Hybridization of sugar alcohols into brucite interlayers via a melt

intercalation process
Kazuya Morimoto
a
, Kenji Tamura
b,
, Tamao Hatta
c
, Seiko Nemoto
c
, Takuya Echigo
b
, Jinhua Ye
b
,
Hirohisa Yamada
b
a
Graduate School of Science and Engineering, Ehime University, 2-5, Bunkyo-cho, Matsuyama 790-8577, Japan
b
National Institute for Materials Science (NIMS), Environmental Remediation Materials Unit, 1-1 Namiki, Tsukuba 305-0044, Japan
c
Japan International Research Center for Agricultural Sciences (JIRCAS), 1-1, Ohwashi, Tsukuba 305-8686, Japan
a r t i c l e i n f o
Article history:
Received 10 August 2011
Accepted 19 November 2011
Available online 1 December 2011
Keywords:
Brucite
Xylitol
D-sorbitol
Intercalation
a b s t r a c t
We report the preparation of organic-brucite (BR) hybrids using harmless sugar alcohols (xylitol, XYL, and
sorbitol, SOR). Since XYL and SOR are solid materials at room temperature, the hybridization was inves-
tigated by comparing two separate methods, hydrothermal treatment and melt mixing. BR-sugar alcohol
hybrids were successfully prepared by a melt intercalation method at 175 C. X-ray diffraction and Fou-
rier transform infrared spectroscopy analyses indicated that organic molecules were intercalated into the
brucite layers, overcoming the barrier of hydroxyl bonds between the BR layers. Moreover, X-ray photo-
electron spectroscopy and thermal analyses showed that the intercalated materials at 175 C resulted in
the formation of covalent MgOC bond linkages on the interlayer surface of BR.
2011 Elsevier Inc. All rights reserved.
1. Introduction
Brucite, BR [magnesium hydroxide, Mg(OH)
2
] is a hydrous layer
mineral, which has been used as a non-toxic industrial material in
applications such as pharmaceutical substances, cosmetic products
[1], catalysts [2], ame retardants [3], and inorganic absorbents [4].
Despite its many practical applications, there have been remarkably
few attempts to construct hybrids of brucite using hostguest com-
plexation. When brucite is organically modied as a nano-hybrid
material, its applicability becomes broader. For example, in terms
of harmless materials, the possibility of using an intercalation
compound based on brucite (an aluminum-free biomedical mate-
rial) as a molecular container for drug delivery systems (DDS) is very
attractive. However, it is difcult to expandeachlayer by hostguest
intercalationreactions because the octahedral layers of brucite carry
no electrical charge, instead being held together tightly through
hydrogen bonding.
Nevertheless, a few reports based on the glycothermal reaction
of layered hydroxides can be found. One approach for preparing or-
ganic-brucite hybrids is through the formation of covalent linkages
on the hydroxyl groups of a layer surface. The incorporation of gly-
cols such as ethylene glycol and glycerol at higher temperatures
has been reported [5]. In another report, the formation of an ethyl-
ene glycolgibbsite [Al(OH)
3
] intercalation compound was studied
[6]. The reaction of gibbsite (one of the polymorphs of aluminum
hydroxide) in ethylene glycol at high temperatures yielded a glycol
derivative of boehmite. In each of these cases, only small molecular
polyols such as ethylene glycol and glycerol have been used to
form the intercalation compounds.
XYL and SOR, which belong to the sugar family, are not hazard-
ous materials according to the Regulation of Hazardous Substances
and are found in numerous food products. If these sugar alcohols
could be xed into brucite interlayers, the resultant hybrids would
have applications as harmless materials in controlling the stability
of an intercalant and in sustained release applications (properties
required for DDS). The purposes of this study are to nd a prepara-
tive methodology for sugar alcohol-brucite hybrids and to charac-
terize them in detail. In this new effort, XYL and SOR were used as
the nontoxic intercalants. This paper reports the intercalation and
interlamellar grafting of these polyols. The intercalation was per-
formed directly in the melt of the sugar alcohol at temperatures
above its melting point.
2. Experimental
2.1. Materials preparation
BR reagent (Rare Metallic Co., Ltd.) was used as a starting mate-
rial. XYL (melting point: 9296 C) and SOR (melting point: 97
100 C) were used as sources of sugar alcohols and were purchased
from Wako Pure Chemicals (Japan). Each sugar alcohol powder
(2 g) was melted at 175 C in a glass vial, and then mixed well with
0021-9797/$ - see front matter 2011 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2011.11.048

Corresponding author. Fax: +81 29 860 4667.

E-mail address: TAMURA.Kenji@nims.go.jp (K. Tamura).
Journal of Colloid and Interface Science 368 (2012) 578583
Contents lists available at SciVerse ScienceDirect
Journal of Colloid and Interface Science
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brucite powder (0.1 g). The mixtures were held at 175 C in a ther-
mostatic oven for 24 h under atmospheric conditions. The products
obtained were washed with methanol and centrifuged. No removal
of sugar alcohols was observed through this washing treatment.
Thereafter, the solid products were dried using a vacuum freeze-
drier. The samples are denoted XYL-BR and SOR-BR.
For comparison, samples treated with an aqueous solvent were
prepared. For that purpose, 4 g of a sugar alcohol was dissolved in
4 mL distilled water. The solution was mixed with 0.1 g of BR. The
suspension was hydrothermally aged using a Teon

-lined stain-
less steel crucible at 175 C for 24 h in a thermostatic oven. After
treatment, the solid product obtained was isolated by centrifuga-
tion and washed with methanol.
2.2. Characterization
The samples were subjected to X-ray diffraction (XRD; Ultima IV,
Rigaku) measurements using Cu Ka radiation (k = 0.15406 nm) un-
der conditions of 40 kV, 30 mA, and 2/min scanning. The morphol-
ogy of the sugar alcohol-brucite samples was observedusing anSEM
(JSM-6700FT, Jeol) at 7 kV. Fourier transform infrared spectroscopy
(FTIR) spectra were obtained with an ATRFTIR spectrometer (IR
Afnity, Shimadzu) on a diamond crystal from 400 to 4000 cm
1
.
Thermogravimetric-differential thermal analysis (TG-DTA) was per-
formed using a Thermoplus TG8120 thermogravimetric analyzer
from Rigaku under a nitrogen ow at a uniform heating rate of
10 C/min up to 600 C.
X-ray photoelectron spectroscopy (XPS) was conducted to fur-
ther investigate the electronic state of the starting material and
the intercalatedsamples preparedby the melt intercalationmethod.
The XPS spectra were collected using a VG-Scienta ESCA-300 (Swe-
den) with a monochromatized Al Ka X-ray source (hv = 1486.6 eV)
at a power of 1.0 kWand a base pressure of 7.3 10
8
Pa in the ana-
lytical chamber. The analysis chamber was equipped with a sputter
gun, inwhichAr gas was usedto sputter cleanthe sample [Mg(OH)
2
]
surface. Electrostatic charging due to the poor electrical conductiv-
ity of sugar alcohol samples was minimized by using a ood gun.
Using a takeoff angle of 90, survey scans were performedto identify
the C, O, and Mg elements. Narrowregion XPS spectra of the C1s and
O1s were acquired with an analyzer pass energy of 75 eV, a step en-
ergy of 0.02 eV, a time per step of 0.5 s, a slit of 0.3 mm, with three
sweeps, and a ood gun of 4 eV. Electron binding energies were cal-
Fig. 1. Powder XRD patterns of brucite with sugar alcohols prepared by (A) the melt
intercalation method and (B) hydrothermal treatment. Proles of: (a) starting
brucite, (b) xylitol supplemented brucite, and (c) D-sorbitol-supplemented brucite.
Fig. 2. SEM images of (a) BR, (b) XYL-BR, and (c) SOR-BR powders.
Fig. 3. The ATRFTIR spectra of brucite with sugar alcohols prepared by (A) the melt
intercalation method and (B) hydrothermal treatment: (a) starting brucite, (b)
brucite with xylitol, and (c) brucite with D-sorbitol.
K. Morimoto et al. / Journal of Colloid and Interface Science 368 (2012) 578583 579
ibratedwithrespect tothe C1s lineat 284.5 eV(CC), anda nonlinear
least-squares curve-ttingprogramwas employedwitha Gaussian
Lorentzian (Voigt) function. Energy differences between theoretical
and measured C1s lines were generally less than 4 eV.
3. Results and discussion
3.1. Structural characteristics of XYL-BR and SOR-BR
Fig. 1A(a) shows the XRD pattern of the brucite starting mate-
rial. The prole shows a d value of 0.48 nm corresponding to the
(001) reection [7]. After the melt intercalation reaction with
XYL, the peak corresponding to the brucite phase (0.48 nm) nearly
disappeared with the concomitant appearance of a new peak at
0.87 nm [Fig. 1A(b)]. Faint peaks at 2h values of 18.4 arose from
the unexpanded phases of brucite. No peak due to the MgO phase
was generated. These results indicate the occurrence of interlayer
expansions of brucite layers resulting from the incorporation of
XYL molecules. In the case of SOR, the relatively broad peak ob-
served at 1.09 nmis a newly constructed phase with the disappear-
ance of the brucite peak (0.48 nm) [Fig. 1A(c)].
By subtracting the thickness of the brucite layers (0.48 nm) from
the observed d values [7], the interlayer spacing (Dd) values of the
XYL-BR and SOR-BR hybrids were calculated to be 0.39 and
0.61 nm, respectively. In comparison, the observed Dd values for
an ethylene glycol-brucite hybrid and a glycerol-brucite hybrid are
0.35 and0.81 nm, respectively [6]. For smectite clays, whichare eas-
ily expandable, the interlayer expansion is reported to be 0.43 nm
for both ethylene glycol and glycerol. Thus, the present results sup-
port the formation of monolayer organic complexes for XYL [8,9].
The molecules may possess a attened monolayer arrangement be-
tween the BR layers. In contrast to the XYL-BR hybrid, the Dd value
for the SOR-BR hybrid (0.61 nm) was much larger, but was still too
small for a bilayer arrangement (Dd 0.8 nm). These results suggest
that SOR molecules formed a monolayer with the molecular long
axes inclined toward the BR layer or a pseudo-bilayer arrangement.
Fig. 1Bshows the XRDpatternof the sample treatedwithanaqueous
solvent. No new peak other than the d
001
peak of the initial brucite
appeared. Thus, nointercalationof sugar alcohol molecules occurred
under these conditions.
Fig. 2 shows SEM images of the starting BR and the XYL-BR and
SOR-BR hybrid powders. The starting BR is composed of planar par-
ticles that vary in size from about 100 nm to larger than 500 nm
[Fig. 2(a)], while the BR treated with XYL is composed of aggregates
of several lm, which consist of BR platelets held together by XYL
molecules [Fig. 2(b)]. In Fig. 2(c), one can see that SOR-BR particles
Fig. 4. (A) TG curves, (B) DTA proles, and (C) DTG proles under a nitrogen ow at a uniform heating rate of 10 C/min for (a) starting brucite, (b) brucite with xylitol, and
(c) brucite with D-sorbitol derived by the melt intercalation.
580 K. Morimoto et al. / Journal of Colloid and Interface Science 368 (2012) 578583
form aggregates of different sizes varying from a fraction of a
micrometer up to ten micrometers in both length and width. The
surfaces of BR layers are coated completely by SOR molecules.
3.2. Hybridization mechanisms of sugar alcohols into BR interlayers
Fig. 3 shows the FTIR absorption spectra of starting BR, BR trea-
ted with XYL, and BR treated with SOR. Starting BR exhibits a sharp
absorption peak at 3694 cm
1
, which is due to the stretching fre-
quency of internal hydroxyl groups [Fig. 3A(a)] [10]. The absorp-
tion band observed at 409 cm
1
is associated with the MgO
lattice vibration. The spectra of the XYL- and SOR-BR hybrids dif-
fered from the starting BR, but were similar to each other [Figs.
3A(b) and A(c)]. The stretching vibration of internal hydroxyl
groups at 3694 cm
1
completely disappeared in both samples.
The doublet at ca. 28002900 cm
1
in the spectra corresponds to
the asymmetric and symmetric stretching vibrations of CH bonds
in the sugar alcohols. The OH stretching vibration of the combina-
tion of sugar alcohols and expanded brucite appeared in the range
30003600 cm
1
[11]. The absorption band of the MgO lattice
vibration also was detected at approximately 410 cm
1
. Further-
more, characteristic peaks associated with metallic alkoxides were
identied near 830 and 1070 cm
1
in the spectra of the XYL-BR and
SOR-BR hybrids [12,13]. These results suggest the partial formation
of MgOC linkages through dehydroxylation [6]. These results
along with the XRD analyses conrmed that both XYL and SOR
molecules inltrated into the brucite interlayers and broke the hy-
droxyl hydrogen bonds at temperatures above their melting points
(under nonaqueous conditions). For the hydrothermally treated
samples, no signicant change was found in the absorption spectra,
with the internal OH band remaining at 3694 cm
1
(Fig. 3B).
Fig. 4 shows the TG, DTG, and DTA proles of starting BR and the
XYL-BR and SOR-BR hybrids. The weight decrease process at around
380 C for BR was endothermic and is attributed to the dehydration
of structural water [Fig. 4C(a)]. The total weight loss of BR, subjected
totemperatures of upto 600 C, was estimatedto be 32%[Fig. 4A(a)],
which lead to the transition from Mg(OH)
2
to MgO. On the other
hand, the hybrids consisting of BR and sugar alcohol decomposed
through several successive processes at around 70 C, 280 C, 400
450 C [Fig. 4B(b) and B(c)]. The rst process was associated with
an endothermic response in DTA and is attributed to the desorption
of physisorbed water molecules [Fig. 4C(b) and C(c)]. The next two
processes were highly exothermic, suggesting thermal degradation
of the sugar alcohol moiety took place at these temperatures, while
BRandsugar alcohol reagents showedonlyendothermic peaks [Figs.
4C(a) and5C]. Total weight losses of the XYL-BRandSOR-BRhybrids,
up to 600 C, were estimated to be 58% and 66%, respectively
[Fig. 4A(b) and A(c)]. The weight loss peak maximumin DTGproles
Fig. 5. (A) TG curves, (B) DTG proles, and (C) DTA proles under a nitrogen ow at a uniform heating rate of 10 C/min for (a) XYL reagent and (b) SOR reagent.
K. Morimoto et al. / Journal of Colloid and Interface Science 368 (2012) 578583 581
of XYL-BRandSOL-BRhybrids occurrednear 389and411 C, respec-
tively (see Fig. 4B). Importantly, these temperatures were higher
than those of the starting brucite and the XYL (322 C) and SOR
(349 C) reagents (Fig. 5B).
Fig. 6shows the XPS C1s, O1s, andMg2s narrowspectra of starting
BR and the XYL-BR and SOR-BR hybrids. In the scans of XYL and SOR,
the binding energy of C1s photoelectrons from the CC species was
strongly observed near 284.5 eV (not shown). The C1s region scans
of XYL-BR and SOR-BR were resolved into three component peaks.
In addition to the peak from the hydrocarbon environment at
284.5 eV, the peaks at 285.2 eV for XYL-BR and at 285.6 eV for
SOR-BR were assigned to a carbon singly bound to oxygen formed
by the dehydroxylation reaction, and the shoulders on the higher
binding energy side at 287.6 eV for XYL-BR and at 288.2 eV for
SOR-BR were assigned to a carbon doubly bonded to oxygen [shown
inFig. 6A(b) andA(c)] [1419]. The O1s peaks inthe scanof BR(529.2
and531.0 eV, whichare labeledas 1and2, respectively) were attrib-
uted to the presence of oxide OMg and hydroxide HOMg, respec-
tively [Fig. 6B(a)] [1719]. In comparison, the main peaks from the
O1s scans of the intercalated XYL-BR and SOR-BR were due to the
carbonyl and oxide species fromsugar alcohols and brucite, respec-
tively [Figs. 6B(b) andB(c)]. Uponintercalationof the sugar alcohols,
signicant changes were observedfor their relative full widthat half
maximum (FWHM). Especially remarkable was the increase of the
FWHM of the O1s peaks for the hybrid sample (e.g., XYL-BR, 2.5 eV
instead of 1.7 eV for the XYL; SOR-BR, 2.25 eV instead of 1.6 eV for
the SOR). Fig. 6C shows narrow spectra of the Mg2s. The sugar alco-
hol treated samples show higher Mg2s binding energies (89 eV for
XYL-BR and 88.4 eV for SOL-BR) than the starting BR (87.4 eV). The
slightly increased binding energy of the magnesiumcore lines could
be due to reduced shielding on the Mg core. Both behaviors, the
broadening of the O1s peak and the Mg2s peak shift observed in
the hybrids, suggest a possible formation of an MgOC linkage to
the MgOH surface.
Table 1 shows the atomic concentration results from the XPS
scans. The XYL-BR and SOR-BR samples clearly have increased
carbon and reduced oxygen content at the surface compared to
BR. To clarify changes in the oxygen ratios for each sample as a
function of degree of grafting, the values for XYL-BR, SOR-BR, and
BR were normalized according to magnesium content, and then
the values for XYL and SOR were normalized according to the car-
bon content of the XYL-BR and SOR-BR samples, respectively (Table
2). The SOR-BR indicates half the carbon ratio than the XYL-BR.
This may be because the physically adsorbed SOR was removed
by argon etching before the XPS measurement. This means that
the XYL molecules are efciently incorporated into the BR interlay-
ers. Furthermore, it is very interesting to compare the O atomic ra-
tios of the hybrid materials (XYL-BR and SOR-BR) and the values of
the O atomic ratio of BR plus that of the sugar alcohols. The oxygen
levels for the hybrids were low compared to the mixture of BR and
sugar alcohols: 2.1 for XYL-BR hybrid versus 2.8 for mixture of BR
and XYL, and 1.8 for SOR-BR versus 2.1 for mixture of BR and SOR.
These results also strongly suggest that the BR and sugar alcohols
had not simply mixed, but that a covalent linkage between the su-
gar alcohols and brucite surface had been formed through MgOC
bonds. This is consistent with the exothermic DTA proles of the
hybrids [curves (b) and (c) in Fig. 4C], suggesting BR incorporated
the sugar alcohols through dehydration.
During the melt-mixed process, the formation of the brucite-su-
gar alcohol derivatives (covalent linkage) must involve the dis-
placement of hydroxyl groups in the coordination sites of
magnesium into the alkoxyl group. Although this is the reverse
reaction of alkoxide hydrolysis, the alkoxides and hydroxides are
in equilibriumand it is known that some alkoxides can be prepared
by continuous removal of water from the reaction system [20,21]:
MOH
n
nROH MOR
n
nH
2
O 1
where M represents alkali or alkali earth metal, and R represents an
alkyl group C
n
H
2n+1
. However, when the hydrothermal process is
Fig. 6. XPS narrow spectra of (a) starting BR, (b) XYL-BR, and (c) SOR-BR: (A) XPS spectrum of C1s, (B) XPS spectrum of O1s, and (C) XPS spectrum of Mg2s.
Table 1
The atomic concentrations of the surface of samples using XPS (atomic%).
Sample O1s C1s Mg2s
XYL-BR 44.3 34.1 21.6
SOR-BR 50.0 22.7 27.3
BR 56.8 43.2
XYL 47.0 53.0
SOR 48.6 51.4
Table 2
Changes in oxygen ratios of each sample as a function of degree of grafting. The values
for XYL-BR, SOR-BR, and BR were normalized according to Mg content, and then the
values for XYL and SOR were normalized according to the C content of the XYL-BR and
SOR-BR samples, respectively.
Sample C O Mg
XYL-BR 1.6 2.1 1.0
SOR-BR 0.8 1.8 1.0
BR 1.3 1.0
XYL 1.6 1.5
SOR 0.8 0.8
582 K. Morimoto et al. / Journal of Colloid and Interface Science 368 (2012) 578583
utilized, the addition of water shifts the equilibrium composition to
the left-hand side of the reaction (1). Therefore, by hydrothermal
treatment, sugar alcohol molecules are not incorporated into the
brucite interlayer region.
4. Conclusions
In conclusion, the successful incorporation of sugar alcohols
(XYL and SOR) into BR was achieved via a melt intercalation proce-
dure within 24 h at 175 C. The XRD and FTIR analyses conrmed
that the melted sugar alcohol inltrated into the interlayers with
a breaking of the hydroxyl bonds in brucite and also that the
hydrothermal treatment of brucite with sugar alcohols had no ef-
fect. It was observed that, during this study, hydroxide and alcohol
were in equilibrium with alkoxide and water, similar to a previous
work [6]. However, in this study, the equilibrium was observed
using, for the rst time, solid sugar alcohols. Because of this equi-
librium, alkoxide is generated from the hydroxide under glycother-
mal conditions. Glycothermal reaction between the BR and sugar
alcohols is a convenient route for the synthesis of organicinor-
ganic hybrids, avoiding the effect of water. This is signicant be-
cause there are many organic chemicals which have poor water
solubility that are used in biofunctional substances, such as drugs,
enzymes, cosmetic chemicals. While many wet colloidal processes
use inorganic particles, this melt process could be used to produce
new types of hybrid that may lead to innovative technology in
many elds. To give a specic example, the combination of sugar
alcohols and/or other biomolecules produces new matrices for
DDS that can be used for direct encapsulation of drugs and to de-
velop bionanocomposite materials with drug-intercalated brucite
systems. In comparison with other DDS, the system proposed here
has the advantages of easy processing and the use of abundant,
inexpensive, and safe biomolecules. The possibility of using brucite
may allow the extension of this approach to the immobilization of
diverse drugs as well as to applications in topical therapies, such as
food, drugs, cosmetics, and medical applications.
Acknowledgments
This work was supported by a Grant-in-Aid for Scientic Re-
search category C (23550235) from the Ministry of Education, Cul-
ture, Sports, Science and Technology (MEXT) of the Japanese
Government.
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