PDF About Lalala

1 Introduction
Although, amine oxides were known and studied

before 1900, it was not until 1939, with the issuance of
an I.G. Farbenindustrie patent that material such as
dimethyldodecyl amine oxide were recognized as sur-
factant. After a further 22 years their utility in liquid
household formulations was disclosed and widespread
interest was generated. The substitution for the tradi-
tional fatty alkanolamides as foam booster in dishwash-
ing was the specific example which brought recognition
to the amine oxides. Their favourable weight/effect
ratio offsets the considerably higher cost in this applica-
tion (1).
Reaction of hydrogen peroxide with secondary or
primary amines does not result in commercially useful
materials (2), but with tertiary amines a variety of com-
mercial useful materials obtained which are used not
only in various types of cleaning formulations but also,
proving their utilities in liquid bleach products (surfac-
tant basis), textile industry (anti-static agent), rubber
industry (foam stabilizer), polymer industry (polymer-
ization catalyst), anti-corrosion compositions, lime soap
dispersant, and in deodorant bars (anti-bacterial agent),
due to their compatible synergistic effect and environ-
ment friendly nature. Amine oxides are exothermic,
second order reaction products of tertiary amines and
hydrogen peroxide (3). The nature of tertiary amine in
amine oxides may be aliphatic, aromatic, heterocyclic,
alicyclic or combination thereof. In current amine
oxides the surfactant precursor is generally a C
12
- C
18
alkyldimethyl amine (4).
Amine oxides come under the special class of surfac-
tant known as amphoteric surfactant. The basic reason
behind that is, amine oxide changes from net cationic
via zwitterionics to nonionics on going from low to
high pH; which confirms its amphoteric nature.
This paper presents a detailed review on amine
oxides, with special emphasis on the chemistry of oxi-
dation, physico-chemical studies, various applications
and anti-microbial activity with variation in chain
length. The last part of this paper is briefly focused on
the safety of amine oxides.
99
Correspondence to: V.K. TYAGI, Department of Oil and Paint Technology, Harcourt Butler Technological Institute, Kanpur - 208002, INDIA
E-mail: vinod_tyagi1960@yahoo.com, sudhir_s6@rediffmail.com
JOS
Journal of Oleo Science ISSN 1345-8957 print / ISSN 1347-3352 online
http://jos.jstage.jst.go.jp/en/
Sudhir Kumar SINGH, M. BAJPAI and V.K. TYAGI
JOURNAL OF OLEO SCIENCE

Copyright 2006 by Japan Oil Chemists Society
J. Oleo Sci., Vol. 55, No. 3, 99-119 (2006)
Abstract: Amine oxides are amine-based surfactants, represent one of the smaller classes
of surfactants as compared to alcohol ethoxylates and sulfonated and sulfated anionic
surfactants. However, the uniqueness of the hydrophile in such surfactants provides specific
properties that are difficult, if not impossible, to replicate by the use of classic nonionic and
anionic surfactants. The aim of the present paper is to survey the most important developments
and understandings of the chemistry of amine oxide production, its physico-chemical studies,
applications and environmental properties.
Key words: amine oxide, amine-based surfactant, hydrophile, physico-chemical,
environmental
REVIEW
Amine Oxides: A Review
Edited by M. Iwahashi, Kitasato Univ., and accepted September 20, 2005 (received for review August 29, 2005)
Department of Oil and Paint Technology, Harcourt Butler Technological Institute
(Kanpur-208 002, INDIA)
S.K. Singh, M. Bajpai and V.K. Tyagi
2 The Chemistry of Oxidation for Amine
Oxide Formation
The generally accepted mechanism for oxidation of
tertiary amines with hydrogen peroxide involves the
ammonium peroxide as an intermediate followed by
splitting off water. Previous work (3) strongly suggests
the reversibility of the formation of the ammonium per-
oxide. The proposed mechanism is as follows:
From the above proposed mechanism, the rate of for-
mation of amine oxide can be derived; using steady-
state approximation. The rate of formation of amine
oxide can be written as,
I
Since, the concentration of intermediate is so small
that it cant be measured, so, it has to be replaced by the
concentrations that can be measured.
From proposed mechanism we have,
(II)
Now, because the concentration of (R
3
N. H
2
O
2
)* is
always extremely small, one may assume that its rate
of change be zero {This is called steady-state approxi-
mation (5)}.
Hence,
(III)
From equations (I), (II) and (III) we get,
or
(IV)
where K is overall rate constant and
K = k
1
k
3
/ (k
2
+ k
3
)
So, from equation (IV) it is evident that overall order
of reaction for amine oxide formation is 2, and is in
complete agreement with the experiment.
It has been observed that the degree of conversion of
tertiary amines to its amine oxides is dependent on the
purity of the tertiary amines. With commercially avail-
able undistilled tertiary amine yields in the range of
85% to 87% are obtained. But with freshly redistilled
tertiary amine and with 10% molar excess hydrogen
peroxide the yield may go upto 99% (1).
During the synthesis of amine oxides information on
the amount of unreacted tertiary amine present is need-
ed in order to follow the reaction. A number of analyti-
cal procedure including chromatographic procedures
have been devised to obtain this information. But all of
these procedures have some limitations. Wang and Met-
calfe (6) developed a simple, rapid, non aqueous titra-
tion procedure that makes use of the anamalous salt
behaviour of amine oxides. A modified solvent and
titrant is used to obtain two potential breaks in the titra-
tion. The first break corresponds to half of the amine
oxide. The second break represents the second half of
the amine oxide plus any unreacted amine. With this
information the amine oxide and unreacted amines can
be calculated.
3 Synthesis of Amine Oxides
31 Synthesis of Dimethylalkyl Amine
Oxides and Cyclic Amine Oxides
Friedli et al. (3) prepared dimethyllauryl amine oxide,
N-laurylmorpholine oxide, N-laurylpiperidine oxide
and N-lauryl-3- methyl piperidine oxide with their
respective amines by reacting with 51% aqueous hydro-
gen peroxide at 75. Their rates of formation indicates
that the reaction is of second order and two piperidine
versions form slower than dimethyl-lauryl amine oxide,
while lauryl morpholine reacts much faster.
32 Synthesis of 2-alkoxy-N, N-
dimethylethyl Amine N-oxides
Hayashi et al. (7) prepared 2-lauryloxy-N,N-
dimethylethyl amine N-oxide with its amine by react-
ing with 30% aq hydrogen peroxide at room tempera-
ture. The amine oxide was concentrated in a drying box
under reduced pressure resulted into a crystalline solid
amine oxide. Such amine oxides are stable up to 100,
but decomposes rapidly to vinyl ethers at 150. At low
temperature they deoxygenated to their tertiary amine.
Hygroscopic property decreases as length of the alkyl
chain increases.
33 Synthesis of Alkyl Benzene Derived
Amine Oxides
Marmer and Linfield (8) prepared aromatic amine
oxides via a three step route from a variety of pure 1-
phenylalkanes and also from a commercial detergent
alkylate mixture. The process includes (i) sulfonation of
R NO
K R N H O
3 3 2 2
=
[ ][ ]
R NO
k k R N H O
k k
3
1 3 3 2 2
2 3
=
[ ][ ]
+
R N H O 3 2 2
0
.. ( )
=
R N H O
k R N H O k R N H O
k R N H O
3 2 2 1 3 2 2 2 3 2 2
3 3 2 2
.
.
.
( )
=
[ ][ ]
[ ]
[ ]
R NO
k R N H O
3 3 3 2 2 ( )
=
[ ]
.
R N H O R N H O R NO H O
3 2 2 3 2 2 3 2
+ ( )
+ .
k
1
k
3
k
2 rxn.intermediate
100
J. Oleo Sci., Vol. 55, No. 3, 99-119 (2006)
the phenylalkane with chlorosulfonic acid in 1,2-
dichloroethane. (ii) reaction of resulting alkarylsulfonyl
chloride with H
2
N(CH
2
)
3
NMe
2
(Me is for -CH
3
group)
or H
2
N(CH
2
)
3
N(CH
2
CH
2
OH)
2
under anhydrous condi-
tions at room temperature, and (iii) oxidation of result-
ing tertiary amines with 30% aqueous hydrogen perox-
ide at 65. Such aromatic amine oxides were found to
be thermally stable below 125.
34 Synthesis of N, N-dimethylalkyl Amine
N-oxide by Micellar-Autocatalysis
Rathman and Kust (9) investigated the synthesis of
N,N-dimethyldodecyl amine N-oxide in aqueous solu-
tions by micellar autocatalysis. The lipophilic reactant,
dimethyl dodecylamine was initially solubilized in
micellar solutions of the amine oxide surfactant, result-
ing in substantially higher reaction rates. Amine con-
versions of 90-100% were obtained within 2 h at 70.
The effects of reactant concentrations, temperature, and
initial surfactant concentration were studied. This
method is important because of two main reasons: (I)
Micellar auto catalysis provides a method for synthesiz-
ing surfactants without employing volatile organic sol-
vents in the reaction medium, providing potential eco-
nomic and environmental benefits and (II) studies of
micellar auto catalysis can refine and extend the under-
standing of the other types of reactions in aqueous sur-
factant solutions.
4 Analysis of Amine Oxides
Pinazo and Domingo (10) investigated turbidimetric
analysis of amine oxides and amine oxide - anionic sur-
factant mixtures. This automatic analysis has been
shown to be a simple and accurate method to determine
the actives in anionic surfactants as well as the actives
in amine oxides. This technique has been applied to
dilute solutions of these surfactants in the mM range.
Turney and Cannell (11) determined a method known
as alkaline methylene blue method for determination of
anionic surfactants, also this method in conjunction
with the acid methylene blue titration may be used to
determine the amount of amine oxides in formulated
products like detergents etc, based on the cationic
nature of amine oxides at low pH and nonionic nature at
high pH. For concentrations of less than 100 PPM a
spectrophotometric method was used.
5 Physico-Chemical Studies on
Amine Oxides
It is well known that the dissociation constant K of
weak electrolytes at the charged interface are different
from those in their solutions. Funasaki (12) were meas-
ured the dissociation constant K of acid -base indicators
in aqueous solutions of 20 mM dodecyldimethyl amine
oxide (DDAO), 1% Brij 35 (C
12
H
25
-(O-CH
2
-CH
2
-)
23
-
OH), and 20 mM cetyltrimethylammonium bromide
(CTAB) spectroscopically and also determined the
applicability of the equation p
K
= p
Ki
(0.4343 e
0
y
0
/kT),
to the micelle-solubilizate systems. The surface poten-
tial Y
0
of mixed micelles of sodium dodecyl decaoxy
ethylene sulfate and dodecyldimethylamine oxide in the
presence of 0.1 M sodium chloride at 25 have found
by Tokiwa and Ohki is somewhat unreasonable.
Funasaki (13) evaluated more reasonably the surface
potential of these mixed micelles.
It has been known that micelle of ionic surfactants
grows with increasing concentration of added salt. The
electric repulsion between charged headgroups is a
main size - limiting factor in micelle formulation, and
the effect of added salt on the micele size has been
101
J. Oleo Sci., Vol. 55, No. 3, 99-119 (2006)
Fig. 1 Molecular Structures of Respective Amine Oxides
of Section 3.
attributed to the electrostatic shielding effect of counter-
ions on the charged micelle. Ikeda et al. (14) studied
the effects of ionization on micelle size of aqueous
NaCl solution of dimethyldodecyl amine oxide, by
using the light-scattering method for the determination
of molecular weight, from the Debye plot.
Imae and Ikeda (15) measured angular dependence of
light-scattering from micellar solutions of dimethyl-
oleyl amine oxide in water and 10
-4
M NaCl at different
micelle concentrations from the critical micelle concen-
tration (CMC) to 0.15 10
-2
g cm
-3
. The intensity of
light scattered from the micellar solutions increases
with an increase in scattering angle, in contrast to the
usual behaviour. This is caused by the effect of external
interference which is stronger than that of internal inter-
ference.
Dimethyldodecyl amine oxide and dimethyltetrade-
cyl amine oxide are known to form spherical micelles
in water and 0.20 M NaCl solutions; but, if the hydro-
carbon part of nonionics with amine oxide head group
is made longer for e.g. dimethyloleyl amine oxide,
forms rod like micelles in dilute aqueous solutions
determined from light-scattering measurements. Ritsu
Kamiya et al. (16) presented electron micrographs of
rod like micelles regenerated from aqueous solutions of
dimethyloleyl amine oxide and gave support for the
results from the light scattering measurements.
Imae and Ikeda (17) investigated the pH dependence
of upper and lower consolute phase boundaries for
aqueous NaCl solutions of dimethyloleyl amine oxide
at temperatures between 5 and 85 for pH less than 8
at different NaCl concentrations. The consolute phase
boundary is also given as a function of surfactant con-
centration. Toyoko Imae et al. in their another investi-
gation (18) found that aqueous solutions of dimethyl-
alkyl amine oxides (CnDAO, n = 16,18) present the iri-
descence at surface concentrations of 0.3 - 2 wt%, when
the temperature of the solutions is lower than 23 for
C
16
DAO and 46 for C
18
DAO. The Colour changes
from yellowish red to blue with an increase in surfac-
tant concentration, and disappears at pH below Ca.
6.5 for C
16
DAO and below Ca. 4.5 for C
18
DAO (see
Figs. 2 & 3).
Polymer-micelle complexes have found applications
in many industrial products, such as paints and coat-
ings, laundry detergent, and cosmetic products and they
also play a role in tertiary oil recovery. Brackman and
Engberts (19) studied the influence of the nonionic
water soluble polymers poly (vinyl methyl ether)
(PVME), poly (propylene oxide) (PPO), and poly (ethy-
lene oxide) (PEO) on the aggregation behaviour of n-
dodecyldimethyl amine oxide (DDAO), at various
stages of protonation.
Hoffman et al. (20) reported the phase diagram of the
ternary surfactant system tetradecyldimethyl amine
oxide / heptanol / water for small surfactant concentra-
tions. With increasing cosurfactant / surfactant ratio, the
generally observed sequence of the phases L
1
, L
a
and
L
3
is found. These single phases are separated by nar-
row two phase regions. In all these phases the L
3
or so-
called sponge phase has drawn much attention. It is a
low viscous, slightly turbid, and optically isotropic
102
J. Oleo Sci., Vol. 55, No. 3, 99-119 (2006)
Fig. 2 The Phase Diagram under the Visual Inspection for
Aqueous Solutions of C
16
DAO. I, Transparent and
Isotropic Solution; II, Turbid Solution; III,
Iridescent Solution.
Reprinted from J. Colloid Interface Sci., Vol. 131, 601-602,
Copyright with permission from Elsevier.
Fig. 3 The Phase Diagram under the Visual Inspection and
the Crossed Nicol for Aqueous Solutions of
C
18
DAO., visual inspection;
-
-
,
crossed nicol. I, transparent and isotropic solution;
II, turbid solution; III, iridescent solution; IV,
weakly birefringent solution; V, strongly
birefringent solution.
phase which shows flow birefringence under shear.
The interactions between water and nonionic surfac-
tants are important in both fundamental and applied
surface chemistry. Mol et al. (21) determined the struc-
tural parameters of the hexagonal and lamellar phase of
the dimethyldodecyl amine oxide (DDAO)- water sys-
tems using X-ray diffraction. The result obtained are
discussed in the light of the on going debates about (i).
The relative importance of steric / protrusion forces and
hydration forces between surfactant bilayers and (ii) the
molecular origin of the temperature dependence of the
interactions displayed in several nonionic water sys-
tems.
The electrostatic potential is one of the important
factors for the stabilization of dispersed colloidal parti-
cles in aqueous medium. The electrokinetic phe-
nomenon such as electrophoresis, which may be evalu-
ated by mobility, is in close connection with electrostat-
ic potential. Imae and Hayashi (22) performed elec-
trophoretic light scattering measurements for aqueous
NaCl solutions of dodecyl-, tetradecyl-, and
oleyldimethyl amine oxides (C
12
DAO, C
14
DAO &
ODAO). It was observed that Electrophoretic mobility
changed with the degree of protonation (see Figs. 4 to
7).
It is very interesting to investigate the behaviour of
surfactant mixtures, which have different head groups
with synergistic interactions but also different chains
with antagonistic interactions. Hoffman and Possnecker
(23) investigated the mixing behaviour of surfactants by
using the phase separation model. In their investigation
they used pairs of nonionic hydrocarbon surfactants and
perfluorinated anionic surfactants; in one example they
took the tetradecyldimethyl amine oxide as nonionic
surfactant with the mentioned anionic surfactants. With
this anionic surfactant it was possible to reach nearly
identical CMC values of the nonionic and the anionic
surfactant. To create special starting conditions, they
used a hydrophobic tetraethyl ammonium counterion of
the anionic surfactant (see Figs. 8 & 9).
Desnoyers et al. (24) studied the thermodynamic
micellar properties of n-octyldimethyl amine oxide
hydrochloride (OAO.HCl) in water. The apparent molar
volumes and heat capacities of OAO. HCl were meas-
103
J. Oleo Sci., Vol. 55, No. 3, 99-119 (2006)
Fig. 4 Electrophoretic Light Scattering Power Spectra for
0.1 M NaCl Solutions of C
14
DAO at Surfactant
Concentration of 0.510
-2
g cm
-3
with Various
Degrees of Protonation.
Reprinted from Langmuir, Vol. I, 3385-3388, Copyright with
permission from Am. Chem. Soc.
Fig. 5 Electrophoretic Mobility as a Function of Degree of
Protonation for 0.1 M NaCl Solutions of C
14
DAO at
Surfactant Concentration of 0.510
-2
g cm
-3
.
Protonation for 0.03 M NaCl Solutions of ODAO at
Surfactant Concentration of 0.110
-2
g cm
-3
.
ured in water as a function of concentration between 2
and 55 and the apparent molar relative enthalpies of
the same system at 25. Also, the apparent molar
expansibilities were calculated from the temperature
dependence of the volumes (see Figs. 10 to 14).
Okamura et al. (25) investigated supramolecular
assemblies in ternary systems of alkyldimethyl amine
oxide (C
n
DAO, n=12, 16)/Cinnamic acid/ water by
small angle neutron scattering(SANS). The fine struc-
tures of molecular assemblies were quantitatively
examined for solutions with different mixing ratios.
Since SANS is operated at the neutron radiation of 1-
16 wavelength, it results in distances of nanometer
scale such as the shape of small micelles, the crossec-
tion of rod like micelles, and the lamellar thickness and
distance. Such data have never been obtained from
TEM and light scattering experiment. The molecular
arrangement in supramolecular assemblies is discussed
in relation to the structure geometry (see Figs. 15 to
20).
The influence of thermodynamic parameters on the
mechanism of self-organization of surfactants in aque-
ous solutions are of deep interest giving a deep insight
into the new science of complex fluids. The rich phase
behaviours of complex fluid systems is associated with
the fact that particles are molecular aggregates rather
than simple molecules. The aggregates are thermody-
namically stable structures, which change their size and
shape in response to changes in concentration, compo-
sition, counterion species, temperature, pressure and
other conditions. Garski et al. (26,27) studied by means
of small angle neutron scattering (SANS) experiments,
the dependence on concentration and temperature (26),
and pressure (27) of the mean aggregation number (N)
of rodlike tetradecyldimethyl amine oxide micelles in
D
2
O. Small angle scattering with neutrons (SANS) or
with X-rays (SAXS) is one of the most direct methods
for obtaining information about structural details and
their changes and also may help to clarify the results
obtained by other experimental techniques. The combi-
nation of pressure, temperature and SANS or SAXS in
the study of physical properties of micellar systems
opens up new prospects for examining amphiphilic
solutions on a microscopic level.
Zimmerman and Schnaare (28) extended the method
of Rathman and Christian for determining the micellar
activities of dimethyldodecyl amine oxide by pH titra-
tion in the presence of swamping electrolyte to accom-
modate non swamping electrolyte conditions.
Dimethyltetradecyl amine oxide was used as a model
104
J. Oleo Sci., Vol. 55, No. 3, 99-119 (2006)
Protonation for 0.05 M NaCl Solutions of C
12
DAO
at Surfactant Concentration of 10
-2
g cm
-3
. Square
signs are data for 0.1 M NaCl solutions of C
12
DAO.
Fig. 8 Plot of the Surface Tension vs the Logarithm of the
Total Surfactant Concentration of the System (I)
C
14
DMAO/NEt
4
-PFOS in 10 mM NEt
4
OH Solution
at Different Mixing Ratios C
14
DMAO/NEt
4
PFOS: a, 9:1; b,7:3; c, 3.5:6.5; d, 2:8.
Reprinted from Langmuir, Vol. 10, 381-389, Copyright with
Fig. 9 cmc as a Function of the Mole Fraction a of
NEt
4
PFOS for the Mixtures (I) C
14
DMAO/NEt
4
PFOS in 10 mM NEt
4
OH Solution.
Reprinted from Langmuir, Vol. 10, 381-389, Copyright with
surfactant in this study. Amine oxide surfactants exist in
solution either as the unprotonated, electrically neutral
Zwitterionic form (AO
) or as the protonated, cationic

form (HAO
+
).
Myrzakozha et al. (29) reported the molecular orien-
tation and structure in one and multilayer Langmuir -
Blodgett (LB) films of octadecyldimethyl amine oxide
(C
18
DAO) and dioctadecyldimethyl ammonium chlo-
ride (2C
18
DAO) on gold and silver-evaporated glass
slides. It was found that the structures of LB films show
clear dependence upon the number of monolayers and
substrates. The most important finding was that the ori-
entation and order of alkyl chains in the first layers are
changed largely upon the deposition of the second lay-
ers. In their another investigation (30), they reported the
105
J. Oleo Sci., Vol. 55, No. 3, 99-119 (2006)
Fig. 10 Apparent Molar Volumes of OAOHCl at Various
Temperatures; Full Lines are from the Mass-Action
Model.
Reprinted from Langmuir, Vol. 11, 1905-1911, Copyright
with permission from Am. Chem. Soc.
Fig. 11 Apparent Molar Heat Capacities of OAOHCl at
Various Temperatures; Full Lines are from the
Mass-Action Model.
Fig. 12 Apparent Molar Expansibilities of OAOHCl and
OAO at 25; Full Lines are from the Mass-Action
Model.
Fig. 13 Apparent Molar Relative Enthalpies of OAOHCl,
OAO, and OABr at 25; Broken Lines are from
the Mass-Action Model.
Fig. 14 Temperature Dependence of Volume Parameters of
OAOHCl and OAO from the Mass-Action Model;
s are from the Second Series of Measurements.
thermal behaviour of the one - and five - monolayer LB
films of C
18
DAO and 2C
18
DAC on the gold and silver
evaporated glass slides. It has been generally recog-
nized that the interaction between a head group and a
substrate and the longitudinal interaction between
monolayers are two important factors which control the
thermal stability of LB films. LB films have been a
matter of keen interest because of their fundamental
importance in surface science as well as their potential
application in optoelectronics.
Because the elucidation of the relationship between
the structure and function of the films is essential for
both basic studies and applications, structural character-
ization has been made for LB films of various com-
pounds from simple fatty acids to complicated organic
dyes by use of IR, UV-Vis, and Raman spectroscopies
and atomic force microscopy (AFM). Structural
changes in the films induced by aging, doping and
variations in pH and temperature have also been
explored extensively. Myrzakozha et al. (31) presented
an IR study of structure and aging -behaviour of one-
layer LB films of C
18
DAO and 2C
18
DAC. The IR meas-
urements suggests that the alkyl chains of one-layer
LB film of C
18
DAO on a gold-evaporated glass slides
106
J. Oleo Sci., Vol. 55, No. 3, 99-119 (2006)
Fig. 15 SANS Data for the C
12
DAO/Cinnamic Acid/D
2
O
System. Mixing Ratio: , X=0; , X=0.2; ,
X=0.4; , X=0.6.
(Q is Bragg wave number and I is SANS intensity)
Fig. 16 Replots of SANS Data for the C
12
DAO/Cinnamic
Acid/D
2
O System at Mixing Ratios X=0 and 0.2.
12
DAO/Cinnamic
Acid/D
2
O System at Mixing Ratios X=0.45. 0.6
and 1.
Fig. 18 SANS Data for the C
16
DAO/Cinnamic Acid/D
2
O
System. Mixing Ratio: , X=0; , X=0.2; ,
X=0.4; , X=0.6.
have some gauche conformers i.e., less ordered than
that of 2C
18
DAC. It was also noted that the molecular
orientation and structure in the film showed strong pH
dependence, presumably because of the strong interac-
tion between the headgroups and the substrates (see
Figs. 21 to 26).
Kato and Imae (32) investigated the surface forces
between glass surfaces in aqueous hexadecyldimethyl
amine oxide (C
16
DAO) solutions at different surfactant
concentrations and upon addition of cinnamic acid or
HCl. The variation of surface forces depending on the
conditions is discussed, concerning the adsorption
structure of C
16
DAO on glass surfaces. Also, the inter-
surface interaction forces are compared with the forces
which act in molecular assemblies in solutions.
Fukada et al. (33) investigated the lyotropic phase
behaviours of the nonionic and cationic (protonated)
forms of dodecyldimethyl amine oxide (DDAO). Phase
diagrams for DDAO + water, hydrochlric acid salt of
DDAO (DDAOHCL) + water and an equimolar mixture
of DDAO and DDAO HCl, (DDAO (1/2) HCl) + water
systems were determined on the basis of polarized light
microscopy, small angle x-ray diffraction, and differen-
tial scanning calorimetry. Also, water activity was meas-
ured to see the non ideality of water in lyotropic liquid
crystaline phases.
Kiraly and Findenegg (34) determined the material
and enthalpy balances of adsorption of the N,N-
dimethyldecyl amine N-oxide (C
10
DAO) and n-octyl b-
D-monoglucoside (C
8
G
1
) from dilute aqueous solutions
onto hydrophilic silica glass and hydrophobic graphite
(graphitized carbon black) at 298.15 K up to the critical
micelle concentration. An automated flow sorption/
microcalorimeter system was used for simultaneous
measurements of the adsorption isotherm and the
enthalpy isotherm of displacement.
Barlow et al. (35) studied the internal structure of oil
-in-water microemulsion dropletes by SANS using con-
trast variation. The single chain surfactant used was N,
N-dimethyldodecyl amine N-oxide, and the oil phase
was one of two semipolar ethyl esters, ethylhexade-
canoate or ethyl octanoate.
Clays are added to many emulsions designed for
industrial applications. During the emulsification sur-
face active agents adsorb onto clay and produce
hydrophobic colloids. Adsorption of surfactant onto
clays is also of interest for environmental issues and
enhanced oil recovery. Studies of clay - surfactant inter-
actions deal with ionic and neutral compounds. Gevers
and Grandjean (36) studied that
7
Li and
23
Na NMR
spectrum of clay suspension in water have shown how
the smectite structure and nature of alkali counterions
modulate the quadrupolar interaction. These probes,
together with
13
C and
2
H nuclei, have been also used to
study the interaction of dodecyldimethyl amine oxide
with laponite and differently charged saponites dis-
107
J. Oleo Sci., Vol. 55, No. 3, 99-119 (2006)
16
DAO/Cinnamic
Acid/D
2
O System at Mixing Ratios X=0 and 0.2.
16
DAO/Cinnamic
Acid/D
2
O System at Mixing Ratios X=0.4, 0.6, and
1.
108
J. Oleo Sci., Vol. 55, No. 3, 99-119 (2006)
Fig. 21 (a) An IR RA Spectrum of One-Layer LB Film of
C
18
DAO on a Gold-Evaporated Glass Slide. (b) An
IR Transmission Spectrum of a One-Layer LB
Film of C
18
DAO on a CaF
2
Plate. (c) An IR/ATR
Spectrum of a One-Layer LB film of C
18
DAO on a
Ge Prism.
(Aqueous subphase at pH 5.8)
Fig. 22 (a) An IR RA Spectrum of One-Layer LB Film of
2C
18
DAC on a Gold-Evaporated Glass Slide. (b)
An IR Transmission Spectrum of a One-Layer LB
Film of 2C
18
DAC on a CaF
2
Plate. (c) An IR/ATR
Spectrum of a One-Layer LB Film of 2C
18
DAC on
a Ge prism.
(Aqueous subphase at pH 5.8)
Fig. 23 (a) An IR RA Spectrum of an Aged One-Layer LB
Film of C
18
DAO on a Gold-Evaporated Glass
Slide. (b) An IR Transmission Spectrum of an
Aged One-Layer LB Film of C
18
DAO on a CaF
2
Plate. (c) An IR/ATR Spectrum of an Aged One-
Layer LB Film of C
18
DAO on a Ge Prism. All of
the spectra in this figure were measured after the
films were kept in a Desiccator for 24 h.
Fig. 24 (a) An IR RA Spectrum of an Aged One-Layer LB
Film of 2C
18
DAC on a Gold-Evaporated Glass
Slide. (b) An IR Transmission Spectrum of an
Aged One-Layer LB Film of 2C
18
DAC on a CaF
2
Plate. (c) An IR/ATR Spectrum of an Aged One-
Layer LB Film of 2C
18
DAC on a Ge prism. All of
the spectra in this figure were measured after the
films were kept in a desiccator for 24 h.
persed in surfactant solutions (see Figs. 27 & 28).
Kakehashi et al. (37) examined the effects of the
hydrocarbon chain length, the bulkiness of the polar
head group, the added salt concentration, the surfactant
concentration, and temperature on the hydrogen ion
titrations of amine oxides. The surfactants studied are
alkyldimethyl amine oxides (C
n
DAO) with hydrocarbon
Chain lengths of 10-16, and N,N-bis(2-hydroxy ethyl)
alkyl amine oxide (C
n
DHEAO) with hydrocarbon chain
lengths of 10-14. From the results of hydrogen ion titra-
tion, the surface electric potentials were estimated.
Kawasaki and Maeda (38) used Fourier-transform
infrared spectroscopy (FT-IR) coupled with attenuated
total reflection (ATR) to investigate the proposed H-
bond between the head groups of C
12
DAO (a = 0.5) in
both an aqueous medium and the solid state. To clarify
this hydrogen bond (H-bond), they focused on the OH
band of the headgroup of C
12
DAO (a = 0.5 and 1) in
this study (see Figs. 29 to 32).
Dielectric relaxation spectroscopy is a very powerful
method to investigate the motion of molecules possess-
ing electric dipole moments. Itatani and Shikata (39)
examined the dielectric relaxation behaviour of aque-
ous dodecyldimethyl amine oxide (DDAO) solutions by
changing the concentrations of DDAO, NaBr and the
109
J. Oleo Sci., Vol. 55, No. 3, 99-119 (2006)
Fig. 25 (a) An IR RA Spectrum of a One-Layer LB Film
of C
18
DAO on a Gold-Evaporated Glass Slide
Prepared from the Aqueous Subphase at pH 3.0.
(b) An IR Transmission Spectrum of a One-Layer
LB Film of C
18
DAO on a CaF
2
Plate Prepared from
the Aqueous Subphase at pH 3.0.
Fig. 26 (a) An IR RA Spectrum of a One-Layer LB Film
of 2C
18
DAC on a Gold-Evaporated Glass Slide
Prepared from the Aqueous Subphase at pH3.0. (b)
An IR Transmission Spectrum of a One-Layer LB
Film of 2C
18
DAC on a CaF
2
Plate Prepared from
the Aqueous Subphase at pH 3.0.
Fig. 27
7
Li Double-Quantum Filtered Spectra of Lithium-
Exchanged Laponite Suspended in Water (Clay
Content, 17.8 g/L; Li
+
Concentration, 13.0 mM)
(Top, q = 90; Bottom, q = 54.7).
Fig. 28
7
Li Double-Quantum Filtered Spectrum (q =
54.7) of Lithium-Exchanged Saponite (Charge
0.35)(Clay Content, 40.0 g/L; Li
+
Concentration,
37.1 mM) Suspended in Surfactant Solution (0.1
M).
pH value to elucidate dynamic features in micelles of
DDAO in aqueous solutions.
Adsorption and self assembly are central characteris-
tics features of surfactant molecules. The adsorption of
surfactants from solutions onto solid surfaces has been
investigated over many years in relation to numerous
practical applications, as well as the scientific interest.
Hideya Kawasaki et al. (40) investigated the effect of
protonation on the aggregate structures of tetradecyl-
adimethyl amine oxide (C
14
DAO) surfactants at mica-
solution and graphite - solution interfaces by atomic
force microscopy (AFM). C
14
DAO solutions are mix-
tures of the nonionic (C
14
H
25
(CH
3
)
2
N 0) and the ion-
ized (protonated) cationic species (C
14
H
25
(CH
3
)
2
N-
110
J. Oleo Sci., Vol. 55, No. 3, 99-119 (2006)
Fig. 29 (A) FT-IR Spectra of Solid C12DAO with
Different Degrees of Protonation, a (a = 0, 0.5,
and 1), at 25. (B) Comparison of the IR Spectra
of C12DAOHCl with that of C12DAOHNO
3
.
Fig. 30 (A)FT-IR-ATR Spectra of C12DAO with Different
Degrees of Protonation, a (a = 0, 0.5, and 1), in
the Aqueous Liquid Crystalline Phase (Hexagonal)
at 25.
The Weight Percent of the Surfactants is 55.(B)FT-
IR-ATR Spectra of C1DAOHCl in Aqueous
Solutions of Various Concentrations at 25.The
weight percent of C1DAOHCl(from top to bottom)
was 40, 30, 20, and 5. For comparison, the FT-IR-
ATR spectrum of the C12DAOHCl (55 wt%) is
also shown (a). The spectral subtraction of water
from the IR spectra was performed on only
C1DAOHCl spectra of 5 wt%.
Fig. 31 Dependence of a Continuous Absorption Band
(1300-800cm
-1
) of the Solid C12DAO on the
Degree of Ionization, a. The peak intensity I
N
is
normalized by that of the symmetric CH
2
stretching band.
Fig. 32 FT-IR-ATR Spectra of C12DAO with Different
Degrees of Protonation, a (a = 0, 0.5, and 1), in
Aqueous Solutions at 25. The weight percent of
the surfactants is 55.
OH). The composition a
M
(the degree of ionization) in
the micelle is determined by pH under a given ionic
strength. The mixture of the protonated and unprotonat-
ed species show an extreme synergism due to the short
range attractive interaction between the headgroups.
Pettersson and Rosenholm (41) reported on
microcalorimetric studies of the adsorption of
alkyldimethyl amine oxides (C
n
DAO with n = 8, 10 and
12) on mesoporous and slightly negatively charged sili-
ca gel from aqueous solutions at 298.15 K. Since the
pH was natural, the study of C
n
DAO concerns adsorp-
tion from mixed nonionic-cationic surfactant solutions.
Due to increase in pH, the proportion of cationic surfac-
tant decreases at increasing surfactant content. The
adsorption from dilute solution of all surfactants studied
was exothermic and enthalpically driven due to forma-
tion of H-bonding between nonionic headgroups and
surface silanol groups, and due to electrostatic interac-
tions between ionic adsorbates and oppositely charged
dissociated surface silanol groups. Pettersson and
Rosenholm (42) also studied the x-potential of granular
silica gel interacting with aqueous solutions of
C
n
DAO(with n = 8, 10 and 12). The x-potential was
determined by measuring the streaming potential across
the capillary of the plug of sample.
Aqueous mixtures of alkyl amine oxides and dodecyl
sulfates draw much attention owing to their peculiar
physico-chemical behaviour and miscellaneous applica-
tions. Smirnova et al. (43) examined that strong syner-
gistic effects are responsible for the specific phase
behaviour of amine oxide-sodium (magnesium) dodecyl
sulfate micellar solutions. The dissolution temperature
and the CMC value are greatly dependent on relative
surfactant concentration and pH. The phase diagrams in
the two studied systems C
12
AO- Me DS- H
2
O are quite
similar at low pH and differ at the natural acidity. At
low pH, the complex AOH
+
DS
-
is crystallized over a
wide range of surfactant based concentrations (see Figs.
33 to 40).
Solid-solution phase behaviour of surfactant mix-
tures is important both in theoretical and applied
aspects and has been studied extensively. The dissolu-
tion temperature of binary mixed surfactants has been
reported to show a temperature maximum where the
complex between the two components is formed.
Kawasaki et al. (44) studied the effects of protonation
(ionization) of alkyldimethyl amine oxides on the disso-
lution temperature in aqueous media by differential
scanning calorimetry. Effects of alkyl chain-length on
the dissolution temperature for a homologous series of
octadecyl-, hexadecyl-, and tetradecyldimethyl amine
oxide were also examined. It was observed that the
transition temperature and associated thermodynamic
quantities DH and DS increased systematically with the
chain length.
6 Applications of Amine Oxides
The application of these compounds varies with the
size of the main alkyl chain and the substituents on the
nitrogen atom of amine oxide. For example, the coco
range alkyldimethyl amine oxide serve as very effective
foam boosters in light duty detergents and shampoos
111
J. Oleo Sci., Vol. 55, No. 3, 99-119 (2006)
Fig. 33 Dependence of pH on x
HCl
for C
12
AO-NaDS-HCl-
H
2
O and C
12
AO-Mg(DS)
2
-HCl-H
2
O Solutions at
x
AO
= x
MeDS
= 0.0005 and t = 50.
Fig. 34 The Dissolution Temperature versus x
AO
in the
C
12
-AO-NaDS-HCl-H
2
O System at x
total
= 0.001.
(45), while the higher stearyl amine oxides can be used
as hair conditioners (46). Tomah company of Milton,
WI developed a series of amine oxide namely Tomah
AO-728 special, AO-14-2, AO-405 and AO-455 having
property of high foaming, moderate foaming , low
foaming and extremely low foaming respectively, get-
ting application in various types of cleaners. Tomah
AO-728 special is an economical replacement for lauryl
dimethyl amine oxide and many alkanolamides. Tomah
AO-14-2 is considered a more environmentally safe
alternative to solvent coating systems. In particular,
AO-14-2 can replace the use of glycol ethers in clean-
ing compounds. AO-405 and AO-455 are especially
112
J. Oleo Sci., Vol. 55, No. 3, 99-119 (2006)
Fig. 35 The Dependence of the pH Value on x
AO
in the
C
12
-AO-NaDS-HCl-H
2
O Solutions at x
total
= 0.001.
Fig. 36 The Dissolution Temperature as a Function of x
HCl
in the C
12
AO-NaDS-HCl-H
2
O System at x
AO
=
x
NaDS
= 0.0005.
Fig. 37 The Dissolution Temperatures as a Function of
x
NaOH
in the C
12
AO-NaDS-NaOH-H
2
O System at
x
AO
= 0.8 and x
total
= 0.001; x
NaOH
= x
NaOH
/(x
AO
+
x
NaOH
).
Fig. 38 The Dissolution Temperature versus x
AO
in the
C
12
-AO-Mg(DS)
2
-HCl-H
2
O System at Various
pHs; the Total Surfactant Content is 0.1 mol% (0.1
mol%, 10 wt% at Natural pH).
Fig. 39 The Dependence of the pH Value on x
AO
in the
C
12
-AO-Mg(DS)
2
-HCl-H
2
O Solutions of Various
Acidity, x
total
= 0.001.
suited for hard surface applications where low or zero
foam generation is required.
Smith et al. (47) developed, high active alkyldimethyl
amine oxide powder permits the use of this valuable
surfactant in water sensitive formulations such as bar
soaps. Study of the various amine oxide homologs in
key performance properties of soap bars showed them
to be effective foam modifiers, plasticizers and syner-
gistic lime soap dispersants. The solid amine oxides
were found to be a versatile additive which could readi-
ly be formulated into a wide variety of personal care
bars.
Crutcher et al. (48) studied the interaction of solid
alkyldimethyl amine oxide (AX) and ditallowdimethyl
ammonium chloride (DTMAC) and ditallowdimethyl
ammonium sulfate (DTMAS) quats in representative
types of fabric softener systems with particular focus on
synergistic behaviour. Softening, whiteness retention,
wetting, static build up and detersiveness were evaluat-
ed for laundry rinses, laundry detergents and dryer
sheets. In laundry rinses, blends of amine oxide and
DTMAC proved to be synergistic for improving the
wetting of cotton towels. Although no synergism was
observed in laundry detergents, formulations containing
amine oxide (AX) gave better detersiveness than sys-
tems with DTMAC without the splotching associated
with the quaternary salt. In dryer sheets, it was discov-
ered that blends of amine oxide and DTMAS gave syn-
ergistic softening of cotton towels and were unexpect-
edly effective in preventing static charge build up on
polyester fabric (see Figs. 41 to 55).
Guest and guest-guest interactions. Recently photo-
physical and photochemical properties of intercalation
compounds have attracted increasing interest. By use of
dodecyldimethyl amine N-oxide. Ogawa (49) prepared
smectite / dodecyldimethyl amine N-oxide intercalation
compounds a specific type of surfactant - modified
clays. Intercalation compounds with two different
arrangement of the intercalated dodecyldimethyl amine
N-oxide were obtained, depending on the adsorbed
amounts.
Several instances of synergistic interaction have been
identified between amine oxides and alcohol ethoxy-
lates in various surfactant formulations. Miller et al.
(50) examined whether these benefits could be observed
within the framework of generic hard surface cleaning
formulations. Comparative evaluations were also car-
ried out to determine the performance characteristics of
low- and zero-phosphate systems in which
alkyldimethyl amine oxides and linear alcohol ethoxy-
lates are used. Best cleaning was observed with 1:1
mixtures of the subject surfactants, but substantial
improvements over alcohol ethoxylate alone also were
noted with formulations that contained lower ratios of
amine oxide. These system displayed good cleaning
performance when tested on vinyl floor tiles soiled
with an oily/ particulate soil.
Melnikova and Lindman (51) investigated pH con-
trolled DNA condensation in the presence of dode-
cyldimethyl amine oxide (DDAO). Interactions between
DNA and amphiphilic systems have attracted much
attention from the pharmaceutical perspective: e.g,
cationic lipid systems are found to be effective as a
nonviral vehicle for controlled gene transfer. In the
investigation it was observed that positively charged
DDAO ions in vesicular form behave as a more effi-
cient DNA-condensing agent than those in the micellar
form.
Aqueous mixtures of the single - chain zwitterionic
surfactant alkyldimethyl amine oxide (C
14
DMAO) with
other surfactants and cosurfactants are known to pro-
duce a very rich phase behaviour with different
microstructures when the amphiphilic composition is
varied. From all the phases, the vesicle (L
a
) phase is of
particular interest and has attracted a large number of
investigations because of the potential for these equilib-
rium aggregates to serve as good biological model
membranes as containers for encapsulation and eventu-
al release of drugs, flavors, and fragrances, and as
113
J. Oleo Sci., Vol. 55, No. 3, 99-119 (2006)
Fig. 40 The Dissolution Temperature as a Function of x
HCl
in the C
12
AO-Mg(DS)
2
-HCl-H
2
O System at x
AO
=
x
Mg
1/2
DS
= 0.0005.
114
J. Oleo Sci., Vol. 55, No. 3, 99-119 (2006)
Fig. 41 Laundry Rinse: Softness Rating. Variability =
0.3 for 95% confidence level.
Reprinted from J. Am. Oil Chem. Soc., Vol. 69, 682-689,
Copyright with permission from Am. Oil Chem. Soc.
Fig. 42 Laundry Rinse: Whiteness Rating. Variability =
Fig. 43 Laundry Rinse: Wetting Rating after Four Cycles.
Fig. 44 Laundry Rinse Synergy: Softness Rating.
Variability = 0.3 for 95% confidence level.
Fig. 45 Laundry Rinse Synergy: Whiteness Rating.
Fig. 46 Laundry Rinse Synergy: Wetting Rating after Four
Cycles.
115
J. Oleo Sci., Vol. 55, No. 3, 99-119 (2006)
Fig. 47 Laundry Rinse Synergy: Antistatic Activity after
One Cycle. Values for untreated fabrics are:
polyester, 2.63 kV; cotton/polyester, 1.01 kV;
cotton, 4.09 kV.
Fig. 48 Laundry Detergent: Softness Rating. Variability =
Fig. 49 Laundry Detergent: Whiteness Rating. Variability
= 0.5 for 95% confidence level.
Fig. 50 Laundry Detergent: Wetting Rating after Four
Cycles.
Fig. 51 Laundry Detergent: Detersiveness Rating from
Tergotometer Evaluations of Dust-Sebum Cotton/
Polyester Test Fabric.
Fig. 52 Dryer Sheet Synergy. Softness rating. Variability =
microreactors for the formation of a range of inorganic
nanoparticles. Hao et al.(52) investigated a cationic /
anionic surfactant system that consists of the zwitteri-
onic alkyldimethyl amine oxide (C
14
DMAO) and the
anionic dihydro-perfluorooctanoic acid (C
6
F
13
CH
2
COOH, DHPFOA, pKa = 3.35). In the investigated sys-
tem, the cationic surfactant is produced by the protona-
tion of the amine oxide by the perfluorooctanoic acid.
As a result of this proton transfer reaction, the mixed
system does not contain excess salt as do other studied
cationic / anionic surfactant systems. With increasing
concentrations of DHPFOA; L
1
-phase, a viscous L
1
-
phase, a two phase L
1
/L
a
-region, and slightly vis-
coelastic L
a
-phase were observed. The main purpose of
this investigation was to demonstrate that in many cases
vesicles in aqueous mixtures of cationic and anionic
surfactants do not form spontaneously but may be the
result of the shear forces that are due to the mixing of
the components.
7 Anti-Microbial Activity of Amine Oxides
with Variation in Chain Length
Alkyldimethyl amine oxides has been shown to have
pronounced anti-microbial activity when used individu-
ally or in combination with alkyl betaines. Although
several studies have been conducted with these com-
pounds in combinations, only equimolar concentrations
of the C
12
/C
12
and C
16
/C
14
chain lengths for the betaine
and the amine oxide, respectively, have been investigat-
ed.
Birnie et al. (53) investigated the anti-microbial
activity of a wide range of chain lengths (C
8
to C
18
) for
both the amine oxide and betaine and also attempted to
correlate their micelle - forming capabilities with their
biological activity. Anti-microbial activity was found to
increase with increasing chain length for both homolo-
gous series up to a point, exhibiting a cut off effect at
chain lengths of approximately 14 for amine oxide and
16 for betaine. Additionally, the C
18
oleyl derviative of
both compounds exhibited activity in the same range as
the peak alkyl compounds. Although each of these
compounds have shown pronounced anti-microbial
activity alone against a variety of microorganisms, they
have also been used in combination to exhibit a syner-
gistic effect (54).
The variation in length of the long-hydrocarbon tail
is thought to influence the extent of anti-microbial
116
J. Oleo Sci., Vol. 55, No. 3, 99-119 (2006)
Fig. 53 Dryer Sheet Synergy: Whiteness Rating.
Fig. 54 Dryer Sheet Synergy: Wetting Rating after Four
Cycles.
Fig. 55 Dryer Sheet Synergy: Antistatic Activity after One
Cycle. Values for untreated fabrics are: polyester,
10.9 kV; cotton/ polyester 2.2 kV; cotton, 2.9kV.
activity. Like most other surfactants, they are believed
to be membrane perturbants, disrupting the cell mem-
brane of the microorganism. It is believed that interac-
tion with the surface of the microorganism is a function
of the polar head groups of the amine oxide, betaine or
mixture of these molecules and that the hydrocarbon
tail subsequently becomes integrated with the lipid
bilayer of the cell membrane. This integration causes a
disruption in the membrane and inevitably causes leak-
age of the cell contents. The length of the alkyl chain of
the surfactants is thought to contribute to the extent of
this membrane disruption, because the higher chain
lengths may be incorporated into the lipid bilayers of
the plasma membrane. The increased hydrophobic
effect of these longer chain tails may aid in this disrup-
tion.
8 Safety of Amine Oxides
Amine oxides have low potential for bioaccumula-
tion in aquatic tissues, indicating low potential for bio
concentration in terrestrial organisms, also this is highly
removed by conventional sewage treatment. Sansoni
(55) demonstrated that amine oxides surfactants are
nonvolatile and readily biodegradable under aerobic and
anaerobic conditions, according to SDA research.
All available information on amine oxides demon-
strates it has low-to-moderate level of toxicity.
Acknowledgment
The authors are grateful to late Prof. R.K. Khanna,
Department of Oil and Paint Technology, H.B. Techno-
logical Institute Kanpur, for his valuable guidance and
motivation.
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1 Introduction

Although, amine oxides were known and studied

JOURNAL OF OLEO SCIENCE

) or as the protonated, cationic

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