.g. the potassium ion, referred to as
structure breakers [16] may hinder the
formation of water-lignin hydrogen bonds. At
low concentration, the solubility of a charged
macromolecule increases due to Debye-Hckel
55
viscosity of the black liquor from ~10 cP

(50 % w/v solid content at 80C) to ~2.5 cP
for <0.1 M of salt concentration as evident
from Table 4.
electrostatic effects [17]. For example, if the

molecule is a polyanion (as in the case of the
lignin molecule formed as a result of its deprotonation) the cation from the added salt will
cluster around the negative charges on the
polymer. This effective charge neutralization
may possibly decrease the intermolecular Hbonding [18] resulting in a reduction in the
viscosity. The salt-induced change in water
structure may become particularly important at
a certain optimum salt concentration, because
one or more solute molecules are required to
be present at all the polyanion sites within the
lignin macromolecules. At this concentration,
the solubility is affected and a substantial
change in solution viscosity may occur [19]. In
order to optimize the viscosity reduction, the
proper anion must be paired with the cation.
The four anions i.e. bromide, permanganate,
dichromate and thiocyanate have been
compared. KCN, KBr and KMnO4 reduce the
CONCLUSION
Thick black liquor (TBL) obtained during the

processing of Kahu grass in a Kraft process
was investigated with respect to its viscosity
behaviour. The studies revealed that the
viscosity values were substantially affected
(greater than 60%) by the addition of some
salts like KBr, KSCN, KMnO4 and K2Cr2O7.
The results are explained in terms of a
decrease in intermolecular H-bonding present
in solution, by these salts.
4.5
KBr
K2Cr2O7
KMnO4
KSCN
3.5
l
n
2.5
1.5
0.5
0
0.0028
0.00285
0.0029
0.00295
0.003
0.00305
0.0031
0.00315
0.0032
0.00325
1/T (K)
Fig. 4. Plot of the n of the coefficient of the viscosity of the black

liquor (50% solid content) containing different salts versus 1/T.
56
REFERENCES
1.
K. Niemela and R. Alen, In: Analytical

Methods in Wood Chemistry, Pulping
and Paper Making, E. Sjostrom and E.
Alen (eds), Springer, Berlin (1999).
10.
J. P. Casey, Pulp and Paper: Chemistry

and Chemical Technology, 3rd ed;
Wiley-Interscience, USA (1981).
11.
F. C. Klaessing and J. F. Donald,

U.S. Patent No. 4, 255, 309 (1981).
2.
J. Small and A. Fricke, Ind. Eng.

Chem. Prod. Res. Dev. 24, 608 (1985).
12.
R. K. Jain and A. T. Gupta, Ind. Paper

and Pulp Tech. Assoc. 5(3), 107 (1993).
3.
J. Louhelainen, R. Alen, J. Zielinski and

P. E. Sagfors, J. Pulp Pap. Sci. 28(9),
285 (2002).
13.
R. J. Spontak, J. E. Roberts, V. A.
Prevysh and S. A. Khan, U.S. Patent No.
5, 635, 027 (1997).
4.
M. Boone, Tappi Kraft Recovery

Operations Short Course 93 (1991).
14.
5.
P. Ramamurthy, A. Mujumdar, A. Van

Heiningen and G. Kubes, TAPPI
195-202 (1992).
A. Fricke, Physical properties of Kraft

black liquor, Summary report-Phases I
and II. DOE report no. DOE/CE/40606T5 (DE 88002991)(1987).
15.
L. Soderhjelm, Paperi ja Puu. 70(4),

354 (1988).
M. O. Wight, A. Co and A. L. Fricke,

AIChE Symp.Series 77(207), 9 (1981).
16.
D. Balzer, Langmuir 9, 3375 (1993).
17.
M. Mandel, Chemistry and Technology

of Water Soluble Polymers, Chapter 10,
Plenum Press, New York, USA (1983).
6.
7.
E. Milanova and G. M. Dorris, J. Pulp

Paper Sci. 16(3), 94 (1990).
8.
R. Ryham, Intl. Chem. Recovery Conf.

Proc. 581 (1992).
18.
L. Soderhjelm, 8thAnnual Appita Conf.

41, 299 (1987).
D. Voet and J. Voet, Biochemistry, John

Wiley and Sons, New York, USA (1990).
19.
I. Robb, Chemistry and Technology of

Water Soluble Polymer (edited by
C.A.Finch), Plenum Press, New York,
USA (1983).
9.
57
DESIGN, SYNTHESIS AND BIOLOGICAL

EVALUATION OF NOVEL CARBAPENEMS
G.H. Hakimelahi1, A.A. Moosavi-Movahedi2, A.A. Saboury3,
V. Osetrov4, G.A. Khodarahmi5 and K.-S. Shia6
1,2,3
Institute of Biochemistry and Biophysics, University of Tehran, Tehran, Iran

E-mail: hosein@chem.sinica.edu.tw
1,4
Institutes of Chemistry and Biomedical Sciences, Academia Sinica, Taipei 115,
Taiwan, Republic of China
1,5
Department of Medicinal Chemistry, Faculty of Pharmacy, Isfahan University of
Medical Sciences, Isfahan, Iran
6
Division of Biotechnology and Pharmaceutical Research, National Health Research
Institutes, Taipei 114, Taiwan, Republic of China
Keywords: Carbapenem, -lactam, antibiotic.
ABSTRACT
Racemic trans-3-hydroxycarbonyl-6-(phenylacetamido)carbapenem 13 and trans-3-phosphono-6(phenylacetamido)carbapenem 17 were synthesized. Formation of the carbapenem nuclei in 13
involved an internal Wittig reaction of the corresponding monocyclic -lactam 10 using NaH in
THF. The key step in the transformation of carbapenam 15 to 3-phosphonocarbapenem 17
involved either a decarboxylative-bromination reaction and subsequent elimination or a
bromination reaction followed by decarboxylative-elimination. Carbapenem 13 was found to
possess antibacterial activity, comparable with imipenem (+)-3, against Staphylococcus aureus
FDA 209P, S. aureus 95, Escherichia coli ATCC 39188, Klebsiella pneumoniae NCTC 418,
Pseudomonas aeruginosa 1101-75, P. aeruginosa 18S-H, and Xanthomonas maltophilia GN
12873.
Like imipenem ((+)-3), carbapenem 13 was not stable to X. maltophilia
oxyiminocephalosporinase type II. Its phosphonate analog 17, however, was neither a significant
antibacterial agent nor a good -lactamase inhibitor.
INTRODUCTION
Penicillins (i.e., penicillin G ((+)-1)) exert a

certain biological activity by acylating serine
residues of transpeptidases, where the crosslinking of peptidoglycans does not take place
[1,2]. Bacteria become resistant to antibiotics
either through genetic mutations or by
acquiring resistant genes from other bacteria
[3]. The rapid development and spread of
mechanisms of bacterial resistance however,
are making virtually all -lactam antibiotics
obsolete [3]. The main cause of bacterial
_____________________________________
resistance to -lactam antibiotics is the

-lactamases,
which
are
related
in
evolutionary terms to transpeptidases [4].
Bacteria may synthesize the -lactamase in the
presence of frequently used antibiotics. Thus,
to overcome the destructive action of an
inducible -lactamase, the structure of the lactam may be altered to become insensitive to
hydrolysis by the -lactamase while
maintaining its potency as an antibiotic [5].
As such, generations of penicillins were
developed [6].
*Present mailing address: TaiGen Biotechnology, 138 Shin Ming Rd., Taipei, Taiwan 114
E-mail: hosein@taigenbiotech.com.tw; hosseinhakimelahi@canada.com
59
of penicillin G ((+)-1); the B-ring therein is

identical to that of imipenem ((+)-3)).
Carbapenems 46 exhibited imipenem-like
antibacterial activity and penicillin G-like
-lactamase inhibitory property. We hypothesized that the antibacterial spectrum of 46
may have its origin in the structural features of
the B-ring [5]. Their -lactamase inhibitory
property, however, may have resulted from the
feature of the A-ring and its C-6 substituent
with a cis configuration. However, it is not
clear whether the 6-(phenylacetamido)-side
chain or its cis configuration in carbapenems
46 is essential for their stability towards
-lactamase CXaseII.
Carbapenems, as a new generation of

penicillins, were introduced by the discovery
of thienamycin ((+)-2) [7-9] (Figure 1).
Subsequently, many carbapenem derivatives
(i.e., imipenem ((+)-3)) [10-14] have been
prepared. The side chain at the C-6 position
of most carbapenems possesses the trans
configuration to the pyrroline nucleus, but the
C-6 substituted in penicillins has a cis
configuration to the 1,3-azathiolane nucleus.
A few years ago, we synthesized carbapenems
()-46 [5] (Figure 1), which share the basic
carbapenem nucleus with imipenem, but differ
in the stereoconfiguration of the side chain at
the C-6 position. Unlike imipenem, which has
a trans configuration at the C-5 and C-6
positions, those carbapenems possess a cis
configuration like penicillin G ((+)-1).
Herein we report the synthesis of trans-3hydroxycarbonyl-6-(phenylacetamido)-carbapenem ()-13 that has antibacterial activity
similar to that of imipenem ((+)-3)) and cis-6(phenylacetamido)carbapenems 46. A key
finding of this work is that unlike 46, but like
(+)-3, this new compound was found to be
sensitive to CXase-II. We also synthesized
trans-3-phosphono-6-(phenylacetamido)carbapenem ()-17, which neither showed
significant inhibitory property toward CXase-II
nor exhibited significant antibacterial activity.
Xanthomonas maltophilia produces oxyiminocephalosporinases type I (CXase-I) and type II

(CXase-II) [5]. Unlike other carbapenems
[15]
(e.g.,
imipenem
((+)-3)),
cis(phenylacetamido)carbapenems 46 were
found to be resistant to CXase II [5]
Interestingly, penicillin G ((+)-1) also
exhibited significant stability towards
-lactamase CXaseII.
The A-ring in
carbapenems 46 is structurally similar to that
OH
H
PhH2COCHN
Me
S(CH2)2NH2
O
CO2H
CO2H
Penicillin G (+)-1
Thienamycin (+)-2
OH
PhH2COCHN
Me
5
3
CO2H
Imipenem (+)-3
IUPAC Numbering System
N
1
1
6
(CH2)2NHCH=NH
B
N
4
O
CO2H
()-4 R = H
()-5 R = CO2H
()-6 R = CO2Me
Conventional Numbering System
Fig. 1. Chemical Structures of Penicillin G as well as trans- and cis-Carbapenems.
60
-lactam 9 in 90% yield [19]. Compound 9

was then transformed to the ketone 10 (77%
yield) by use of mercuric trifluoroacetate and
mercuric oxide in ethyl acetate [20]. Sodium
borohydride reduction of 10 in methanol
afforded
(2-hydroxy-2-phenylethyl)azetidinone 11 in 70% yield. By using sodium
hydride in tetrahydrofurane, we accomplished
the cyclization of monocyclic -lactam 10 to
bicyclic -lactam 12 in 75% yield [21].
Finally, removal of the tert-butyl group by use
of silica gel-supported trifluoroacetic acid in
methylene chloride was achieved to afford
carbapenem ()-13 in 40% yield.
RESULTS
Synthesis of Carbapenem ()-13 (Figure 2).
Racemic tert-butyl
2-amino-2-dimethylphosphonoacetate (7) [16] was treated with
phenylpropargyl aldehyde to produce the
corresponding Schiff base, which upon
reaction with azidoacetyl chloride in
methylene chloride gave azido--lactam 8 in
40% overall yield. The coupling constant
(2.0 Hz) of the two hydrogen atoms on the
-lactam ring indicated the trans relationship
of the two substituents [17,18]. The azide
group in 8 was reduced by H2S and Et3N, and
the resultant amine was acylated with
phenylacetyl chloride to 3-(phenylacetamido)-
Bu t O 2 C
R2
PO(OMe)2
NH 2
R1
a
(40% )
N
PO(OMe)2
()-7
Bu t O 2 C
8 R1 = C
CPh, R 2 = N 3
9 R1 = C
(77% )
CPh, R 2 = NHCOCH 2 Ph
(70%)
10 R 1 = CH 2 COPh, R 2 = NHCOCH 2 Ph
11 R 1 = CH 2 CH(OH)Ph, R 2 = NHCOCH 2 Ph
(90%)
PhH 2 COCHN
e
(75% )
Ph
N
O
CO 2 R 3
12 R 3 = Bu t
(40% )
a Reagents:
(a) 1. PhC
()-13 R 3 = H
CCHO, 2. N 3 CH 2 COCl, Et 3 N; (b) 1. H 2 S, Et3 N, 2. PhCH 2 COCl, pyridine;
(c) (CF 3 CO 2 )2 Hg, HgO, H 2 O; (d) NaBH 4 , MeOH; (e) NaH, THF; (f) CF 3 CO 2 H/silica gel.
Fig. 2. Synthesis of carbapenem 13 .
61
carbonate and bromine; note that the C2C3

double bond formation in 16 may occur either
by bromination of the 2-position in 15,
followed by
decarboxylative-elimination
reaction
or
through
decarboxylativebromination of the 3-position in 15, followed
by an elimination reaction (for the proposed
mechanisms see Figure 4).
Dimethyl
phosphonate 16 was then reacted with
trimethylsilyl bromide in methylene chloride
to produce the target phosphono-carbapenem
()-17 in 40% yield [22].
Synthesis of 3-Phosphonocarbapenem
()-17 (Figure 3). For the preparation of
carbapenem 17, the diastereoisomeric
-lactam 11 was treated with methanesulfonyl
chloride
in
the
presence
of
1,8diazabicyclo[5.4.0]undec-7-ene (DBU) in
CH2Cl2 to produce carbapenam 14 in 80%
yield. Compound 14 was subsequently treated
with trifluoroacetic acid/silica gel to give acid
15 in 60% yield. Conversion of carbapenam
15 to carbapenem 16 (20% yield) was
accomplished using alumina-supported potassium
PhH2COCHN
CH2CH(OH)Ph
PhH2COCHN
a
(80%)
Ph
N
PO(OMe)2
(MeO)2OP
ButO2C
CO2R4
14 R4 = But
()-11
(60%)
15 R4 = H
PhH2COCHN
c
(20%)
Ph
N
O
PO(OR5)2
16 R5 = Me
(40%)
aReagents:
()-17 R5 = H
(a) MeSO2Cl, DBU, CH2Cl2; (b) CF3CO2H/silica gel; (c) K2CO3/Al2O3 /Br2, CH2Cl2;
(d) Me3SiBr, CH2Cl2.
Fig. 3. Synthesis of carbapenem 17 .
62
Decarboxylative-bromination
Base
PhH 2COCHN
PhH 2 COCHN
Ph
N
O
Br
Br
O
(MeO)2 OP
C
O
Base
(MeO)2OP
Br
15
Elimination
Bromination
PhH 2 COCHN
PhH 2 COCHN
Br
Ph
N
O
Ph
Ph
N
H
(MeO)2OP
Base
16
PO(OMe)2
O
Decarboxylative-elimination
Fig. 4. Proposed mechanisms for the conversion of carbapenam 15 to carbapenem 16.
Biological Activities.
The screening
experiments in vitro for the antibacterial
activity of the carbapenems ()-13 and ()-17
were carried out as described [23,24].
Penicillin G (+)-1 and imipenem (+)-3 were
used as reference compounds. The results are
summarized in Table 1.
Minimum inhibitory concentration was also

determined for the newly synthesized trans
carbapenem 13 in combination (1:1 w/w) with
cis carbapenem 6 against X. maltophilia GN
12873. The value (g/mL), expressed as

mean standard error from two independent
determinations, was 2.87 0.36.
Moreover, we tested the -lactamase
inhibitory property of the carbapenems ()-13
and ()-17 [25]. Penicillin G (+)-1 and
imipenem (+)-3 were also used in vitro as
reference compounds.
The results are
63
Table (1). Minimum inhibitory concentrationsa (MIC, g/mL) of carbapenems ()-46,

()-13, ()-17 as well as the reference compounds (+)-1 and (+)-3 against
microorganisms.
S. aureus
-lactam
FDA
209P
(+)-1
(+)-3
()-4
()-5
()-6
()-13
()-17
0.28
0.01
0.13
0.02
0.01
0.06
70
E. coli K. pneumoniae
95b,c
> 128
12.9
32
12
8.0
14
> 128
ATCC
39188
NCTC 418
2.97
0.45
0.99
0.50
0.24
1.1
> 128
> 128
0.4
1.8
0.49
0.17
0.60
82
P. aeruginosa
1101-75
18S-Hb
> 128
3.6
9.0
5.4
0.82
3.0
60
> 128
36
31
27
11
28
100
X. maltophiliad
GN 12873
> 128
> 128
10
8.9
13
> 128
> 128
aThe lowest concentrations of antibiotics needed for the prevention of visible growth of microorganisms,
reported as the average values of triplicate determinations (standard errors for the compounds with MIC less
than 36 g/mL are in the range of 0.00 1.75). MIC values were obtained by use of an agar dilution method
whereby organisms were deposited onto medicated agar plates by the replication device of Steers et al. [24].
b-Lactamase-producing organism. cMethicillin-resistant organism. dOxyiminocephalosporinases type I
and type II-producing organism.
Table (2). Minimum protective concentrationsa (MPC, g/mL) of carbapenems ()-46,

()-13, ()-17 as well as the reference compounds (+)-1 and (+)-3 against
-Lactamases.
-lactamase of
Compoundb
S. aureus
95
P. aeruginosa
18S-H
(+)-1
(+)-3
()-4c
()-5c
()-6c
()-13
()-17
2.12
28.95
3.45
2.20
0.98
20.98
95.7
1.20
30.21
4.21
2.38
1.02
23.06
75.76
-lactamase of X. maltophilia
GN 12873
CXase-I
CXase-II
25.22
42.17
29.98
25.50
14.61
35.42
85.87
30.04
056
33.64
29.43
16.73
1.04
48.61
aThe average values of duplicate determinations (standard errors are in the range of 0.01
7.44) for
the ability of compounds to inhibit the hydrolysis of 3-[E-(2,4-dinitro)styryl]-(6R,7R)-7-(2thienylacetamido)-3-cephem-4-carboxylic acid by -lactamases from S. aureus 95, P. aeruginosa
18S-H, and X. maltophilia GN 12873. MPC values, determined by the procedure of O'Callaghan
et al. [25] are the lowest concentrations of -lactams needed to protect the indicator from hydrolysis by
-lactamases under standard test conditions within 1.0 h. The hydrolysis of indicator was evidenced
by a distinct red color. bAll compounds were stable (> 15 h) in the absence of -lactamases at 37 C in
a phosphate buffer solution (pH 7.0). cData are taken from reference 5.
64
DISCUSSION
-Lactamases catalyze the hydrolysis of
-lactam antibiotics, deactivating them. These
enzymes are behind the most widespread
resistance mechanism to drugs of the
penicillin family (i.e., penicillin G ((+)-1))
[26]. Imipenem ((+)-3) is stable to most
-lactamases [27] yet highly susceptible to
CXase II (Table 2). Consequently, it did not
show activity against X. maltophilia (see
Table 1). In contrast to imipenem ((+)-3), cis6-(phenylacetamidio)carbapenems ()-46 are
much more stable to CXase II (see Table 2).
As such, they showed notable activity against
X. maltophilia (Table 1).
Unlike cis
carbapenems ()-46, the newly synthesized
trans-6-(phenylacetamidio)carbapenem ()-13
was found not to be stable to CXase II (see
Table 2). Thus, it did not exhibit significant
activity against X. maltophilia (Table 1).
Apart from X. maltophilia, the activity of

trans-6-(phenylacetamidio)carbapenem ()-13
against Staphylococcus aureus FDA 209P, S.
aureus 95, Escherichia coli ATCC 39188,
Klebsiella
pneumoniae
NCTC
418,
Pseudomonas aeruginosa 1101-75, and P.
aeruginosa 18S-H is similar to those of
carbapenems ()-46 and imipenem ((+)-3), as
shown in Table 1.
Thus, the common
carbapenem nucleus in these compounds play
a prominent role in their antibacterial
activities. On the other hand, the -lactamase
inhibitory property of trans carbapenem
()-13 is more comparable with that of
imipenem ((+)-3), and the -lactamase
inhibitory property of cis carbapenems ()-46
is very similar to that of penicillin G ((+)-1),
indicating that the stereoconfiguration of the
-lactam ring junction is more vital than the
nature of C-6 substituent for -lactamase
inhibition (see Table 2).
Unlike trans
carbapenems
(+)-3
and
()-13,
cis
carbapenems ()-46 reduced the ability of
CXase II to destroy the -lactam nucleus.
Similarly, penicillin G ((+)-1) appears to be
stable to the enzyme, yet it is not active
against X. maltophilia. This may be due to the
impermeability of the outer membrane of X.
maltophilia to penicillin G ((+)-1) relative to
carbapenems ()-46 [28,29].
-Lactam antibiotics (e.g., carbapenems) exert

certain biological activity by acylating serine
residues of transpeptidases [1,2]. As such,
recognition of a -lactam by the active site of
penicillin-binding proteins (i.e., transpeptidases or -lactamases) is essential for
-lactamases
antibacterial
activity
or
inhibitory
property.
Unlike
trans-3hydroxycarbonyl-6-(phenylacetamido)carbapenem ()-13, trans-3-phosphono-6-(phenylacetamido)carbapenem ()-17 did not exhibit
either significant antibacterial activity or
-lactamases inhibitory property against
pathogenic microorganisms. Therefore, the
presence of a carboxylate functionality at the
3-position of carbapenems is apparently
important for their recognition by the
penicillin-binding proteins.
The -lactamase inhibitory property of trans

carbapenem 13 against CXase II allowed it to
exert a large synergistic effect on the
antibacterial agent cis carbapenem 6. Thus, a
1:1 mixture of ()-13 with ()-6 exhibited
notable activity against X. maltophilia GN
12873. There is no doubt however, that there
would be a difference in the penetration
capability of these two independent moving
molecules, cis carbapenem 6 and trans
carbapenem 13, towards the periplasmcontaining -lactamase. If, even partially,
hydrolytic destruction of the antibiotic 6
occurs prior to that of the -lactamase
inhibitor 13, then the inhibitor cannot induce
complete synergistic effect on the antibiotic.
Consequently, a change in strategy for the
killing of resistant bacteria that makes the lactamase is needed. This may include the
inhibition of the -lactamase (i.e., Cxase II)
just prior to the acylation of the
transpeptidase. This would be the next step in
this area based on our findings. The complete
results will be published elsewhere.
CONCLUSIONS
Two new carbapenems were synthesized by

chemical methods and their structureactivity
relationship was explored. These compounds
include trans-3-hydroxycarbonyl-6-(phenylacetamido)carbapenem ()- 13 and trans-3phosphono-6-(phenylacetamido)carbapenem
()- 17 .
65
Results from the biological tests indicate that

unlike cis-3-hydroxycarbonyl-6-(phenylacetamido)carbapenems ()-46, the carbapenem
()-13 was not stable to X. maltophilia
oxyiminocephalosporinase type II (CXase-II).
Thus, it did not show notable activity against
X. maltophilia. However, this newly synthesized
carbapenem was found to be active against S.
aureus FDA 209P, E. coli ATCC 39188, K.
pneumoniae NCTC 418, P. aeruginosa 110175 as well as the -lactamase producing
organism P. aeruginosa 18S-H and
methicillin-resistant organism S. aureus 95.
On the other hand, trans-3-phosphono-6(phenylacetamido)carbapenem ()-17 was
found not to be a significant antibacterial
agent or a -lactamase inhibitor. A mixture of
cis carbapenem 6 and trans carbapenem 13 in
a ratio of 1:1(w/w) was found to possess
notable activity against X. maltophilia GN
12873 in vitro.
Work on the chemical
combination of -lactamase inhibitors (i.e.,
trans carbapenem 13) and -lactam antibiotics
(i.e., cis carbapenem 6) is in progress. The
complete results will be reported in the future.
EXPERIMENTAL
General. For anhydrous reactions, glassware
was dried overnight in an oven at 120 C and
cooled in a desiccator over anhydrous CaSO4
or silica gel. Reagents were purchased from
Sigma (St. Louis, USA) or Fluka
(Switzerland). Solvents, including dry ether
and tetrahydrofuran (THF), were obtained by
distillation from the sodium ketyl of
benzophenone under nitrogen. Other solvents,
including chloroform, dichloromethane, ethyl
acetate, and hexanes were distilled over CaH2
under nitrogen.
Absolute methanol and
ethanol were purchased from Merck
(Germany) and used as received.
Melting points were obtained with a Bchi

510 melting point apparatus. Infrared (IR)
spectra were recorded on a Beckman IR-8
spectrophotometer. The wavenumbers reported
are referenced to the 1601 cm1 absorption of
polystyrene. NMR spectra were obtained on a
Varian XL-300 (300 MHz) spectrometer.
DMSO-d6, D2O, or CDCl3 was used as
solvent; Me4Si ( 0.00 ppm) was used as an
internal standard. All NMR chemical shifts
are reported as values in parts per million
(ppm) and coupling constants (J) are given in
66
hertz (Hz). The splitting pattern abbreviations

are as follows: s, singlet; d, doublet; t, triplet;
q, quartet; br, broad; m, unresolved multiplet
due to the field strength of the instrument; and
dd, doublet of doublets. Microanalyses were
performed on a PerkinElmer 240-B
microanalyzer.
Purification refers to gravity column
chromatography on a Merck Silica Gel 60
(particle size 230400 mesh). Analytical TLC
was performed on precoated plates purchased
from Merck (Silica Gel 60 F254). Compounds
were visualized by use of UV light I2 vapor, or
2.5% phosphomolybdic acid in ethanol with
heating.
Preparation of Silica Gel-Supported
Trifluoroacetic Acid (CF3CO2H/SiO2).
While shaking, to neutal silica gel (10 g,
Merck Kieselgel 60, particle size 0.0630.200
mm, 70-230 mesh) CF3CO2H (6.0 mL) was
added, dropwise. The mixture was shaken
under reduced pressure (0.1 torr) for 1.0 h to
give a white powder, which contained 25%
(by weight) of CF3CO2H. This reagent was
found active for at least 2 months by storage in
a well-capped bottle.
Preparation of
Alumina-Supported
Potassium Carbonate (K2CO3/Al2O3).
Aluminium oxide (10 g, activated, basic,
Brockmann I, 150 mesh) was mixed with a
solution of K2CO3 (1.6 g) in water (5.0 mL).
Evaporation of water under reduced pressure
(0.1 torr) for 7.0 h gave a dry white powder,
which contained 15% (by weight) of K2CO3.
This reagent was found active for more than 6
months by storage in a well-capped bottle.
Tert-Butyl 2-(trans-3-Azido-2-oxo-4-phenylethynyl-1-azetidinyl)-2 dimethylphosphonoacetate (8). To a solution of tert-butyl 2amino-2-dimethylphosphonoacetate (7, 2.4 g,
0.01 mol) in dry CH2Cl2 (50 mL) was added
phenylpropargyl aldehyde (1.3 g, 0.01 mol)
and MgSO4 (25 g). After stirring at 25 C for
6 h, the mixture was filtered, Et3N (1.01 g,
0.01 mol) was added, followed by dropwise
addition of N3CH2COCl (1.2 g, 0.01 mol) at
25 C. After stirring for 2 h, the solution was
washed with H2O (2 x 50 mL), dried (MgSO4),
and evaporated to give the crude -lactam,
which was purified by use of column
chromatography on silica gel. Elution with
CH2Cl2 gave 1.74 g (40% yield) of the oily
azido -lactam 8 as a mixture of two

1
diastereoisomers. H-NMR (CDCl3): 1.51
(2 s, 9 H, C(Me)3), 3.583.98 (m, 6 H, 2
OMe), 4.63 (d, J = 18.0 Hz, 1 H, CHP), 4.78
(d, J = 2.0 Hz, 1 H, HC(4)), 4.90 (d, J = 2.0
Hz, 1 H, HC(3)), 7.317.47 (m, 5 H, Ph).
IR (CH2Cl2): 2225 (CC), 2100 (N3), 1773
(-lactam), 1742 (ester) cm1. MS: 406
+
+
+
(M - N2), 377 (M - C(Me)3), 351 (M - N3CH=
+
C=O), 265 (M - PhCCCH=CHN3). CI-MS:
+
+
435 (M + 1), 378 (M + 1 - (CMe)3). Anal.
calcd for C19H23N4O6P (434.38): C, 52.53; H,
5.34; N, 12.90. Found: C, 52.60; H, 5.35; N,
12.82.
Tert-Butyl 2-(trans-2-Oxo-3-phenylaceta-mido4-p h e n y l e t h y n y l -1-azetidinyl)-2-dimethylphosphonoacetate (9). H2S was bubbled
for 45 min into a solution of 8 (4.34 g, 0.01
mol) in CH2Cl2 (100 mL) and Et3N (1.20 g,
0.012 mol) at 0 C. The stirred solution was
allowed to warm-up to 25 C. After 1 h, N2
gas was bubbled into the solution for 30 min.
Then, pyridine (1.58 g, 0.02 mol) was added
followed by dropwise addition of phenylacetyl
chloride (1.55 g, 0.01 mol). After 1 h, the
solution was washed with H2O (3 x 100 mL)
and brine (80 mL). Then, it was treated with a
mixture of MgSO4 (20 g) and charcoal (20 g).
Filtration and evaporation followed by
purification by flash chromatography on silica
gel (AcOEt/hexane 3:7 as eluant) afforded
1
4.74 g (90% yield) of 9 as a foam. H-NMR
(CDCl3): 1.49 (2 s, 9 H, C(Me)3), 3.50 (br.s,
2 H, CH2CO), 3.68, 3.99 (2 d, J = 12.0 Hz, 6
H, 2 OMe), 4.75 (d, J = 20.0 Hz, 1 H, CHP),
4.86 (d, J = 2.5 Hz, 1 H, HC(4)), 5.06 (dd, J
= 8.0, 2.5 Hz, 1 H, H-C(3)), 6.36 (d, J = 8.0
Hz, 1 H, NH), 7.22 (s, 5 H, Ph), 7.317.46 (m,
5 H, CCPh). IR (CH2Cl2): 3410 (NH), 1774
(-lactam), 1740 (ester), 1680 (amide) cm1.
Anal. calcd for C27H31N2O7P (526.56): C,
61.59; H, 5.93; N, 5.32. Found: C, 61.63; H,
5.82; N, 5.40.
Tert-Butyl 2-(trans-2-Oxo-3-phenylaceta-mido-4phenacyl-1-azetidinyl)-2-dimethyl-phosphonoacetate (10). A mixture of 9 (0.50 g, 0.95
mmol), HgO (0.50 g, 2.34 mmol), and
(CF3CO2)2Hg (0.99 g, 2.34 mmol) in AcOEt
(40 mL) containing H2O (0.5 mL) was stirred
at 25 C for 5 h. The mixture was then cooled
to 0C and H2S was bubbled through for 10
min. After stirring at 25C for 30 min, HgS
was removed by filtration and the solvent was

evaporated. Purification by use of flash
chromatography on silica gel (AcOEt/hexane
3:7 as eluant) gave 0.40 g (77% yield) of 10 as
1
a foam. H-NMR (CDCl3): 1.48 (2 s, 9 H,
C(Me)3), 3.58 (d, J = 7.0 Hz, 2 H, CH2COPh),
3.60 (s, 2 H, CH2CO), 3.69, 4.00 (2 d, J = 12.0
Hz, 6 H, 2 OMe), 4.35 (dt, J = 7.0, 2.5 Hz,
1 H, H-C(4)), 4.73 (br.d, J = 22.0 Hz, 1 H,
CHP), 4.89 (dd, J = 6.8, 2.5 Hz, 1 H, H-C(3)),
6.25 (d, J = 6.8 Hz, 1 H, NH), 7.257.78 (m,
10 H, 2 Ph). IR (CH2Cl2): 3350 (NH), 1772
(-lactam), 1745 (ester), 1680, 1682 (amide,
ketone) cm1. Anal. calcd for C27H33N2O8P
(544.57): C, 59.55; H, 6.11; N, 5.14. Found:
C, 59.67; H, 6.18; N, 5.32.
Tert-Butyl 2-[trans-4-(2-Hydroxy-2-phenylethyl)-2-oxo-3-phenylacetamido-1-azetidinyl]-2-dimethylphosphonoacetate (11). To
a solution of 10 (0.54 g, 0.99 mmol) in
methanol (20 mL) NaBH4 (0.076 g, 2.0 mmol)
was added at 0 C. After stirring at 25C for
1.5 h, phosphate buffer solution (NaH2PO4,
pH 5.33, 20 mL) was added. The solution was
extracted with AcOEt (45 mL) and washed
with H2O (40 mL). The organic layer was
dried (MgSO4), evaporated, and the residue
was purified by use of flash chromatography
(AcOEt/hexane 4:6 as eluant) to afford 0.46 g
1
(86% yield) of 11 as an oil.
H-NMR
(CDCl3): 1.46 (2 s, 9 H, C(Me)3), 1.98 (ddd,
J = 15.0, 9.5, 3.4, Hz, 1 H, HC-C(4)), 2.24
(ddd, J = 15.0, 10.0, 4.8 Hz, 1 H, HC-C(4)),
3.20 (d, J = 5.2 Hz, 1 H, OH, exchanged with
D2O), 3.56 (br.s, 2 H, CH2CO), 3.58, 3.98
(2 d, J = 12.5 Hz, 6 H, 2 OMe), 4.18 (ddd, J =
9.5, 4.8, 2.2 Hz, 1 H, H-C(4)), 4.66 (d, J =
20.0 Hz, 1 H, CHP), 4.72 (dd, J = 7.0, 2.2 Hz,
1 H, H-C(3)), 4.94 (ddd, J = 10.0, 5.2, 3.4 Hz,
1 H, PhCHO), 6.45 (d, J = 7.0 Hz, 1 H, NH),
7.15, 7.26 (2 br.s, 10 H, 2 Ph). IR (CH2Cl2):
3395 (OH), 3310 (NH), 1770 (-lactam), 1740
(ester), 1670 (amide) cm1. Anal. calcd for
C27H35N2O8P (546.59): C, 59.33; H, 6.45; N,
5.12. Found: C, 59.41; H, 6.50; N, 5.18.
Tert-Butyl (5RS, 6SR)-7-Oxo-6-(phenylacetamido)-3-phenyl-1-azabicyclo[3.2.0]hept-2ene-2-carboxylate (12). To a solution of 10
(0.54 g, 0.99 mmol) in dry THF (20 mL) at
-30C NaH (0.024 g, 1.0 mmol) was added.
The solution was stirred for 1 h at the same
temperature, and then for a further 2 h at 25C.
The reaction mixture was quenched with
67
aqueous NH4Cl-solution (3%, 15 mL),

extracted with ether, dried (MgSO4), and
evaporated
under
reduced
pressure.
Chromatography of the residue on silica gel
(CH2Cl2/CHCl3 8:2 as eluant) afforded 0.30 g
1
(75% yield) of 12 as an oil.
H-NMR
(CDCl3): 1.56 (s, 9 H, C(Me)3), 3.38 (dd,
J = 18.0, 7.5 Hz, 1 H, H-C(4)), 3.58 (dd,
J = 18.0, 10.0 Hz, 1 H, H-C(4)), 3.60 (s, 2 H,
CH2CO), 3.99 (ddd, J = 10.0, 7.5, 2.0 Hz, 1 H,
H-C(5)), 5.01 (dd, J = 8.0, 2.0 Hz, 1 H,
H-C(6)), 6.38 (d, J = 8.0 Hz, 1 H, NH), 7.25
(s, 5 H, Ph), 7.56 (m, 5 H, Ph). IR (CH2Cl2):
3410 (NH), 1790 ( -lactam), 1745
(ester), 1700 (C=C), 1680 (amide) cm1. MS:
+
243 (M -P h C H 2 C O N H C H = C = O ) , 186
+
(M -PhCH2CONHCH=C=O-C(Me)3). CI-MS: 419
+
(M +1). Anal. calcd for C25H26N2O4 (418.49):
C, 71.75; H, 6.26; N, 6.69. Found: C, 71.53;
H, 6.38; N, 6.88.
(5RS, 6SR)-7-Oxo-6-(phenylacetamido)3-phenyl-1-azabicyclo[3.2.0]hept-2-ene-2carboxylic Acid (13). To CF3CO2H/silica
gel (2.50 g), a solution of 12 (0.40 g, 0.96
mmol) in CH2Cl3 (8 mL) was added. After 15
h stirring at 25C, the solid material was
filtered and washed with CH2Cl2 (3 x 15 mL).
The combined filtrate and washings were
evaporated to afford a crude foam.
Chromatography on silica gel (AcOEt as
eluant) gave 0.14 g (40% yield) of 13, mp
1
127-129C. H-NMR (CDCl3/DMSO-d6/D2O):
3.36 (dd, J = 17.0, 7.6 Hz, 1 H, H-C(4)),
3.56 (dd, J = 17.0, 10.0 Hz, 1 H, H-C(4)), 3.59
(s, 2 H, CH2CO), 3.97 (ddd, J = 10.0, 7.6, 2.2
Hz, 1 H, HC(5)), 5.03 (d, J = 2.2 Hz, 1 H,
H-C(6)), 7.30 (s, 5 H, Ph), 7.51 (m, 5 H, Ph).
IR (CH2Cl2): 33003420 (OH, NH), 1786
(-lactam), 1710, 1696 (C=O, C=C), 1670
(amide) cm1. Anal. calcd for C22H18N2O4
(362.38): C, 69.60; H, 5.01; N, 7.73. Found:
C, 69.38; H, 5.18; N, 7.89.
Tert-Butyl (2RS, 3RS, 5RS, 6SR)-7-Oxo-6(phenylacetamido)-3-phenyl-2-dimethylp h os p h on o -1-azabicyclo[3.2.0]heptane2-carboxylate (14). To a solution of 11 (0.55
g, 1.0 mmol) in CH2Cl2 (20 mL) containing
DBU (0.48 g, 3.10 mmol) methanesulfonyl
chloride (0.35 g, 3.0 mmol) was added dropwise
at 0C. After stirring for 1 h at 25C and 4 h
at reflux temperature, it was washed with H2O
(2 x 50 mL), dried (MgSO4), and evaporated.
Chromatography of the residue on silica gel
68
(CHCl3/AcOEt 1:0.5 as eluant) gave 0.42 g

1
(80% yield) of 14 as a foam.
H-NMR
(CDCl3): 1.47 (2 s, 9 H, C(Me)3), 2.29 (ddd,
J = 13.0, 6.0, 5.5 Hz, 1 H, H-C(4)), 2.41 (ddd,
J = 13.5, 13.0, 9.5 Hz 1 H, H-C(4)), 3.45, 3.82
(2 d, J = 11.0 Hz, 6 H, 2 OMe), 3.58 (br.s,
2 H, CH2CO), 3.98 (ddd, J = 9.5, 5.5, 2.2 Hz,
1 H, H-C(5)), 4.47 (dd, J = 13.5, 6.0 Hz, 1 H,
H-C(3)), 5.13 (dd, J = 7.5, 2.2 Hz, 1 H,
H-C(6)), 6.29 (d, J = 7.5 Hz, 1 H, NH), 6.857.30 (m, 10 H, 2 Ph). IR (CH2Cl2): 3360
(NH), 1784 (-lactam), 1745 (ester), 1670
(amide) cm1. Anal. calcd for C27H33N2O7P
(528.57): C, 61.35; H, 6.29; N, 5.30. Found:
C, 61.42; H, 6.33; N, 5.41.
(2RS, 3RS, 5RS, 6SR)-7-Oxo-6-(phenylacetamido)-3-phenyl-2-dimethyl-phosphono-1azabicyclo[3.2.0]heptane-2-carboxylic Acid
(15). Compound 15 was obtained from 14 in
60% yield as described for the conversion of
12 13, except that for purification a mixture
of AcOEt/MeOH 9:1 was used as eluant. M.p.
1
94-96C.
H-NMR (CDCl3/D2O): 2.23
(ddd, J = 13.0, 6.0, 5.5 Hz, 1 H, H-C(4)), 2.36
(ddd, J = 13.5, 13.0, 9.6 Hz, 1 H, H-C(4)),
3.48, 3.95 (2 d, J = 12.0 Hz, 6 H, 2 OMe),
3.50 (br.s, 2 H, CH2CO), 3.88 (ddd, J = 9.6,
5.5, 2.3 Hz, 1 H, H-C(5)), 4.39 (dd, J = 13.5,
6.0 Hz, 1 H, H-C(3)), 5.08 (br.d, J = 2.3 Hz, 1
H, H-C(6)), 6.90-7.25 (m, 10 H, 2 Ph). IR
(CH2Cl2):
3300-3410 (NH, OH), 1782
(-lactam), 1710 (acid), 1676 (amide) cm1.
Dimethyl (5RS, 6SR)-7-Oxo-6-(phenylacetamido)-3-phenyl-1-azabicyclo[3.2.0]hept2-ene-2-phosphonate (16). To a solution of
15 (0.47 g, 0.99 mmol) in CH2Cl2 (10 mL)
containing Br2 (0.32 g, 2.0 mmol)
K2CO3/Al2O3 (6.0 g) was added at 25C. The
reaction mixture was stirred at the same
temperature for 24 h. Filtration, evaporation,
and purification of the residue by use of silica
gel (CHCl3 as eluant) afforded 16 (0.09 g,
1
20% yield) as a foam. H-NMR (CDCl3/D2O):
3.33 (dd, J = 16.0, 7.4 Hz, 1 H, H-C(4)),
3.60 (dd, J = 16.0, 10.0 Hz, 1 H, H-C(4)), 3.57
(s, 2 H, CH2CO), 3.69, 3.94 (2 d, J = 11.0 Hz,
6 H, 2 OMe), 3.99 (ddd, J = 10.0, 7.4, 2.0 Hz,
1 H, H-C(5)), 5.03 (d, J = 2.0 Hz, 1 H,
H-C(6)), 7.24 (s, 5 H, Ph), 7.47 (m, 5 H, Ph).
IR (CH2Cl2): 3425 (NH), 1786 (-lactam),
1695 (C=C), 1678 (amide) cm1. CI-MS: 427
+
(M +1).
(5RS, 6SR)-7-Oxo-6-(phenylacetamido)3-phenyl-1-azabicyclo[3 . 2 . 0 ]hept-2-ene2-phosphonic Acid (17). To a solution of 16

(0.43 g, 1.0 mmol) in CH2Cl2 (15 mL) was
added trimethylsilyl bromide (0.46 g, 3.0
mmol). After stirring at 25C for 5 h, a
mixture of MeOH and H2O (5:1, 15 mL) was
added. Evaporation and purification of the
residue by chromatography on silica gel
(AcOEt as eluant) gave 0.16 g (40% yield) of
1
17. Mp 118-119C. H NMR (CDCl3/
DMSO/D2O): 3.30 (dd, J = 16.5, 7.7 Hz,
1 H, H-C(4)), 3.58 (dd, J = 16.5, 9.4 Hz, 1 H,
H-C(4)), 3.55 (s, 2 H, CH2CO), 3.97 (ddd, J =
9.4, 7.7, 1.8 Hz, 1 H, H-C(5)), 5.05 (d, J = 1.8
Hz, 1 H, H-C(6)), 7.20 (s, 5 H, Ph), 7.46 (m,
5 H, Ph). IR (nujol): 33003460 (NH, 2 OH),
1782 (-lactam), 1690 (C=C), 1675 (amide)
+
cm1. CI-MS: 399 (M +1).
Antibacterial Activity Test.
The agar
dilution method was used to study the
antibiotic activity [23,24]. The inocula were
prepared by use of the heart infusion broth
(Difco Laboratories) to make 104 dilutions of
the overnight cultures. Tubes of the seeded
antibiotic-containing media were incubated at
37C for 20 h. The lowest concentration of
antibiotic that prevented visible growth of
microorganisms
was
then
determined
(Table 1).
-Lactamase Inhibitory Property Test.
To solutions of phosphate buffer (3 mL, 0.05
M,
pH
7.0)
containing
3-[E-(2,4dinitro)styryl]-(6R,7R)-7-(2-thienylacetamido)
-3-cephem-4-carboxylic acid (52.0 g) and
different concentrations of the tested
-lactams, individually, 0.04-1.2 units of
-lactamases from S. aureus 95, P. aeruginosa
18S-H, and X. maltophilia GN 12873 were
added at 37C. The lowest concentrations of
-lactams needed to protect the indicator from
hydrolysis by -lactamases, within 1.0 h, were
then determined by the procedure of
O'Callaghan
et al. [25].
Results are
ACKNOWLEDGEMENT
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SYNTHESIS AND CHARACTERIZATION OF SOME

NEW HETEROCYCLIC TELLURIUM(IV)
DITHIOCARBAMATE COMPLEXES
A. Z. Al-Rubaie1 and M. Y. Al-Luaibi2
1
Department of Chemistry, College Science, Gerian University,

Gerian P.O. Box 64200, Libya
E-mail: alrubaie49@yahoo.com
1,2
Department of Chemistry, College of Science, University of Basrah, Basrah, Iraq
Keywords: Tellurium (IV), dialkyldithiocarbamates, heterocycle, tellurides.
ABSTRACT
The heterocyclic tellurium(IV)-dithiocarbamate complexes of general formula C4H8Te(S2CNR1R2)2,
C8H8Te(S2CNR1R2)2,
C 1 0 H 1 2 Te (S 2 CNR 1 R 2 ) 2 , C 8 H 8 Te(C H 3 ) (S 2 CNR 1 R 2 ) and
C10H12Te(CH3)(S2CNR1R2) (where R1 = R2 = CH3, R1 = R2 = C2H5 and R1 = H, R2 = CH2CH2CH2Br)
have been prepared by reacting diiodo and iodo heterocyclic tellurium compounds with sodium
dialkyldithiocarbamate salts. The new complexes were characterized by elemental analyses, IR,
NMR, mass spectra and conductance measurements. In all complexes, the dithiocarbamate ligands
showed bidentate behaviour.
INTRODUCTION
Many complexes of dithiocarbamate with dand p-block metal ions have been prepared
[1,2,3,4],
while
the
corresponding
organotellurium type complexes have been
reported much less [5,6,7,8]. Tellurium(IV)
dithiocarbamate complexes have been used as
accelerators in rubber vulcanization [9] and as
stabilizers for polypropylene [10].
Organotellurium(IV)-dithiocarbamate complexes
have been the targets for several structural
studies.
The tris-substituted species, is
exemplified by PhTe(S2CNEt2)3, which involves
a distorted pentagonal bipyramidal structure
[8], (two of the dithiocarbamates are bidentate
International Journal of Scientific Research,Vol. 14, 2005
and one is anisobidentate). In the bis-substituted

species, such as Me 2 Te(S 2 CNEt 2 ) 2 [11],
Ph2Te(S2CNEt2)2 [12] and C8H8Te(S2CNEt2)2
[13] both, bidentate and anisobidentate ligands
have been found but not in the same molecule
[13].
As an extension of our previous work on the
synthesis and spectral investigations of new
organotellurium compounds [14,15,16,17], we
report in this paper, the synthesis of new
heterocyclic-tellurium(IV)-dithio-carbamate
complexes and investigate the composition and
properties of these new complexes. Figure 1
gives the new Tellurium(IV)-dithiocarbamate
structures and numbers used in this paper.
71
S
Te
S
R1
R
Te
2
S
S
N
R1
S
R
1
R1
R2
R2
4: R1=R2= CH3; 5: R1=R2 = C2H5; 6: R1= CH2CH2CH2Br; R2= H.
H3C
Te
H3C
R1
N
S
CH3
H3C
Te
N
R1
H3C
R2
10
CH3
CH3
CH3
Te
S
S
N
11
CH3
CH3
Fig. 1. New heterocyclic tellurium-dithiocarbamate structures.
72
EXPERIMENTAL
a) Physical measurements
The IR spectra were recorded in the range
4000-200 cm-1 on a Pye-Unicam SP3-300
spectrometer using KBr discs. 1H and 13C
NMR spectra were measured on a Brucker
MW-250 at 250 MHz or on a Varian VXR200 (200 MHz) with TMS as internal
reference.
Mass spectra of the complexes were measured
at 70 eV with a MAT-1125 Finnigan mass
spectrometer; the peaks shown relate to 130Te.
Microanalyses for carbon, hydrogen and
nitrogen were carried out on a Perkin-Elmer
240B elemental analyzer or on a CHN CorderMT3-Yanaca. Conductivity
data were
measured with a WTW conductivity meter
LBR, using a standard conductivity cell with
cell constant of 0.81 cm-1. Melting points
were measured by a Gallenkamp melting point
apparatus and are uncorrected.
b) Synthesis
1,1-Diiodo-1-telluracyclopentane [17], 2,2diiodo-1,3-dihydro-2-telluraindene [18], 2,2diiodo-5,6-dimethyl-1,3-dihydro-2 telluraindene
[19], and 2-iodo-2,5,6-trimethyl-1,3-dihydro2-telluraindene [19] were prepared as
previously described. Sodium dithiocarbamate
ligands were prepared by the reaction of the
corresponding amine with carbon disulphide
(mole ratio 2:1) in sodium hydroxide and
ethanol media according to a general literature
method [20,21]. The products were purified
by recrystallization and verified by their
melting points, IR and elemental analysis.
The complexes 1,1-bis(dimethyldithio-carbamato)1-telluracyclopentane(1),1,1-bis-(diethyldithiocarbamato)-1-telluracyclopentane (2),1,1-bis((3bromopropyl)dithiocarbamato)-1-telluracyclopentane(3), 2,2-bis(dimethyldithiocarbamato)1,3-dihydro-2-telluraindene(4) 2,2-bis(diethyldithiocarbamato)-1,3-dihydro-2-telluraindene(5),
2,2-bis((3-bromopropyl) dithiocarbamato)1,3-dihydro-2-telluraindene(6), 2,2-bis(dimethyldithiocarbamato)-5,6-di-methyl-1,3-dihydro2-telluraindene( 7 ), 2,2-bis(diethyldithiocarbamato)-5,6-dimethyl-1,3-dihy dro-2telluraindene(8) and 2,2-bis(3-bromopropyl)dithiocarbamato)-5,6-dimethyl-1,3-dihydro-2-
telluraindene (9) were prepared by the

following general method and as described for
the preparation of complex 7:
2,2-bis(dimethyldithiocarbamato)-5,6-dimethyl-1,3-dihydro-2-telluraindene(7).
2,2-Diiodo-5,6-dimethyl-1,3-dihydro-2-telluraindene (0.15 g; 1 mmol) in dichloromethane

(30 ml) was mixed with a solution of sodium
dimethyldithiocarbamate (0.29 g; 2 mmol) in
dry ethanol (20 ml). The mixture was stirred
under nitrogen for 3 h, after which the solvent
was removed under reduced pressure.
Dichloromethane was added to the residue
with vigorous stirring, filtered to remove
sodium iodide and then the solvent was
removed. Methanol (10 ml) was added to the
product with stirring and filtered. The crude
product was recrystallized from ethanol to
give pale yellow crystals.
2-Diethyldithiocarbamato-2,5,6-trimethyl1,3-dihydro-2-telluraindene (10).
This compound was prepared by the following

method:
To a solution of 2-iodo-2,5,6-trimethyl-1,3dihydro-2-telluraindene (1.21 g; 3 mmol) in
dichloromethane was added (with stirring
under nitrogen), a solution of sodium
diethyldithiocarbamate (0.53 g; 3 mmol) in
methanol (30 ml) at room temperature. The
stirring was continued for 1 h, after which the
solvent was removed by evaporation. The
product was treated with dichloromethane and
filtered to remove sodium iodide. Removal of
solvent and recrystallization from ethanol gave
a pale yellow precipitate.
2-Dimethyldithiocarbamato-2-methyl-1,3dihydro-2-telluraindene (11).
This compound was prepared by a procedure

identical to that for 10 by using 2-iodo-2methyl-1,3-dihydro-2-telluraindene (1.12 g;
3 mmol) and sodium dimethyldithiocarbamate
(0.43 g; 3 mmol). A pale yellow precipitate
was obtained in good yield.
Physical and analytical data for compounds
1-11 are presented in Table 1. Figure 1 gives
the new tellurium(IV)-dithiocarbamate structures.
73
Table (1). Analytical and physical properties of the new complexes 1 11.
Compound
Yield (%)
M.p. (oC)
Analysisa (%)
C
57
112-114
28.15
(28.32)
4.62
(4.75)
6.37
(6.60)
5.25
72
96-97
35.24
(35.02)
5.67
(5.87)
5.75
(5.83)
6.47
65
100-102
23.46
(23.63)
3.22
(3.63)
4.28
(4.59)
5.75
70
143-145
35.46
(35.61)
4.25
(4.27)
5.67
(5.93)
4.33
68
144-146
40.96
(40.92)
5.13
(5.34)
5.29
(5.30)
4.75
54
131-133
29.62
(29.20)
3.81
(3.37)
3.68
(4.26)
5.22
86
156-158
38.22
(38.41)
4.65
(4.83)
5.32
(5.60)
5.58
84
142
43.32
(43.18)
5.54
(5.79)
4.86
(5.03)
6.35
59
129
31.41
(31.51)
3.34
(3.82)
4.28
(4.08)
6.85
10
62
138
45.42
(45.15)
5.96
(5.64)
3.31
(3.42)
29.5
11
71
153
39.27
(39.17)
4.67
(4.58)
3.82
(3.71)
28.7
Calculated values are in parentheses.
Isolated yields, melting points and analytical

data for the newly synthesized complexes
listed in Table 1, indicate the formation of 1:2
complexes (i.e. 1-9) and 1:1 complexes (i.e. 10
and 11), Figure 1. All the resulting complexes
are pale yellow solids and soluble in common
organic solvents.
74
Mb
(-1 cm2 mol-1)
10-3 M DMSO solution.
The most important IR peaks of the complexes

are listed in Table 2. The presence of a single
and strong band due to a (CSS) mode in the
range 965-1015 cm-1 in the spectra of all
complexes is strongly indicative of bidentate
behavior of the dithiocarbamate ligands in the
complexes [11,22]; otherwise a doublet is
expected in the region 1000 70 cm-1 in the
case of monodentate type coordination
[23,22,24].
The position of the (C=N) mode, in the range

1470-1540 cm-1, gives further conformation of
the above suggested behaviour; this band
undergoes a blue shift in all complexes
compared with the free ligands [25]. The IR
spectra for all complexes showed new bands
of relatively medium intensity in the regions,
340-360 cm-1 and 290-320 cm-1 assigned to
symmetrical and unsymmetrical (Te-S),
respectively [21]. Furthermore, the (Te-C)
mode occurred in the region 525-550 cm-1
which agrees well with previous work
[19,22]. In complexes 3, 6 and 9 a band of
medium intensity was observed around 3150
cm-1, which can be attributed to (N-H) of the
corresponding 3-bromo-propyldithiocarbamate
ligand.
10 and 11 the expected ratios of the aromatic

to aliphatic protons were observed. The
methylene protons (1 and 3) appear as singlets
for the 1:2 complexes (i.e. 5, 7, 8 and 9), Table 2.
In the case of complexes 10 and 11, the
presence of a methyl group on the tellurium
atom clearly destroys the equivalence of the
two protons within the methylene group, and
changes the methylene spectrum to a simple
AB pattern.
The coupling constant
2
J1a1b (= 2J2a2b) is ~14Hz, a value consistent
with an sp3 hybridized carbon atom [17,19],
Table 2.
The 13C spectra of complexes 4, 5, 7 and 8

were recorded in a solution of CDCl3 at room
temperature, and only one dithio 13C resonance
(i.e. S2C-) is observed at around 195 ppm as
well as only one signal for the cyclic
methylene adjacent to tellurium at ~ 40.0 ppm,
Table 3. Each methyl and methylene carbon
atoms of the dithiocarbamate give a single
resonance. Thus, it may be concluded that the
two dithicarbamate ligands in each complex
are equivalent [11,12,13].
The molar conductance values for complexes

1-9 in DMSO at room temperature lie between
4-7 ohm-1 cm2 mol-1, which indicates that
these are non-electrolytes while complexes 10
and 11 are 1:1 electrolyte [26], as seen in
Figure 2 and Table 1.
Some representative 1H NMR data are given in
Table 2. In the spectra of complexes 5, 8, 9,
11
100
Molar conductance
Molar conductance
10
80
60
40
20
0
0
0.02
0.04
(Concentration)
0.06
1/2
0.08
120
100
80
60
40
20
0
0
0.02
0.04
(Concentration)
0.06
0.08
1/2
Fig. 2. Plot of molar conductance ( M ; -1 cm2 mol-1) versus (concentration)1/2

for complexes 10 and 11 in DMSO solution.
75
Table (2). IR and 1H NMR spectral data for the complexes 1-11.
IR (cm 1)
Compound
H NMR( ppm vs. TMS)
1470s, 970s, 550w, 360s, 310m
1480s, 980s, 540w, 340m, 299m.
3150s, 1430s, 995s, 530w, 360m, 310m.
1485s, 965s, 535w, 360m, 290w-m.
1485s, 985s, 525w, 355m, 295m.
3160m,1435s, 1005s, 525w, 360s, 305m.
1490s, 975s, 540w, 340m, 300m.
2.23(CH3, s, 6H); 3.43(CH3, s, 12H);

4.48(Te-CH2, s, 4H); 6.95(Ar-H, s, 2H).
1490s, 980s, 530w, 360w, 310w.
3160s, 1440s, 1015s, 530w, 355m,

295m.
1.19(CH3, t, 12H); 2.16(CH3, s, 6H);

3.83(CH2, q, 8H); 4.16(Te-CH2, s, 4H);
6.97(Ar-H, s, 2H).
2.16(CH3, s, 6H); 2.23(CH2, p, 2H);
2.99(CH2, t, 2H) 3.48(Te-CH2, q, 4H);
5.26(NH, s, 1H); 7.05(Ar-H, s, 2H).
10
1482s, 985s, 540m, 360m, 320m.
1.58(CH3, t, 6H); 2.93(CH2, q, 4H);

2.17(CH3, s, 6H); 4.01(Te-CH2, q, 4H, J=
14.6 Hz); 7.05(Ar-H, s, 2H).
11
1485s, 1010s, 535m, 355m, 310m.
2.13(CH3, s, 6H);
3.45(CH3, s, 6H);
4.08(Te-CH2, q, 4H); 7.12(Ar-H, s, 4H).
1.21(CH3, t, 12H); 3.90(CH2, q, 8H);

4.45(Te-CH2, 4H); 7.11(Ar-H, s, 4H).
Table (3). Carbon-13 NMR data for selected complexes in CDCl3*.

Complex
(13C(1))
(13C(2))
(13C(3))
(13C(4))
(13C(5))
40.1
136.2
124.8
127.9
34.9, 193.4
40.3
136.7
125.8
128.7
9.5, 35.7, 192.7
40.8
135.2
129.6
137.1
18.7
9.5, 195.7
41.7
134.9
130.1
137.0
18.7
9.3, 45.4, 194.6
Other (13C)
* Carbon assignment as illustrated below:
3
4
2 CNR
5
H 3C
Te
76
8H 8
Te(S
CNR
2)2
CNR
Te
S
CNR
H 3C
10
12
Te(S
2 CNR
2 CNR
2)2
The mass spectra of 5 and 8 show reductive

elimination of the disulphide, Et2N.C(S)SS(S)C.NEt2, from the parent compound. The
disulphide shows a fragmentation pattern
similar to that shown by disulphide
compounds [27,28], and may be represented as
follows:
[Et 2 N.C(S)S S(S)C.NEt 2 ]+
+H
-R,
[Et 2 N.C(S)S - H]+ -SH
[Et 2 N.CS]
-S
[Et 2 NCS]
All the above ions are seen in the spectra. No

metastable ion was observed to support the
above fragmentation pattern. The molecular
ion peak is absent and the highest ion peak
observed at m/z 426 which corresponds to
Te[S2C.NEt2]2+. The base peak is associated
with the ion [Et2N.CS]2+. Other fragments
such as TeS2CNEt2+, C10H12Te+, C8H8Te+,
C10H12+, C8H8+, C9H9+, Ph+ and CS+ were also
observed.
CONCLUSIONS
A new series of heterocyclic tellurium(IV)dithiocarbamates were prepared and

characterized.
In all compounds, the
dithiocarbamate ligands show bidentate
behaviour.
ACKNOWLEDGEMENT
The authors thank Professor S. Uemura, Kyoto

University, Japan, and Professor N. Al-Masoudi,
Konstnz University, Germany, for providing
some CHN analyses, NMR and mass spectra.
REFERENCES
1. C. Preti, G. Tosi and A. Zannini, J. Molec.

Struct. 65, 283-292 (1986).
2. T. Ning, G. Xinmin, Z. Hailianc and
T. Minyu, Polyhedron 9, 859-862 (1990).
3. M. Ali, W. R. McWhinnie, A. A. West
and T. Hamor, J. Chem. Soc., Dalton
Trans. 899-906 (1990).
4. W. Zhang, Y. Zhong, M. Tan, N. Tang
and K. Yu, Molecules 8, 411-417 (2003).
5. N. I. Al-Salim, A. A. West and W. R.

McWhinnie, J. Chem. Soc. Dalton Trans.
2363-2371 (1988).
6. S. Huseby, In Proceeding of Fourth
International Conference on the Organic
Chemistry of Selenium and Tellurium,
Berry, J., and McWhinnie, W.R., (eds),
University of Aston in Birmingham,
298-369 (1983).
7. J. E. Dreak and M. L. Y. Wong,
J. Organomet. Chem. 377, 43-49 (1989).
8. S. Husebye, Phosphorous, Sulphur and
Silicone 136-138, 377-395 (1998).
9. A. K. Singh and Basumatary, J. Organomet.
Chem. 364, 73-77 (1989).
10. M. A. K. Ahmed, S. S. Ali, W. R.
McWhinnie and G. Scott, J. Appl. Poly.
Sci. 32, 4857-4864 (1986).
11. D. Dakternieks, R. DiGiacomo, R. W.
Gable and B. F. Hoskin, J. Am. Chem.
Soc. 110, 6762-6768 (1988).
12. D. Dakternieks, S. Huseby, R. DiGiacomo,
R. W. Gable and B. F. Hoskin, J. Organomet.
Chem. 349, 305-314 (1988).
13. D. Dakternieks, S. Huseby, R. DiGiacomo,
R. W. Gable and B. F. Hoskin,
J. Organomet. Chem. 353, 35-43 (1992).
14. A. Z. Al-Rubaie and A. F. Hassian,
Polyhedron 11, 3155-3157 (1992).
15. A. Z. Al-Rubaie, N. I. Al-Salim and
S. A. N. Al-Jaddan, J. Organomet. Chem.
443, 67-70 (1993).
16. A. Z. Al-Rubaie, A. M. Finggan, N. I. AlSalim and S. A. N. Al-Jaddan, Polyhedron
15, 2575-2581 (1995).
17. A. Z. Al-Rubaie, H. Al-Shirryda, P. Granger and
S. Chapelle, J. Organomet. Chem. 287,
321-327 (1985).
18. A. Z. Al-Rubaie, W. R. McWhinnie,
P. Granger and S. Chapelle, J. Organomet.
Chem. 234, 287-292 (1982).
77
19. A. Z. Al-Rubaie and E. A. Al-Masoudi,

Heteroatom Chem. 2, 417-425 (1992).
25. C. OConnor, J. D. Gilbert and G. Wilkinson,

J. Chem. Soc. A 84-86 (1969).
20. W. Walter and K. D. Bode, Angew. Chem.

79, 285-298 (1967).
26. W. J. Greay, Coord. Chem. Rev. 7, 81-122

(1971).
21. M. A. K. Ahmed, W. R. McWhinnie and

P. Granger, Polyhedron 5, 859-862 (1986).
27. F. Takami, S. Wakhara and T. Maeda,

Tetrahedron Lett. 12, 2645-2648 (1971).
22. T. N. Sirvastava
and V. Kumar,
J. Organomet. Chem. 107, 55-61 (1976).
28. V. Garcia-Montalvo, A. R.-Toscano,

A. Badillo-Delgado and R. Cea-Olivares,
Polyhedron 20, 203-208 (2001).
23. F. Bonati and R. Ugo, J. Organomet. Chem.

10, 257-268 (1967).
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1571-1585 (1952).
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78
Int. J. Sci. Res.,Vol. 14 (2005), pp. 79-81
JORDAN LAID BARE

Robin Harte1 and Cora Stack2
1
School of Mathematics, Trinity College, Dublin, Republic of Ireland

E-mail: rharte@maths.tcd.ie
2
Department of Mathematics, Institute of Technology, Tallaght, Republic of Ireland
E-mail: cora.stack@it-tallaght.ie
Supported by Enterprise Ireland Basic Research Grant SC/2002/0266
ABSTRACT
The dark secret of the Jordan decomposition is that nilpotent matrices break into exact
and zero components.
Suppose T : X X is a linear operator on a

real or complex vector space: then an
invariant subspace for T satisfies T(Y)
Y X. The trivial invariant subspaces are
O = {0} and X. Among the invariant subspaces
of T we shall identify its platforms:
1. Definition: A platform for the linear
operator T:XX is a maximal linear subspace
XX for which
T-1(0)XT(X)X.
S (0) T(X).
1.2
When an operator is nilpotent then its

platforms also reduce, in the sense that they
admit invariant complements:
2. Theorem: If T : XX is nilpotent, in the
2
sense that T = 0, and if XX is a platform for
T, then there is XX for which
T(X) X ; XX = O; X + X = X.
T-1(0)XT(X) and XT-1(0).
2.2
Proof. The first part of this is given by

Herstein [4] Lemma 6.5.4): look at XX
which is maximal with respect to the first two
conditions of (2.1) and claim that there is
implication
Tx X + X x X + X.
Indeed it is clear that

1.1
Zorns condition is easily checked for XX

which satisfy (1.1), so that platforms exist. For
example O is always a platform, and the whole
space X is a platform for T i (T,T) is exact,
where (S,T) is exact i
-1
There is inclusion
2.1
Tx = y + z X + X 0 = T x = Ty + Tz
Tz = -Ty XX= O
giving y = Ty with yX by the platform
property (1.1): now consider the subspace
W = X + K(x-y).
We note that TW W, since T(x-y)X, and
claim that
xX + X XW = O.
To see this argue
z + (x-y) X x X +X X
X+X = 0 z XX = O.
The maximality of X thus forces X+X = X.
Towards (2.2), the first part is just the platform
property (1.1), while the second follows from
maximality: if there were z X for which
Tz 0 then X + Kz would also satisfy (1.1)
79
3. Theorem : If T : XY and S : YZ
satisfy ST = 0 : XZ then there are XX and
In the situation of (2.1) we can write
T 0
:
T ~
0 T
Y,YY for which
X
~ X X
X
with (T,T) exact and T = 0.
2.3
YY = Y.
We can be more explicit: if we take

X1 = T(X) and T(X2) = X1 with
T-1(0)X2 = O and (X1 + X2) X3 = X
S-1(0)YTXY and Y S-1(0) with
Proof. If we write
2.4
R = T
0
then X = X1 + X2 is a platform for T with

invariant complement X = X3.
To be even more explicit, take a Hamel basis
for X1 = T(X) of the form T(e), and then take
X2 to be the space with basis e; with a basis
for the space X3 we have a representation for
vectors xX
x = x1 . (Te) + x2 .e + x3 .
= j x1jT(ej) + j x2j ej + kx3k k .
2.5
With respect to this basis we find, provided we

have arranged for X3 to be T-invariant, the
traditional Jordan form:
0 I 0
T ~ 0 0 0 .
0 0 0
3.1
2.6
0 0
0 0 : WW =
S 0
X

Y
Z

3.2
then we have
2
ST = 0 : XZR = 0 : WW ;
3.3
also
T 1 (0)
0
R(W) = T ( X ) and R-1(0)= S 1 (0) . 3.4

Z
S (Y )
By (2.2) there are R-invariant subspaces W

and W, with direct sum W, for which
R-1(0)WR(W) and WR-1(0). Writing
them in terms of subspaces of X, Y and Z, this
gives X = XX and Y = YY with
When more generally T = 0 for some k 3

then (2.3) and (2.4) become more elaborate: if
3
for example T = 0 we find a decomposition
X = X1X2X3X4 into invariant subspaces
X = X1 + X2 + X3 and X = X4 for which
2
T-1(0)XT (X), equivalently

T-2(0)XT(X), with XT-2(0) :
2.7
the analysis of the induced operator

T:XX is then given by Theorem 2.
Notice how the greater degree of ambiguity on
the complementary space X is compensated
for by a heightened degree [3] of exactness on
the platform. We can try to be clever, and do
all these powers at the same time, and more;
the trick [1] is to reduce a product ST = 0 to an
operator with square zero:
80
T-1(0)X = O ; XT-1(0);
S-1(0)YTXY ; YS-1(0)
More explicitly, if we write W = W1W2W3
as in (2.3) then we have
W 1 = T ( X ) ; W2 =
S (Y )
X2

Y2 ; W3 =
O

X3

Y3
Z
3
with
T(X2) = T(X) with T-1(0)X2 = {0}
and X3 T-1(0)
3.5
and
S(Y2) = S(Y) with S-1(0)Y2 = {0}
and Y3S-1(0)
3.6
S-1(0)(TX + Y2) T(X2) Y2 .
3.7
precisely when the pair (T,T) is exact in the

sense (1.2). Dierent possibilities for the
Jordan form of T thus oer a subdivision of
the Taylor spectrum of the original system of
operators.
and
REFERENCES
1. R. E. Harte, Proc. Royal Irish Acad. 81A,

71-79 (1981).
If in particular T = SU = US : XX = Y = Z
this gives
S-1(0)(TX+Y2 ) T(X2) Y2 with
X3 T-1(0) .
3.8
Theorem 2 applies when the operator

T : XX is derived [1] from the Koszul
complex of a commuting system of operators
on a Banach space: 0Cn is outside the
Taylor spectrum of the commuting system
2. R. E. Harte, Invertibility and Singularity,

Dekker (1988).
3. R. E. Harte, Proc. Amer. Math. Soc. 119,
793-801 (1993).
4. I. N. Herstein, Topics in Algebra, Wiley
(1975).
81
CONVEX RANDOM INTEGRAL FUNCTIONALS

AND EPICONVERGENCE
K. Messaoudi1, M. L. Leghmizi2 and M. Zerguine3
1,3
Universit de Batna, Facult des Sciences,

Dpartement de Mathmatiques, 05000 Batna, Algeria
2
Centre Universitaire de Mdia, Dpartement de Mathmatiques, Algeria
Keywords: Random integral functionals, epiconvergence, ergodic theory, AMS (1991).

49J45, 60Fxx, 60G10, 73B27.
ABSTRACT
The limit analysis, by epiconvergence technics, of a sequence of convex random integral
functionals is studied by an easy and new approach. The almost sure epilimit is found, by using the
subadditive ergodic theorem, by [3]. An example of such functionals and their epilimit is given.
The main result of our paper, generalizes the one obtained by [4] in the determinist case and
confirm the one presented by [7,8], in connection with the compactness method.
x, convex in a and satisfies the following

p-growth conditions in a
1. INTRODUCTION
Let be the class of the integral functionals

G : Lp(A) x Ob {+} of the form
g(x,u(x))dx if uW 1, p(A);
G(u, A)=A
+ if uLp(A) \W 1, p(A),
A is any element of the set Ob of all open
bounded regular subsets of the Euclidien space
d, d*. For 1<p<+ and A in Ob, Lp(A) and
W1,p(A) denote respectively the Lebesgue and
the sobolev spaces, equipped with their usual
(x
norms,u = u ,...,u is the vector valued

1
xd
weak derivatives and the integrand g:(x,a)

a g(x,a) from dd into + is measurable in
|a|pg(x,a) (1+|a|p),
(1)
and are two given real positive constants,

and |.| denotes the norm in d.
In this paper, we deal with the asymptotic

behavior as n0; n, of the following
sequence of the random integral functionals
obtained by action on the random function
F() in , of the homothety operator of factor
n (see Sec.3).
(*) Fn( )(u, A)= A
f ( )( x ,u(x))dx if uW 1, p (A);
if uLp (A) \W 1, p (A).
83
The element which is present in () is given

in the fixed probability space (,,P), and will
describe the random distribution of
heterogeneities in the medium. Following the
same pattern as our paper [12], we are able:
(a) To characterize via an ergodic theorem
by [3], the integrand fhom(a) of the expected
epilimit. We will show in Sec.3, corollary 3.3
that for every a in d and P-a.e.
f hom(a )= inf
nN *
meas(nY )
min f()(x,a+u(x))dxdP() ,
uW01, p(nY) nY
Y=]0,1[ , meas(nY) denotes the Lebesgue

measure of nY and W 10, p (nY) is the closed
subspace of
W 1, p (nY ) of the functions with
null trace on the boundary (nY ) of nY.

(b) To demonstrate in sec.4, theorems 4.1
that the integral functional Fhom(u,A) whose the
integrand is fhom(a) will represent the epilimit
of () for the strong topology of Lp(A).
(c) As a consequence of variational
properties of epiconvergence, we will prove in
sec.4, corollary 4.2 the convergence of the
minima.
(d) To give in Sec.5 an example where ()
can be interpreted as the energy of a dielectric
medium in A, subjected to the electric
potential u, whose structure is an n-cubical
lattice with cells occupied by two different
materials with dielectric constants and ,
chosen independently by a Bernoulli's law.
Note that there is very important recent works
in this field. For further details, we
recommend the reader to consult the
references, [1,2], [13-19].
2. VARIATIONAL PROPERTIES OF
EPICONVERGENCE
Let (X,) be a Banach space, and let {Fn, F,

n} be a family of functionals mapping X
into {+}. Let us recall the following
notion of convergence, witch is called
epiconvergence or in its general setting convergence. For an overview about
epiconvergence, we refer the reader to [4,6].
84
Definition 2.1. We say that the sequence

(Fn)n -epiconvergences to F at x in X iff the
two following sentences hold:
(i) There exists a sequence (xn)n of (X,)

-converging to x such that,
F(x) lim sup Fn(xn).
n +
(ii) For every sequence (xn)n, converging to x in X,

F(x) lim inf Fn(xn).
n +
When this property holds for every x in X, Fn

is said to be -convergent to F in X, and we
write F=-epilimitFn. We state now the
variational properties of epiconvergence, see
for instance [4].
Proposition 2.1. Assume that, (F n ) epiconverges to F, and let H be a -continuous
functional from X into . Then
(i) -epilim it(Fn+H)=F+H.
(ii) If now (xn)n is a sequence in (X,)

such that, Fn(xn)Fn(x)+n where n>0, and if
furthermore (xn)n is -relatively compact.
Then any cluster point x of (xn)n is a
minimizer of F and
liminf Fn (x )., xX =min{F(x )., xX }= F x .
n +
()
3. PRELIMINARY RESULTS
For every zd and every r*+, we shall

need to define in the class , the two
following operators z and r
z G(u, A)=G( z u, z + A)= g(x+ z,u(x))dx;

A
r G(u, A)=G(r u,rA)= g( x ,u(x))dx;
r
where zu(x)=u(x-z), ru(x)= 1 u(rx) and
r
rA={rx/ xA}.
A
Let ( ) be the smallest -field on such

that all the evaluation maps FF(u,A),
uLp(A), AOb are ( ( ) , ({+}))
measurable, where ({+}) denotes the
Borel -field of {+}. We define for every
u in Lp(A) and for every A in Ob the (, ( ) )
measurable map F by:
f ( )(x,u(x))dx if uW 1, p (A);
F( )(u, A)= A
+
otherwise.
tG(u a +la,A)+(1t)G(u b +lb,A),

so
a
b
A (G,ta+(1-t)b)G(tu +(1-t)u +tla+
Let =P o F-1 be the probability image of F

such that the previous family (z)zd on the
probability space (,( ), ) , is an ergodic
group of -preserving transformations, that is
to say:
(a) z is ( ) -measurable;
(b) o z(E)=(E), for every E in ( )
and every z in d;
(c) z o t=z+t, -z=z-1, for every z and t
d
in ;
(d) (E){0,1} for every set E in ( )
such that z(E)=z+E=E for every z in d
(ergodicity).
On the other hand, from (1) we have

m(a)(1+|a|p. Therefore m(.) is convex and
finite, thus it is continuous and then
subdifferential. According to [4]
m(a)-m(b)m(a),(a-b)|m(a)||ab|C(1+|a|p-1)|a-b|C(1+|a|p-1+|b|p-1)|a-b|,
where m(a) denotes the subdifferential of the
function m at the point a. When we put b in
place of a, we obtain the result.
Let I be the set of all intervals [a,b[ where a

and b belong to d. Let us now define for
every a in d, for every A in I and for every G
in ,
A G, A=min G u +la , A , uA ,
where la is a linear function whose gradient is
a. Then we have:
(i) is subadditive, that is, for every AI

such that there exists a finite family (Ai)iI
of disjoint sets in A, whose union A, then
Ai (.);
A (.)
{(
})
(i) for every zd and for every r*+, z and

r are measurable from (,( )) into
itself.
A(r G,a) 1r A(G,a)
=
, A (zG,a)= z + A (G,a)
1
meas(A)
It is clear that for every a in d, the set map

A A (.,a) from I into L (,( ), ) satisfies
the following three conditions of a discrete
subadditive process, see for instance [3]:
iI
(ii) is covariant, that is, for every A in I,

every z in d, z + A = A o Z ;
Proposition 3.1.
(ii)
(1-t)lb,A)t A (G,a)+(1-t) A (G,b)+.
meas(r A)
(iii) There exists a constant C, such that for

every a and b in d
A(G,a) A(G,b)
p 1
p 1
C 1+ a + b
a b .
meas (A) meas (A)
(iii) (M )=
inf
: A(G,a)
d(G ), AI, meas( A)0 >-.
B( ) meas( A)
Furthermore this process is ergodic and the

following inequality holds.
Proposition 3.2. For every a in d,
A(.,a )
L1 (,( ), )
(1+|a|p)meas(A).
Proof.
Proof.
(i) and (ii) are obvious. Let us prove (iii),

( G, a )
setting for every a in , m(a)= A
,
meas (A)
d
m(a) is convex indeed, for every t]0, 1[, for

every a,b in d and for every >0, there exist
u a and u b in W 10, p (A) such that
G(u a +la,A)< (G,a)+ ;
G(u +lb,A)< A (G,b)+ ,

b
Since G(.,A) is convex, then

G(t(u a + la) + (1-t) (u b + lb),A)
Since the function u a G(u+la,A) is convex on

W1,p(A) and bounded, thus it is continuous,
furthermore from the separability of W1,p(A)
there exists a dense sequence (uk)k such that
{(
)}
A(G,a )= min G uk +la , A .

k N
Therefore the map G a G(uk+la,A) is

measurable, we conclude that G a A (G,a) is
( ( ), ())measurable, according to (1) we
have A(.,a )
L1 (, ( ), )
(1+|a|P)meas(A).
85
As a consequence of the M. A. Ackoglu and

U. Krengel [3] results, we have:
Corollary 3.3. There exists a subset of
with P() = 1 and a function fhom : d
such that, for all in , for all open cube Q
in d and for all a in d
tQ(G,a )
N *
(tQ ) =kinf
f hom(a )= lim
t + meas
kY (F( ),a )
dP( ).
meas(kY )
f hom(r)
( )
tQ(G,r)
tQ G,an
f hom(r) f hom an + f hom an
meas(tQ)
meas(tQ)
( )
( )
( )
tQ G,an tQ(G,r )
..
meas(tQ ) meas(tQ )
Using the proposition 3.1 (iii), for the last term

and going to the limit as n+ and t+,
we
obtain
for
every
r
in d;
tQ(G,r )
. It remains in the end,
meas(tQ )
Also, fhom is convex and satisfies (1).
fhom(r)= lim
Proof.
to prove that fhom satisfies the growth condition

(1). The upper bound is just the consequence
of the proposition 3.2. For the lower bound,
using (1) and the convexity of r a |r|p, we get
t +
From the theorem 2.4, the lemma 3.4 and

remark p.59 by [3], for every a in d there
exists a set Ea in ( ) with (Ea)=1 and a real
fhom(a) such that, for all G in Ea
kY (G,a )
kY (G,a )
= inf
d(G )
k + meas(kY ) kN * ( ) meas(kY )
-1
Setting =F I Ea , we obtain for
aQ d
f hom(a )= lim
every a in d and for every in
f hom(a )= inf
kN *
kY (F( ),a )
dP( ) .
(
)
meas
kY
(2)
Let Q be any open cube in d with side .

Setting for every t in *+, k-=[t]-1; k+ =[t]+1;
Q-=k-(Y+z) and Q+=k+(Y+z) where z,zd
where [t] denotes the integer parth of t. It is
clear that Q-tQQ+ and meas(tQ) is
equivalent to meas(k+Y) and meas(k-Y).
Thanks to (2), the covariance of and the
inequality A (G,a) B (G,a)+(1+|a|P)
meas(A\B); whenever BA in Ob. We get, for
every a in d and for every in
f hom(a )= lim
k +Y z F( ),a
t +
limsup
t +
meas(tQ )
liminf
t +
tQ(F( ),a )
meas(tQ )
k Y z F ( ),a
tQ (F ( ),a )
lim
= f hom (a ).
meas(tQ ) t + meas(tQ )
We extend the previous step to every a in d,

will be a fixed element in . From the
proposition 3.2, we prove that the map
a a fhom(a) defined for every a in d by
fhom(a)= lim
t +
tQ(G,a)
meas(tQ )
is continuous, so one
can extend fhom to d by setting rd,

hom
fhom(r)= lim f (an), where (an)n is any
n +
sequence in d converging towards r. Then

we have:
86
tQ(G,r)
p
r =
meas(tQ)
1
min
meas(tQ )
a +u(x ) dx, uW01, p(tQ ) .

tQ
After going to the limit when t+, we

obtain the result.
4. THE MAIN RESULT
This section is devoted to verify by the

concept of the epiconvergence that, the
integral functional
f hom(u(x))dx if uW 1, p(A);
F hom(u, A)= A
+
otherwise,
is the P-a.e, epilimit (where is given

by the corollary 3.3) of the process
Fn()(u,A):= F( )(u, A) , that is ().
n
Theorem 4.1. For every A in Ob and for every

u in W1,p(A), Fhom(u,A)=-epilimitFn()(un,A),
where denotes the strong topology of Lp(A).
Proof. It remains to prove the assertions (i)
and (ii) in the definition 2.1 by steps.
Verification of (i).
First step. We assume that A in Ob, u =

la and un-la W 10, p (Q) (see for instance [7]).
Then, for every >0, there exists a finite
family (Qi)iI() of disjoints open cubes include
in A, such that meas A \ U Q i . From
i l ( )
hom
(1) and the definition of F , we have:
Fhom(u,A)
(u,Qi)+(1+|a|p).
hom
il( )
Since by corollary 3.3.and proposition 3.1 (ii),

we have for every i I()
( )
( )
F hom u,Qi = meas Qi f hom (a )=
( )
Qi
(F( ),a )
)
(F ( ),a )
liminf F ( )(u ,Q ).
meas(Q ) lim
meas(Q )
n
meas Qi lim
n +
meas n Qi
Qi
n +
n +
converging towards u in W1,p(A), then the

sequence vn, is bounded in Lp(A) by a
constant that does not depends on and n.
Then we obtain
Fn ( ) vn,, A C u u
Lp ( A )
( )
+ Fn ( ) un, A
(4)
where C will denote any constant that does not

depends on and n, hence
liminf Fn ( ) vn, , A C u u
n +
Lp ( A )
( )
liminf Fn ( ) un, A
n +
(5)
Using the previous step, the superadditivity

and the non decreasing properties of the set
function B a lim inf Fn()(u,B), we obtain
By (3), (4), (5) and the continuity of Fhom(.,A),

we
get,
when
tends
to
0,
F hom(u, A)liminf Fn ( ) un, A , which ends the
F hom(u, A)
proof of (i)
epiconvergence.
n +
( )liminf F ( )(u ,Q )+ (1+ a )

liminf F ( )(u , A)+ (1+ a ).
n +
iI
n +
lim vn , , i = u , i in L ( Ai )
n +
hom
inf Fn (u n , ,i , Ai ) .
F (u ,i , Ai ) nlim
After summation over i, with

superadditivity of lim inf, we obtain
Fhom(u,A) lim inf Fn()(vn,,A).
U QiA
il ( )
F hom(u, A) F hom u, Qi =
iI()
hom
meas(Qi )f
(a)=
the
)
( )
( )
( )
(u u )
+ F ( )(u , A)
( )
f ( ) x ,vn, , u u + Fn ( ) un, A
n
p 1
C 1+ vn,
u u dx + Fn ( ) un, A
A
C 1+ vn,
Assume
that
p 1
Lp ( A)
Lp A
( )
liminf Fn ( ) un, A <+ .

n +
Qi, where meas U Qi =

jJ()
and the corollary 3.3, we get
lim
(3)
il ( ) U J ( )
hom
Using the convexity inequality of f, we have
of
() with lim ()=0. From the definition of
iI ( )
n+
definition
First step. We assume that A in Ob and

u an affine continuous function la, ad. Let
>0 and (Qi)iI(), (Qj)jI(), two finite family of
open disjoint cubes with side of the lattice
in d spanned by ]0,[, such that
n +
the
Verification of (ii).
Second step. We assume that A in Ob

and u in W1,p(A). Using the density of
piecewise affine continuous function in
W1,p(A) by [9], there exists a sequence (u) of
piecewise affine continuous functions,
converging towards u in W1,p(A) and a finite
partition (Ai)iI() of A, such that its restriction
u,i is affine on Ai. Setting vn, = u + un - u with
vn,,i=vn, over Ai . By the previous step we
have, for every iI()
in
By letting 0, we conclude the result.
Fn ( ) vn, , A
( )
n +
(6)
(F ( ),a ).
Qi
iI ( )
The suitable sequence (un())nN will be

deduced from the approximate minimizers of
Q Fn ( ),a . . Precisely, let vin,() be in
i
W 10, p (A) such that
(
)
(F ( ),a ).+ card(I() J ( )) ,
Fn ( ) vni , ( )+la ,Qi
Qi
Since
vn,=un+(u-u), by using (1), we conclude

that (un)n is bounded in LP(A), and since u
we define vn,() and un,() in W 10, p (A), by

vn,()=v in , () in Qi and un,()=vn,()+u.
From (6), we obtain:
87
F hom(u, A) lim
n +
(F ( ),a ).
iI ( )
Qi
limsup Fn ( ) un, ( ), Qi
n +
iI ( )
(7)
Therefore, from (7) we have

p
F hom (u, A)limsup Fn ( ) un, ( ), A ( )1+ a 2 ,
n +
finally
F hom (u, A)limsuplimsup Fn ( ) un, ( ), A

0
n +
(8)
Lp ( A)
= vn,
( )
p meas Qi +
( ) ( )
iI J
p
C (meas( A)+ ),
n +
where un()=un,(n)().
(Ai)iI is a finite partition of A, for every iI,

AiOb. Using the first step, there exists
un,iW1,p(Ai), such that
lim un,i( )=ui in Lp Ai
n +
F hom u , A =limsup F ( ) u ( ), A ,
n
i i
n,i
i
n +
( )
Setting A=A1A2 ={xA, dist(x,)<}

for >0, where is the interface between A1
and A2, the argument can be easily extended to
a finite number of subsets. Let be a D(A)
88
Using (1), we obtain

limsup Fn ( )(tun , A)
n +
f ( ) x ,un,i (x )dx +
n
p
1+ u(x ) dx +
limsup
n +
Ai
i =1
(1t ) u (x)u
d1+ t
n, i
(x )
p
(x ) dx.
Because un,i converge to ui in Lp(Ai), and from

the previous step
F hom(u, A)limsup
n + i =1 Ai
then
n +
lim (1t )
i =1
Ai
(1t )meas( A),

and
f ( ) x ,un,i(x )dx
n
(1t ) u (x)u
1+ t
n,i
(x )
dx =
F hom (u, A)limsup limsup limsup Fn ( )(tun , A) .

t 1
Second step. Let A be in Ob and u a

piecewise affine continuous function. We set
u =la +bi in each Ai, with aid, bi, where
Ai
card(I ( ) J ( ))
where C is a constant that depends on p, and

. From (8), (9) and the diagonalization
argument (see [4]), there exists a map n a (n)
such that (n)0 when n+ and
lim un( )=u,
n +
F hom(u, A)limsup F ( ) u ( ), A ,
n
n
+ lim (1t )
Lp ( A)
f ( ) x ,tun (x )dx
n
i =1
2
x
t 1 (x ) f ( ) ,un,i(x )dx+
A
n
i =1 i
2
x
t f ( ) ,u(x )dx +
A
n
i =1 i
2
x t
+(1t )
f ( ) ,
ui (x )un,i(x ) (x )dx.
(
)
1
t
Ai
n
i =1
Fn ( )(tun , A)=
n + i =1 Ai
Thanks to the lemma 4.3 by [12]

un u
Since f()(x,.) is convex and t(1-(x))+t(x)

+(1-t)=1, therefore
Fn ( ) un, ( ), Qi +
M Q Fn ( ),a +
i
iI ( ) iJ ( )
p
Fn ( ) un, ( ), Qi + 1+ a meas
Qi +
iI ( )
iJ ( )
tun =t 1 un,i +t u + (1t ) t u un,i ,

(1t )
Fn ( ) un, ( ), A Fn ( ) un, ( ),
Qi
iI ( ) J ( )
M Q Fn ( ),a +
iI ( ) J ( )
( )
( )
Then, u n W 10, p (A) and for 0<t<1; i=1,2
On the other hand
function, such that =1 on , = 0 on

A\2, 01 and
1 un,1 + u on A1 ,
un =
1 un,2 + u on A2
n +
Using again the diagonalization argument,

there exists a map n a ((n),t(n)), such that
((n),t(n))(0,1) when n+ and
F hom(u, A)limsup Fn ( ) t(n )un (n ), A
taking un=t(n)u
unu in Lp(A).
n +
(n),n
, an easy computation yields
Third step. For uW1,p(A), there exists

a sequence (uk)kN of piecewise affine
continuous functions, such that (uk)kN
converging to u for the strong topology of
W1,p(A) by [9]. From the second step, there
exists a sequence (uk,n)nN in W1,p(A), such that

lim u =uk in Lp (A);
n + k, n
F hom(u , A) limsup Fn ( ) u , A .
k
k, n
n +
Therefore
( )
u n
k +
n +
By the continuity of Fhom and the

diagonalization lemma, there exists a sequence
(uk(n),n)nN in W1,p(A), such that
lim u
=u in Lp(A);
n + k(n ), n
F hom(u, A) limsup Fn ( ) u
k(n ), n , A .
n +
which ends the proof.

As a consequence of theorems 4.1, and the
proposition 2.1, we have:
Corollary 4.2. For every hLq(A), where

1 + 1 =1 , then
p q
min Fn()(v, A) hvdx .
vW01, p ( A )
converges to
min F hom(v, A) hvdx .
vW01, p ( A )
Furthermore, there exist a subsequence

u(n)() and u respectively solutions of the
above minimization problems, such that
u(n)() converges to u in Lp(A).
Proof.
Let H n ( )(v )= Fn()(v, A) hvdx ,
H hom(v ) F hom(v, A) hvdx . We denote by arg
minHn (respectively argminHhom) the set of the

solutions of the associated minimization
problem to Hn (respectively to H), and let
unargminHn, since Hn(un)meas(A) and
un p 1 h un dx meas( A) .
(10)
L ( A) A
From (1), (10) and the Young inequality

aba p +
meas( A)+ 1
meas( A)+ 1
p11 q
b , applied for a = |un|, b = |h| and
= , we have for each n in

2C
Then, un
meas( A)+ 1
meas( A)+ 1
limsup F hom uk , A limsuplimsup Fn ( ) uk, n, A .

k +
Lp ( A)
(2C )
p11
hu
A
n dx
q
h dx + un
2C
(2C ) h dx+ 21C u

(2C ) h dx+ 12 u
W01, p ( A )
p11
p11
dx
p
n
dx
Lp ( A)
C , (where, C is the poincar's
constant and M denotes a different constant

that does not depend on n). Hence by RellichKondrakov theorem, there exits a subsequence
u(n) of un and uW 10, p (A), such that: u(n) u
weakly in W 10, p (A) and u(n) u strongly in
Lp(A). Since Hn epiconverges to Hhom for the
strong topology of Lp(A), then uarg
minHhom.
EXAMPLE
Let (Xz)zd be a family of independent
random variables defined on a given
probability space (,,P) by: for every in
, Xz(){,}, where , *+ , such that
P{; Xz()=}=r and P{; Xz()=}=
1-r, with r]0,1[. For a given reel positive
sequence n and z in d, let I z n be the

characteristic
function
of
the
cube
n
d
Q z ={x ; n zi xi < n (zi+1), i = 1,...,d}.
Define, for every and for every xd;
( , x )= 1 , x =
X z ( )I z n (x ) ,
n
n zZ d
and
the
random integral functional
f()(x,u(x))dx if uW 1,2(A);
F()(u, A)= A
+
otherwise ,
where
f ( )(x,a )= 1 (, x ) a ,
2
uL2(A)
and
AOb. It is clear that, the function f()(x,a) is

x-measurable, a-convex and satisfies (1), with
=min(,) and =max(,). Let us now
define, for every uL2(A) and every AOb
x
1,2
( )2
( )
F ()(u, A)= A1,n u x dx if uW A ,
n
+
otherwise
.
89
It is well known that the following bilateral

shift (s)sd defined on the probability space
(,,P), by: for every in , every z,s in d
Xz(s) = Xz+s() is a group of P-preserving
transformations and ergodic (see for example
[11]).
Following the corollary 3.3, theorem 4.1, there

exists with P() = 1, such that for
every uL(A), for every AOb and for every
in , we have F ( )(u , A) epiconverges to
For every AI, ad and , we define as

in the Sec.3 the following minimum
for the strong topology of L2(A), where

ad;
S A(,a )= min 1 (, x )u(x )

A
dx, u la W01,2
( A), .
The set map A a SA(,a), satisfies the

conditions below:
(i) The subadditivity is clear.
(ii) The covariance. For AI and sd,
we have:
2
SA+s(,a)=min 1(,x) u(x) dx, ulaW01,2( A+s)
A+s
=min
Xz()Izn (x) u(x) dx, ulaW01,2( A+s)
A+s d
zZ
=min
Xz() Izn (x+s) u(x+s) dx,suslaW01,2( A)
A d
zZ
f hom(u(x))dx if uW 1,2(A),
F hom(u, A)= A
+
otherwise.
f hom(a )= lim
min
ula +W01,2 (kY )
S A+ s (,a )
= min
X z + s ( )I z n (x ) v(x ) , u la W01,2( A)
A
d
zZ
= min
X z s I z n (x ) v(x ) , u la W01,2( A)
A zZ d
= S A s ,a = S A o s (, a ).
( )
( )
Thus SA+z = SA o z for every A in I and for

every s in d.
(iii) Using the inequality (1) and taking u = 0,
we obtain
S A(, a )
90
( )
1+ a meas( A). .
2
L1 (,, P )
(kY )
(1 (,x) u(x) 2dx)dp( )
kY
When d=1,
f hom(a)= lim 1
k + 2k
min
uW01,2 (] k, k[);u(k) = ka,u(k) = ka
1 (, x) u'(x) dx dP .
By writing, the Euler equation of F()(u,A),

we obtain that the function u which attains the
minimum in the expression of fhom satisfies the
equation
Setting v(x)=-su(x) - sa=u(x+s)-sa,

then v(x)=u(x+s), and
k + meas
1 ( , x ) u'(x ) =c , x] k, k [,
u( k )= ka, u(k )= ka,
where c is a suitable real constant. It is

straightforward to check that
1
2k
1 ( , x ) u'(x) dx = 1
k
2k
1 ( , x )1dx a 2 ,
therefore for every in

2
k
( , x ) u'(x ) dx =
{
} k 1
1
1
k 1
k
1
1 2
1
X z ( ) a 2 .
2k k 1 ( , x ) dx a = 2k
z
=
min
uW01,2 (] k, k[);u(k) = ka,u(k) = ka
So by the strong law of large number (see [5])

1
f hom(a )= r1 +(1r ) 1 a 2 =m0 a 2 ,
1
with m0 = r1 +(1r ) 1 , if r = 1 , m0 is the
harmonic mean of and . So, for every u in

W1,2(A)
F hom(u, A)=m0
u'(x ) dx .
REFERENCES
1. A. Braides, Rend. Accad. Naz. Sci. XL
104, 261-281 (1986).
2. A. Braides, I. Fonseca and G. Leoni,
SIAM J. Math. Anal. (2000).
3. M. A. Ackoglu and U. Krengel, J. Reine
Angew. Math. 323, 53-67 (1981).
4. H. Attouch, Variational Convergence For
Functions and Operators, Research Notes
in Mathematics, Pitman, London (1984).
5. L. Breiman, Probability, Blaisdell (1968).
6. G. Dal Maso, An Introduction to
-convergence, Birkhuser, Boston. Basel.
Berlin (1993).
7. G. Dal Maso and L. Modica, Ann. Math.
Pura. App. 346-389 (1985).
8. G. Dal Maso and L. Modica, J. Reine
Angew. Math. 363, 28-42 (1986).
9. I. Eklend and R. Temam, Convex Analysis
and Variational Problems, North-Holland
(1978).
10. I. Fonseca and S. Mller, SAIM J. Math.
Anal. 1-35 (1999).
12. K. Messaoudi and G. Michaille,

Mathematical Modelling and Numerical
Analysis 28, 329-356 (1994).
13. D. H. Hyers, G. Isac and Th.M. Rassias,
Topics in Nonlinear Analysis &
Applications, World Scientific Publ. Co.
Singapore, New Jersey, London (2000).
14. M. L. Mascarenhas and A. M. Toader,
Scale Convergence in Homogenization.
C.M.A.F
Faculdade
de
Cincias,
Universidade de Lisboa Av. Prof. Gamma
Pinto, 2, 1649-003 Lisboa, Portugal
(2000).
15. S. Mller and G. Alberti, J. Math. 761-825
(2001).
16. M. L. Mascrenhas, Proc. of the Royal.
Soc. of Edinburgh 123A, 311-322 (1993).
17. G. Nguetseng, SIAM J. Anal. 20, 608-623
(1989).
18. A. Radjesvarane, Proc of the Royal Soc. of
Edinburgh 127A, 441-455 (1997).
19. A. M. Toader, Memory effects and
-convergence; a time dependent Case.
Centro de Matematica e Aplicaes
Fundamentais, F.C.U.L., Av. Prof. Gamma
Pinto, 2, P-1699-Lisboa, Portugal (1999).
11. U. Krengel, Ergodic Theorems, Walter de

Gruyter, Studies in Math. (1985).
91
Biological Investigations: Form, Function,

Diversity & Process
by W.D. Dolphin; McGraw-Hill
2005 (7th Edition)
This book is intended for use in a two-semester introductory

biology course serving majors in the life sciences.
The book starts by relating the laboratory topics with
chapters in major textbooks in biology. This indeed makes it
easy for lecturers using different textbooks to relate this
laboratory manual to the theoretical material given in
introductory courses.
All laboratory topics are organized into the following
sections. First, Supplies that is needed to carry out the
laboratory. Second, Student Prelab Preparation, basically
covering the major terms and concepts the students should
familiarize themselves with before coming to the laboratory,
as well as questions about how they think the laboratory will
proceed to deal with such terms. Third, Objectives, listing a
concise yet an exhaustive list of learning objectives the
student should gain at the end of each laboratory. Fourth,
Background which details the theory behind each laboratory
experiment. Fifth, laboratory Instructions box that
highlights the procedure to follow, or lists things the
students should be aware of and careful about. The box title
is appropriately coloured to indicate the start of the
procedure. The procedure then details what experiments or
activities that will be carried out in that laboratory session.
The steps for carrying out any procedure are highlighted in
brown colour and allow students to work independently.
Caution boxes are included, where appropriate, to warn
students of hazardous material or situations. Each laboratory
topic is supplemented by an appropriate number of figures
and tables as needed to get a good comprehension of the
laboratory procedure. Coloured figures are used extensively
which helps in highlighting important features in the figure
that students should pay attention to. Tables are included as
appropriate and the title of each table is highlighted with a
green colour. Spaces are provided for the students to write
the results of experiments, observations, sketches and
answers to questions of various formats and types.
Sometimes, optional demonstrations, experiments or
exercises are included. Sixth, Learning Biology by Writing is
a section which asks the student to write a brief laboratory
report about the topic of the chapter. The author also gives
an alternative assignment, which consists of completing the
Laboratory Summary and Critical Thinking Questions, the
seventh and eighth sections of each chapter. Some topics
include a box for important internet resources pertinent to
the topic.
The language of the manual is easy to understand by average

students and I found no typos, misspellings or general
mistakes as I read the various topics.
The laboratory manual consists of 34 topics. The manual
starts off with the laboratory on the scientific method and
concludes with simple statistical analyses (Topic 33) and
estimating population growth (Topic 34). Essentially, it
covers all chapters that one would find in any major
textbook in biology. The procedures were thoughtfully
planned and the author must have given each a considerable
time to design each laboratory for a 3 hour session. The
laboratory topics are not heavily inter-dependent, so a onesemester introductory biology course can be accommodated
for using this manual. As for the topics themselves, I believe
they are appropriately written for introductory biology
laboratory courses, in terms of the subject material, easiness
of carrying out the procedures, and time to finish each topic.
In addition, the manual includes four appendices on
significant figures and rounding, making graphs, simple
statistics and writing a laboratory report.
The inside of the front and back covers include information
about safety in laboratories, which succinctly summarizes
important laboratory safety procedures, and the meaning of
many prefixes and suffixes used in many biological terms.
An added advantage of this manual is the laboratory
preparation guide, available online, to help instructors and
technicians prepare for each laboratory beforehand.
Finally, I would recommend using this textbook for the
basic biology laboratory course at UAE University.
Sofyan Alyan
Department of Biology, College of Science,
UAE University
93
Ecology: Concepts and Applications

by M.C. Molles Jr.; McGraw-Hill
2005 (3rd Edition)
This book is intended for undergraduate students in ecology.

It is assumed that students have the basics of chemistry and
math and have taken a course in general biology. The book
is organized around key concepts in ecology, and that is a
strong advantage over other textbooks in basic ecology.
Each chapter is organized into basic concepts and theories,
applications and case studies. At the end of each chapter,
students find internet links to information related to the main
topics discussed in the chapter. One of the positive additions
in this edition are the inserts providing students with
information, answers to some questions, hypotheses,
predictions or testing. In Chapter 1, for instance, "scientific
methods questions and hypotheses" was the topic. The
author explained scientific methods, with simple examples
and graphical relationships among the components of a
scientific method.
I find the book easy to read and the information is accurate
and well presented; with few exceptions. In Chapter 16, for
example, there is a need for a more detailed and step by step
guidelines on how to calculate species diversity. Application

and real-world examples on how to use diversity indices are
needed. Moreover, other methodologies in estimating
abundance and diversity are to be added. The book is
presently used as a textbook for the Basic Ecology course at
UAE University. I believe it serves the students well.
Obviously, it lacks examples and case studies from the
UAE. This issue is dealt with by providing UAE case studies
related to the topics under study. The supplementary
material has recently been updated and provides valuable
resources for students and instructors. An interactive CD is
available (not as part of the book). It contains presentations,
video clips, animations and every graph/figure of the book.
Taoufik Salah Ksiksi

UAE University
____________________________________________________________________________________________________
Introductory Plant Biology

by K.R. Stern, S. Jansky, J.E. Bidlack;
McGraw-Hill
2003 (9th Edition)
This book is designed as an introductory text in botany. It is

a solid and clear introduction to plant biology which could
be used by both science majors and non-majors. This text is
currently being used at UAE University in the teaching of
the Plant Biology course offered by the Department of
Biology to students from both the College of Science and
the College of Education. The style of the text is clear and
is easily accessible to students. The content is accurate and
scientifically sound. For each chapter, an outline, review
questions, discussion questions, learning online topics and
additional reading lists are provided. New terms are defined
as they are introduced, and are boldfaced and included in a
pronunciation glossary. The illustrations are in colour. In
addition to a conventional sequence presentation of basic
94
botanical principles, the authors emphasize current

ethnobotanical and ecological interests. Moreover, this book
has several teaching and learning supplementary resources
for both instructors and students, such as transparencies, a
CD-Rom, a laboratory manual and an online learning center.
Overall, this book represents a valuable resource, which
introduces the field of plant biology in a clear, objective and
didactic way.
Naima Bouhouche
UAE University
Human Biology
by S.S. Mader; Mc-Graw Hill
2004
This book is being used in the Department of Biology at

UAE University to provide an adequate biology background
to
undergraduate
psychology
students.
The
indistinguishable relationship between biology and
psychology makes biology an essential course for
psychology students. This course begins with providing
students with the fundamentals of life machinery and the
characteristics of living things. These topics naturally lead
onto cell biology and subsequently to organ systems.
Although the relevance of each organ system to behaviour
plays a major role, a good portion of this course is dedicated
to neurons, the brain and behaviour.
Dr. Sylvia Mader, a well-known author in the field of
biology, has written this book with tightly knitted text that
covers the concepts and principles of biology from the
structure and function of the cell to the organization of the
systems. The concept of how all the systems work together
is necessary to understand the unity and diversity of human
behaviour. Modern behavioural problems, need a thorough
understanding of how all the systems work together in the
human body.
The contents of this book are very well developed starting
from the human perspective outlining the process of science,
which direct its readers to the cell, its basic chemistry,
structure and function and finally the organization and
regulation of body systems. The human organization part
leads very well into the maintenance of the human body
which involves a discussion of all the systems and their
functional incorporation. Later on, the author ingeniously
introduces the topics of movement, support, neuro-endocrine
integration, coordination of all five senses and finally goes
on to reproduction development and aging. The last few
chapters in the book deals with important topics such as
human genetics, diseases and evolution.
The author's grasp of each topic is undoubtedly reflected
from the uncomplicated and to the point description of
subject matter through out the book. The layout of the book
is eye catching enough to bring it to the attention of an
undergraduate student. The book is full of coloured
illustrations and internal summary statements, following the
hypothesis [1] regarding the easy method of transferring
knowledge in short visual packets. Explanation of difficult
topics in colourful precise diagrams not only helps students
to focus on the most important concepts, discussed in that
particular section of the chapter but also assists them

visually. There are many boxes in each chapter enveloping
the notions about, how systems work together, bioethical
focus and testing the knowledge.
The author examines students on each topic by giving
objective questions, matching exercises and multiple-choice
questions at the end of each chapter. This is definitely a
very well revised book covering the basic knowledge of
human biology with no obvious errors.
I found this book very helpful achieving the specific goals
for this course. Students in this course are expected to
comprehend biological structure and functions of cells and
organs and to understand their relationship with each other.
They are also expected to gain an appropriate knowledge
regarding the relationship between body and mind, and
recognize how biology can be utilized to understand human
psychology.
This text book has a very rich source of supplementary
material in the form of ESP (Human Biology Essential
Study Partner 2.0 CD-ROM). This learning tool is filled
with over 100 animations and more than 200 educational
events. A self-quizzing component, which allows students to
test their knowledge of a topic before moving onto a new
unit is also included. Additional module examinations give
students the chance to analyze an entire subject area. The
quizzes and unit exams hyperlink students back to the
tutorial sections so they can easily review the material for a
more complete understanding.
The cost of the book is not beyond student's expectations.
Reference
1. A.D. (Tony) McKenzie, Christopher K. Morgan and
Geoffrey K. Watson, HERDSA, 15, 34 (2004)
Fatima Shad Kaneez

UAE University
95
Physical Geology
by C.C. Plummer, D. McGeary and
D.H. Carlson; McGraw-Hill
2005 (10th Edition)
There are many opinions on how introductory physical

geology ought to be taught: what subjects should be
covered, in what order, and with what emphasis. Thus, it is
no surprise that physical geology textbooks are so common.
Despite this, a perusal of the many choices does not present
much difference in the style, layout, or presentation of the
subject. This cannot be said for Physical Geology (10th
Edition) by Plummer, McGeary and Carlson. A simple
examination of the table of contents illustrates this. In most
physical geology texts a discussion of plate tectonics is
presented early. This is no surprise given the importance of
plate tectonics in understanding geologic theory.
The
authors of Physical Geology (10th Edition) leave such a
discussion to a later part of the text. My surprise, however,
turned to appreciation as I read the text. Plummer et al.
have laid material out so as to lead the student from the level
of everyday, personal experience, such as minerals and types
to rocks, step by step, to the Big Picture view of plate
tectonics (and beyond with a discussion of planetary
geology). Thus, students do not discuss plate tectonics in
detail until they have been introduced to the tools that will
help them to better understand it. Each section leads very
smoothly and naturally into the next discussion. Beyond
this, the book is very good on a number of issues. It has
introductions at the beginning of each chapter that present an
overall view of the material, as well as concise summaries at
the end. This use of repetition is a great aid to students
learning new material. The material itself is presented in a
very clear way. The figures and graphics, all of which are in
color, are some of the best I have seen in a textbook of any
kind. This is especially nice because the book is very
comprehensive.
In fact, I found myself trying to think up subjects from the
various subfields of geology just to see if they were there.
They were. Yet, because of the order of presentation and the
96
clarity of the illustrations, the information does not seem

overwhelming. Each section ends with a list of web
resources to aid students and there is also a website with
additional material, such as animations, to supplement the
text. I do think that a list of journal articles and books
should also be presented as additional resources, which,
after the price (~$95), is my biggest complaint. The text
also includes many anecdotal stories (some humorous)
illustrating various principles, but presents them in box
articles so they do not get in the way of the basic material
being presented. In each section there are also other box
articles that treat particular subjects in greater mathematical
detail if the student wishes a more rigorous understanding.
The box articles do lead to one of the few minor complaints
I have with the text. It is sometimes hard to differentiate
between the main text and the box articles. This would be
easily solved by adding a clear border or shaded background
around the box article. Another complaint is that the edition
that I reviewed is advertised as being the International
Edition, yet most of the examples, especially those
discussing resources and economics, are from the U.S.A.
And as good as the graphics are, I think that the graphic of
kimberlite pipes (p. 118) is a little misleading in its lack of
detail. I was also surprised that although discussed, there
was no figure for turbidity currents. These complaints are
very minor however.
The book is comprehensive, clear, accurate and has become
my first choice for use in my classes.
Benjamin R. Jordan
Department of Geology, College of Science,
UAE University
Partial Differential Equations

(Schaums Outlines Series)
by P. DuChateau, and D. Zachmann;
McGraw-Hill
1986
According to its preface, the book is intended to serve as a

supplemental text for a course on partial differential
equations. The book provides an excellent opportunity to
undergraduate majors in mathematics, physics and
engineering to enhance their problem solving skills and
understanding of the subject of partial differential equations.
The book is presented in fourteen chapters that are grouped
into three parts. Each chapter starts by giving a brief account
of the theoretical and mathematical concepts to be discussed,
and then followed by numerous solved examples and
problems which are intended to aid the readers to understand
the underlying theorems and concepts. Each chapter is ended
by a sufficient number of supplementary problems whose
solutions are given at the end of the book in a sketchy
manner to guide the readers in order to enhance their
problem solving skills.
Part I of the book is devoted to qualitative aspects of the
subject of partial differential equations. The classification
and types of partial differential equations are discussed.
Qualitative behavior of solution of evolution, elliptic and
hyperbolic problems are presented.
Part II presents the main and fundamental approaches for
finding exact solutions to linear partial differential
equations. Advanced ideas related to Eigen functions,
integral transformations and Greens functions are
discussed. Some examples of practical implications are

given and their solutions are obtained.
Part III presents techniques to be used to find approximate
solutions to partial differential equations which include
finite difference methods, methods of characteristics and
finite element method. Several computer codes are given
where some of the above methods are implemented to solve
well selected problems.
The book material is well written, the style and language
used is adequate. It is an excellent supplementary source of
problems to be recommended for a course on partial
differential equations. It is worth mentioning that no CD or
any other supplementary product accompany the book itself.
In summary, the book presents the subject material in a
lively and carefully written manner which is fully
comprehensive and useful for mathematics, physics and
engineering majors.
Mohamed Naim Anwar

Department of Mathematics & Computer Sciences,
College of Science, UAE University
97
Intermediate Algebra
by M. Dugopolski; McGraw-Hill
2004
This book is deigned to provide students with the

background to algebra needed for pre-university
mathematics courses. It is suitable for students with no prior
exposure to algebra. Students will have no problem in
reading and understanding the topics presented in this book.
Each chapter begins with an application of algebra in real
life problems. It is accompanied by a photograph and a real
data application graph that helps students visualize algebra
and understand the concepts discussed in the chapter. All
worked problems are presented in a step by step fashion.
Important ideas, such as definitions, rules, summaries and
strategies, are set apart in boxes for quick reference. Colors
are used to highlight these boxes as well as other important
points in the book. At the end of each section there are
enough interesting problems that contain applied problems
and true-false problems. This book is well organized. It has
been carefully revised. It contains many modifications from
the previous edition. It has useful supplementary materials.
Each book contains a registration code. After a student or an

instructor register they can use the entire material made
available from McGraw-Hill that is posted on WebCT or
Blackboard. These materials are really very helpful for the
students and instructors. In addition, internet addresses are
provided as a resource for both students and teachers. The
book ends with answers to selected problems.
If I am teaching a pre-university mathematics course, I will
be very happy to use this book. For this reason, I strongly
recommend this book for mathematicians who teach this
type of course.
Muhammed Ibrahim Syam

____________________________________________________________________________________________________
Statistics for the Behavioral Sciences

by B. Thorne & J. Giesen; McGraw-Hill
2002
This book is deigned to provide students with the statistics

background needed for first year statistics courses. It is
appropriate for students with no prior experience in
statistics. The text itself is easy for students to read and
understand topics from it. With this book, students will be
able to develop a new vocabulary of statistics and to
discover how to combine terms and phrases into longer and
more useful ways. The book is presented in an easy way.
Enough examples are included that explain each concept and
theorem. Real applications are presented throughout this
book. These applications are accompanied by a photograph
and real data application graphs that helps students visualize
statistics and understand the concepts discussed in the book.
All worked problems are outlined in a step by step fashion.
Important ideas, such as definitions, rules, summaries and
strategies, are set apart in boxes for quick reference. Color is
used to highlight these boxes as well as other important
points in the book. At the end of each section there are many
interesting problems that contain applied problems.
Moreover, there is a useful summary at the end of each
section. In addition, the book has a section at the end with
answers to selected problems. The book is well organized
98
and has been carefully revised. It contains many

modifications from the previous editions with useful
supplementary materials. This book shows that statistics can
be approached and appreciated at different levels. The first
level is the practical one which involves the ability to use
statistical tests and methods in an applied setting. The
second one is the intuitive level which involves a feeling for
the principles underlying statistical procedures. In this
book, the statistical procedures require little more than
addition, subtraction, multiplication, division and some
elementary high school algebra. Almost all students, well
prepared in math or less well prepared, can succeed at the
level at which this book is aimed.
If I am teaching a first year statistics course, I will be very
happy to use this book. For this reason, I strongly
recommend this book for people who teach this type of
course.
Muhammed Ibrahim Syam

Chemistry-The Molecular Nature of

Matter and Change
by M. Silberberg; McGraw-Hill
2003
The book certainly seems to be carefully written and welldevised for freshman chemistry students. The author is
evidently imaginative as to the strengths and weaknesses of
the students. His book, in my view, is far better than many
good books used in General Chemistry classes. The book is
readily readable, and uses supplementary materials.
The author seems to have had put together his experience,
acquaintance, and knowledge that he acquired over the years
to come up with such an impressively written book. I could
not overemphasize how organized and well-sequenced the
book is in the clarity of its lay-outs. It is not so much the
knowledge (which should be rife on such introductory
chemistry anywhere) that this book offers but rather the
unequivocal presentation itself. The presentation is uniquely
impressive; the illustrations are clearly spelled out; and the
color variation is well-chosen for underscoring specific
points or conveying important ideas. The colors are selected
in such a way that fundamental concepts are selfhighlighted. The appropriate and careful color variation
plays a pivotal role in catching the readers attention of the
corresponding points. The author seems to be so innovative
that he specifically knows when to pinpoint or emphasize a
concept as may be needed to do so.
Finally, the book offers prominent features in each chapter

such as:
1.
2.
3.
4.
5.
6.
7.
A section summary
Brief solutions to follow up problems
A chapter perspective
Key terms and key equations
Learning objectives
A heavy reliance on pictorial presentation, as opposed
to text presentation, and not just a quick illustration of
a point/concept; concepts/ideas are conveyed
graphically.
Extensive tables, figures, illustrations and step-by-step
worked examples.
In light of the above, the book should not be underutilized in

General Chemistry classes. I strongly recommend the text
overall.
Mohamad Toutounji
Department of Chemistry, College of Science,
UAE University
99

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Jurnal Internasional

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INTERNATIONAL JOURNAL OF

Hamid M.K. Al-Naimiy

EDITORIAL BOARD OF CONSULTANTS

Hamid M.K. Al-Naimiy

Professor Joseph Hill

Professor Hamid M.K. Al-Naimiy

International Journal of Scientific Research, Vol. 14, 2005

VOLUME 14, 2005

Interstellar Bubbles (Front cover graphic)

IJSR FULL PAPERS

Determination of Radiological Doses of Radon and Natural Radionuclides

R. Najeeb, E. Hussain and U. Masood

Synthesis and Characterization of Some Composite Mesoporous Organosilicas

J.E.G. Mdoe and D.J. Macquarrie

Corals as Bio-indicators to Trace Metal Pollution on the Kuwaiti Coral Islands,

A.H. Bu-Olayan, B.V. Thomas and A.H. Shaker

High Level Expression and Single-step Purification of in vivo Biotinylated

Assessment Study on Selective Physical Characteristics of Lubricating Oils

M.A. Rauf, S. Khaliq and S. Manzoor

Effect of Alkali Salts on the Viscosity of KAHU Grass Black Liquor

M. A. Rauf, M. J. Iqbal and Q. M. Malik

Design, Synthesis and Biological Evaluation of Novel Carbapenems

G.H. Hakimelahi, A.A. Moosavi-Movahedi, A.A. Saboury, V. Osetrov,

Synthesis and Characterization of Some New Heterocyclic Tellurium(IV)Dithiocarbamate Complexes

A. Z. Al-Rubaie and M. Y. Al-Luaibi

Jordan Laid Bare

Robin Harte and Cora Stack

Convex Random Integral Functionals and Epiconvergence

K. Messaoudi, M. L. Leghmizi and M. Zerguine

IJSR BOOK REVIEWS

International Journal of Scientific Research, Vol. 14, 2005

Int. J. Sci. Res., Vol. 14 (2005), pp. 1-9

The various mass-loss events not only greatly

Professor of Astronomy there, a post which he still holds.

The mass, energy and momentum deposition is

the driving forces behind these modifications

Fig. 1. The Orion Nebula (M42).

International Journal of Scientific Research, Vol. 14, 2005

The heated gas has a temperature of about

International Journal of Scientific Research, Vol. 14, 2005

(in the stellar wind) never collapses onto the

Fig. 2. The planetary nebula Abell 49 (HST).

Supernova driven bubbles-supernova remnants

supernova remnant evolves with radius

International Journal of Scientific Research, Vol. 14, 2005

Fig. 3. The radiative supernova remnant N49 (HST).

Mass injection into bubbles

Mass transfer between clumps and flows

It follows also that these diagnostics must be

D-type fronts and exits supersonically in

formation [15]. Recent work [16], has shown

termination shock is supposed to be too weak

Fig. 4. The tails in the Helix nebula, NGC 7293 (HST).

question of X-ray emission from interstellar

Rev. MexAASo. Ast

Astrophysics and Space Science

International Journal of Scientific Research, Vol. 14, 2005

19. J. E. Dyson and T. W. Hartquist, MNRAS

1. F. D. Kahn, BAIN 12, 187 (1954).

20. D. F. Cioffi, C. F. McKee and

26. W. J. Henney and C. R. ODell, AJ 118,

10. B. Lasker, ApJ 140, 700 (1966).

International Journal of Scientific Research, Vol. 14, 2005