Colloids and Surfaces A: Physicochem. Eng.

Aspects 441 (2014) 496503

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Hydrophilic gold nanoparticles stabilized with

tris(2-aminoethyl)amine: Preparation and characterization
Vladimir V. Tatarchuk a , Anastasiya P. Sergievskaya a, , Vladimir I. Zaikovsky b ,
Pavel N. Gevko a , Marsel R. Gallyamov a , Pavel E. Plusnin a , Pavel S. Popovezky a ,
Olga V. Antonova a
a
b

Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Ac. Lavrentyev pr., 3, Novosibirsk 630090, Russia
Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Ac. Lavrentyev pr., 5, Novosibirsk 630090, Russia

h i g h l i g h t s

g r a p h i c a l

a b s t r a c t

The synthesis of Au NPs stabilized

with of tris(2-aminoethyl)amine is
presented.
Final product is powder of Au NPs
with protective shells.
Shells compose of the adducts of
tris(2-aminoethyl)amine,
acetone
and boric acid.
The composition of powder is
Au{N(CH2 CH2 NH2 )3 }36 {OC(CH3 )2 }36
{H3 BO3 }32 {NaBO2 }4 {NaCl}4 .
Powder of Au NPs is hydrophilic and
redisperse in water and polar solvents.

a r t i c l e

i n f o

Article history:
Received 28 May 2013
Received in revised form
13 September 2013
Accepted 2 October 2013
Available online 10 October 2013
Keywords:
Gold nanoparticles
Tris(2-aminoethyl)amine
Synthesis characterization
Colloidal solutions
Polar diluents

a b s t r a c t
The synthesis of Au nanoparticles through the reduction of HAuCl4 with sodium borohydride in a mixture
of ethanol and isopropanol in the presence of tris(2-aminoethyl)amine is presented. The resulting powder
preparation is a mixture of primary particles with the average diameter of golden cores 3.2 0.6 nm,
and secondary particles that were formed as a result of agglomeration of the primary ones and have
core diameter up to 20 nm. The Au content of the preparation is 1.94% because Au nanoparticles have
voluminous protective shells composed of the adducts of tris(2-aminoethyl)amine, acetone and boric
acid, formed due to hydrogen bonding. The preparation is hydrophilic and allows one to obtain colloid
solutions in water and polar solvents like acetone, isopropanol, dimethylsulphoxide, and in chloroform
under ultrasonic treatment.
2013 Elsevier B.V. All rights reserved.

1. Introduction
Gold nanoparticles (AuNPs) stabilized with the help of various
chemical compounds are widely used in developing new materials and devices in many areas of human activities [17]. The most

Corresponding author. Tel.: +7 383 330 8248; fax: +7 383 330 8248.
E-mail address: sergievskaya@niic.nsc.ru (A.P. Sergievskaya).
0927-7757/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.colsurfa.2013.10.015

widespread protective reagents are simple and polymer organic

compounds with functional groups containing heteroatoms O, P,
S and N, possessing afnity to Au [8]. Among nitrogen-containing
reagents, rst of all, organic amines are to be mentioned; they may
be have aliphatic [9], aromatic [1012], macrocyclic [13], polymeric
[14,15] and dendrite structure [1523]. Reagents with two and
more terminal amino groups separated from each other by hydrocarbon fragments are used as linkers to control the aggregation of
NPs in solutions and agglomeration in solgel matrices [1126].

V.V. Tatarchuk et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 441 (2014) 496503

As far as tris(2-aminoethyl)amine (TAEA) is concerned, its use

for the synthesis of azacryptand and hyperbranched molecules for
particles stabilization is known [13,19,20,24,27]; it is used also as a
linker in nanostructure design [26,28,29]. We did not nd any published data on the use of TAEA itself as a protective ligand for AuNPs.
At the same time, TAEA is interesting as a simple and available
reagent for obtaining hydrophilic AuNPs. In spite of the relatively
small size of its molecules, one might expect that this reagent, due
to its branched structure and the possibility of intermolecular interactions, would form protective shells of sufcient thickness for the
spatial stabilization of particles in solution and in the solid phase.
So, the goals of the present study included verication of the
possibility to stabilize AuNPs with the help of TAEA, synthesis of
particles in solution, their isolation as a powder and characterization.
2. Experimental
2.1. Materials
Tris(2-aminoethyl)amine (96%, Merk), rectied ethanol (96%),
chemically pure grade concentrated aqueous HNO3 and HCl,
pure grade NaBH4 , 2-propanol, and chloroform were used as
received.
Solution 0.0091 M HAuCl4 in ethanol was prepared by dissolving
the weighed amount of crystalline HAuCl4 3H2 O, synthesized from
metal Au (+99.95%) according to the conventional procedure [30].
2.2. Methods and measurements
The hydrodynamic diameters of AuNPs in colloidal solutions
obtained through redispersion of AuNPs powder in solvents (dha )
were measured by means of the dynamic light scattering (DLS) in a
quartz cell with the sectional area of 1 cm 1 cm at an angle of 90 at
a temperature of t = 20 C with a 90Plus spectrometer (Brookhaven
Inst). The standard deviation for the determined average values,
for the number of measurements dha more than 20, did not exceed
0.2 nm.
The shape and diameters dAu of gold cores of individual NPs
were studied with the transmission electron microscope JEM-2010
(JEOL) with the accelerating voltage of 200 kV. To prepare the sample, a drop of the colloidal solution of the AuNPs in diluent treated
with ultrasound was dried on the substrate made of 200 mesh copper grid covered with a holey carbon lm. Local EDX analysis of
the preparations was performed with EDAX spectrometer (EDAX
Co) with Si-Li detector.
The atomic force microscopy (AFM) study of the AuNPs as a
layer upon the surface was made using the scanning probe microscope Solver Pro (NT-MDT) in the contact force mode in the air
(scan velocity 8.7 /s; step 16 nm; feedback gain 0.98; generator amplitude 0.20 V). To reduce the size effect of the tip, super
sharp diamond-like carbon tips with typical curvature radius 1 nm
were used. Deconvolution of AFM images was not made. The samples were prepared by depositing a drop of the colloidal solution of
the AuNPs in diluent on the substrate made of mica, and subsequent
evaporation of the solvent.
The UV-visible spectra of the solutions were recorded with SHIMADZU UV-1700 spectrophotometer. The IR absorption spectra
wihtin the range 4000400 cm1 were recorded with a Fourier
Transform spectrometer SCIMITAR FTS 2000 in a thin layer between
KBr glass plates for the liquid reagent TAEA and in KBr tablets for
the AuNPs powder.
XRD data were recorded with a single-crystal diffractometer X8
APEX (Bruker, MoK radiation, graphite monochromator) according to the procedure described in [31]. Diffraction patterns were

497

recorded using a two-coordinate CCD detector directed at an angle

of 30 with respect to the direction of the primary beam (detector
resolution: 1024 1024 pixels, the distance from the sample to the
detector: 40 mm, exposure: 5 min). Corundum (NIST SRM-1976)
was used as the external reference. Two-dimensional diffraction
patterns were processed using the FIT2D software [32]. Rening
of the coordinates of diffraction ring center and the distance from
the sample to the detector was carried out using the reference. The
X-ray phase analysis was carried out in the automatic mode with
the help of the database of powdered diffraction standards PDF2 [33]. Crystallite size in AuNPs was estimated using the Scherrer
equation. The calculation was performed for the diffraction peak
(1 1 1) of gold taking into account FWHM of the reference sample
Si. To make a sample, AuNPs powder was mixed with epoxy resin
to dense consistency, the resulting mass was used to form a sphere
0.2 mm in diameter, which was glued at the end of a glass rod like
for the examination of single crystals.
Chemical CHN analysis of the AuNPs powder was made with
the EURO EA 3000 instrument. Analysis for gold and sodium after
the dissolution of the weighed amount of powder in aqua regia,
evaporation and transfer into the solution of 2 M HCl was carried
out by means of atomic absorption in air-acetylene ame using ICE
3000 Series (Thermo Scientic) instrument.
Thermal analysis of the AuNPs powder was carried out using a
TG 2009 F1 Iris (NETZSCH) thermobalance in a corundum crucible
under the atmosphere of air and helium at the gas ow rate of
35 mL/min and heating rate of 10 K/min.
NMR 1 H spectra were recorded with Avance 500 (Bruker) NMR
spectrometer at 500 MHz in D2 O medium.
Photoluminescence spectra were recorded with a Cary
Eclipse spectrouorimeter (Varian) with two ultraspeed scanning monochromators, based on a pulsed xenon lamp and the
Schwarzschild optical system, at the voltage of 700 V, slit width
5 nm, room temperature and excitation with the light wavelength
of ex = 334 nm.
The charge, electrokinetic potential and electrophoretic mobility of the particles were determined by means of nonaqueous
electrophoresis in chloroform medium. The measuring procedure
and data processing method were published [34].
Ultrasonic (US) processing of the suspensions of AuNPs powder
(in order to obtain colloidal solutions) was carried out for 10 min
using the US disintegrator UD11 (Poland) at the oscillation frequency of = 22.0 1.6 kHz and amplitude of oscillation speed
1.6 0.1 m/s.

3. Results and discussion

3.1. Synthesis of AuNPs
Synthesis of AuNPs was carried out in a polar medium in the
mixture of i-PrOH and EtOH. For the successful synthesis, to 20 ml
of i-PrOH under mixing, we added sequentially 6 ml of 0.0091 M
HAuCl4 solution (5.5 105 moles, 10.8 mg Au) in EtOH, 1.4650 g
of liquid TAEA (0.01 mol) and of excess solid NaBH4 . The color of
the reaction mixture changed from yellow to dark red, then the liquid phase was separated from the white precipitate by means of
centrifuging and decanting. It is known that NaBH4 has limited solubility in alcohols [35], therefore the observed precipitate could be
the undissolved NaBH4 or poorly insoluble products of its interaction with components of the solution. Estimation of the amount of
NaBH4 , that passed into the solution, was approximately 2.1 103
moles based on the solubility of NaBH4 in isopropanol (3.7 g/L [35])
and 5.5 104 moles based on the mass difference between the
entered NaBH4 and the separated white precipitate (0.021 g) under
the assumption that the precipitate is NaBH4 . Later spontaneous

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V.V. Tatarchuk et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 441 (2014) 496503

Fig. 1. TEM images and size distribution for AuNPs in total (a) and for primary NPs only (b), HR TEM of agglomerated secondary particle (c), and EDXA of AuNPs (d).

coagulation of AuNPs with the formation of aky violet aggregates started in the transparent red solution. The process was
reversible: the akes got peptized during shaking. After coagulation and centrifuging, the reaction mixture got separated into the
violet precipitate of AuNPs and a colorless with a barely noticeable
yellowish tint transparent solution.
Using only one of the alcohols as solvent, we could not obtain
stable AuNPs because rapid agglomeration of NPs with the formation of black precipitates took place. The reason for the higher
aggregative stability of NPs during the synthesis in the mixture of
alcohols compared with the synthesis in only one of the alcohols is
not yet known. Since the stability of such systems is determined by
the balance of forces of electrostatic repulsion and van der Waals
attraction of the particles [3638], it can be assumed that a mixed
medium creates more favorable conditions for the Coulomb and/or
spatial stabilization of the particles. In the rst case, the medium
can affect the surface change of the particles due to the dielectric
constant, degree of dissociation of the salts present in solution, solvation and adsorption of ions. In the second case, the medium may
affect the interparticle distance due to solvation of TAEA as a protective ligand and due to changes of the system of hydrogen bonds
between molecules TAEA-TAEA and TAEA-alcohol, which denes
the structure and the spatial volume of protective shells of the particles. In addition, the medium undoubtedly affects the kinetics of
the particle formation process, which includes the stages of nucleation, growth and agglomeration of NPs, and formation of the bulk
metal phase [39]. Because of number of factors which are responsible for the stability of the colloidal system and which are depended
from the medium, a special study is needed in order to explain the
synergetic effect observed for the mixture of alcohols.

The precipitate of AuNPs was separated, washed with acetone

three times by decanting, and dried in the air to the constant mass,
which was determined to be 0.5305 g with gold content 1.94% Au
(10.3 mg). The yield of AuNPs powder with respect to Au was 95.4%.
Visually it was evident that the main losses were associated with
smearing of AuNPs powder along the internal surface of the test
tube in which the particles were synthesized.
3.2. Characterization of AuNPs
TEM showed the existence of two subsets of spherical NPs
uniform ne and non-uniform coarse ones. For this reason, the size
distribution has a broad dAu variation range from 2 to 20 nm, is
asymmetric, and the average value is dAu = 5.6 2.8 nm (N = 390). At
the same time, the core size of ne NPs varies within a narrow range
from 2.2 to 4.2 nm with the average value of d Au = 3.2 0.6 nm
(N = 161) (Fig. 1). One can see in the HR TEM images that coarse
NPs are secondary and have twinning structure because they were
formed as a result of agglomeration of ne NPs that belong to the
category of primary particles and have single-crystal cores.
3.3. Powder composition
The EDX spectrum of AuNPs, in addition to the peaks related to
the elements of the substrate (C, Cu), contains intense signals of Au,
N, O, and weak signals of Na and Cl, which are impurities and are
due to the use of NaBH4 and HAuCl4 as reagents (Fig. 1).
The XRD data show that Au is present in AuNPs as the metal with
a fcc lattice; there are no other crystal phases in the powder (Fig. 2).
The diameter of crystallites was found to be 2.7 0.9 nm. This is in

V.V. Tatarchuk et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 441 (2014) 496503

499

Fig. 2. XRD data for AuNPs powder and reference data for fcc Au lattice.

good agreement with the TEM data for the size of primary AuNPs
and conrms the fact that coarse NPs are joints of the primary ones.
The IR and 1 H NMR data provide evidence that TAEA is included
into the composition of the particles. The IR spectrum of AuNPs
contains mainly the same set of bands as TAEA itself (Fig. 3).
The difference for AuNPs is that the intensities of vibration bands
(CN) and (NH2 ) in the region 6501200 cm1 [40] decrease substantially, and a structured band with the maximum at 650 cm1
appears. In addition, in the case of AuNPs broadening and the shift of
vibration bands (NH2 ) and (CH2 ) in the region 25003500 cm1
occur. The reason of these differences can be the interactions of
TAEA with the surface of gold cores due to the donor nitrogen
atoms, and the changes in the character and structure of hydrogen
bonds inside the protective shell of AuNPs because of the possible
donoracceptor interactions of TAEA molecules with the molecules
of other reagents, for example acetone which was used to wash the
precipitate of AuNPs.
The 1 H NMR spectra of AuNPs immediately after the synthesis
and 2 weeks later contain three major pairs of triplets: a, b and c.
They refer to CH2 CH2 groups of TAEA and are characterized
by the intensity ratio a:b:c 1.36:2.28:1.00 and 1.00:1.60:1.13 for
spectra 1 and 2, respectively (Fig. 4). Different ratios between the
groups of peaks a, b and c in spectra 1 and 2 allow us to assume
the presence of three different TAEA forms in solution, each of
them corresponding to one of three pairs of triplets. The earlier
spectrum 1 also exhibits the line of the CH3 -group of acetone,

Fig. 4.

Fig. 3. IR spectra of TAEA and AuNPs powder.

e ( = 2.10 p.p.mp.); its intensity with respect o the major lines of

CH2 CH2 groups (a, b and c) is almost 10 times lower. In addition, both spectra contain a doublet d ( = 0.96 and = 0.10 p.p.m.
for 1 and 2, respectively), which is likely to belong to the amino
group of one of the forms of TAEA; at this stage of investigation, it
has not been yet attributed unambiguously.
Photoluminescence observed for AuNPs powder is due to the
organic shell of AuNPs and is characterized by the spectrum in
the form of a single broad band with a maximum at max = 450 nm
(Fig. 5).
Chemical analysis data of AuNPs powder are presented in
Table 1. On the basis of these data, the experimental molar ratio of
elements the presence of which in the preparation was conrmed
by means of XRD and EDX is Au:C:H:N:Na 1:327:843:148:8.26.
Evidently, the major fraction of AuNPs mass falls at the organic
component, for which C:H:N 1:2.58:0.45. A close elements ratio
C:H:N 1:2.67:0.44 is characteristic of the adduct of TAEA and acetone N(CH2 CH2 NH2 )3 OC(CH3 )2 or C9 H24 N4 O.
The presence of acetone is connected with its use for washing the precipitate and agrees with the IR and 1 H NMR data. The

H NMR spectra of TAEA and AuNPs 20 min (1) and 14 days (2) after preparation of the colloidal solution in D2 O.

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Fig. 6. Visible spectra of colloidal aqueous solutions of AuNPs not washed (1) and
rinsed with acetone (2, as soon as prepared, and 3, 7 days after the solution preparation).

Fig. 5. Photoluminescence spectrum of AuNPs powder.

Table 1
Elemental analysis of AuNPs powder.
Element

Found, % wt

Calculated, % wta

Au
C
H
N
O
B
Cl
Na

1.94 0.04
38.6 0.2
8.3 0.2
20.4 0.4

4.0b

1.87 0.02

1.96
38.8
9.65
20.1
22.3
3.88
1.41
1.83

a
b

Calculated for AuC324 H960 N144 O140 B36 Cl4 Na8 (FW = 10,028 g/mol Au).
Estimation based on TA data.

participation of acetone in the formation of particle shells is indirectly conrmed also by the fact that the violet AuNPs precipitate
isolated without washing with acetone gave not violet but blue
colloidal solution after re-dispersion in water. The spectrum of

this solution had a weakly pronounced basic SPR band in the

region  530 nm along with strong absorption in the red region at
 > 600 nm, which is characteristic of aggregates (Fig. 6). A comparison between the spectra of the products washed and not washed
with acetone provides evidence that non-washed AuNPs get aggregated in water to a higher extent than washed particles. A possible
reason may be the formation of adducts with acetone and corresponding decrease in the possibility for TAEA to act as a linker
between the particles and thus to promote their aggregation.
Calculation on the basis of three independent experimental
values C/Au = 327, H/Au = 843 and N/Au = 148 gives the average
value C9 H24 N4 O/Au = 36 2. If we accept that the impurity elements Na and Cl are present in AuNPs powder in the form
of a salt, then NaCl/Au = Na/Au = 8.26. Calculated mass for the
mixture {Au(C9 H24 N4 O)36 + 8.26NaCl} is 8027 g/mol Au. At the
same time, a conditional mass for the preparation calculated
on the basis of 1.94% Au content is approximately equal to
10,155 g/mol Au. Therefore, except Au, TAEA, acetone and NaCl
admixture, AuNPs powder contains some substance accounting

Fig. 7. Thermal analysis of AuNPs powder in the air.

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501

Fig. 8. Changes in the visible spectrum (a), and in the absorbance at 527 nm and aggregate size during coagulation of AuNPs in colloidal aqueous solution (b, c), cAu = 0.21 mM,
l = 1 cm.

for (1 8027/10,155) 100 20% of the mass. Such a substance

might be the oxygenated boron compounds, for example B(OH)3
as a product of the reaction of NaBH4 with HAuCl4 3H2 O (1) and its
hydrolysis (2) [41,42].
HAuCl4 3H2 O + 3/8NaBH4 Au + 3/8H3 BO3 + 3/8NaCl
+ 29/8HCl + 15/8H2 O

NaBH4 + 4H2 O H3 BO3 + NaOH + 4H2

(1)

(2)

Additional data on the composition of AuNPs were obtained by

means of the thermal analysis of the powder. Decomposition in the
air proceeded in three steps (Fig. 7). At the rst two steps, poorly
separated from each other, the mass loss was 13.2% (70120 C) and
60.2% (120300 C) or 73.4% as a total. This corresponds to a complete removal of the adduct N(CH2 CH2 NH2 )3 OC(CH3 )2 , according
to the data of elemental analysis, its content in the product is estimated as 72.3%. The mass of the solid residue under heating to
1000 C was 14.8% of the initial mass. Decomposition in the atmosphere of helium took place in a similar manner, with close mass
losses 13.5% (70140 C) and 62.0% (140300 C), the residual mass
under heating to 1142 C was about 12% of the initial mass (Fig. S1).
The data of emission spectral analysis of the product of decomposition in the air showed the presence of boron in the residue, thus
conrming the assumption that AuNPs could contain B(OH)3 . In this
case, the product of annealing may be the mixture Au + 18B2 O3 ;
its calculated fraction in powder is 14.3%. According to this, the
initial AuNPs powder should contain about 4.0% B as boric acid
at the molar ratio of B(OH)3 /Au = 36, which coincides with the
detected ratios TAEA/Au = acetone/Au = 36. Note that the amount of
B (2 103 moles), found in AuNPs powder, does not correspond
to the amount of NaBH4 (5.5 104 moles), estimated based on
mass difference between the entered NaBH4 and the separated
white precipitate, but it is in a good agreement with the amount

of NaBH4 (2.1 103 moles), estimated based on the solubility of

NaBH4 in isopropanol [35]. Hence, the white precipitate was not
a pure NaBH4 and contained the products of its transformation.
According to stoichiometry of HAuCl4 the ratio Cl/Au in AuNPs powder should be 4. Then at least 4 of 8 cations of Na+ per 1 Au should
be bounded not with Cl but with anions of boric acid.
So, taking into account all the data, the approxcomposition
of
the
synthesis
product
is
imate
Au{N(CH2 CH2 NH2 )3 }36 {OC(CH3 )2 }36 {H3 BO3 }32 {NaBO2 }4 {NaCl}4 ;
its effective mass is 10,028 g/mol Au, which agrees to the accuracy
of 1% with the experimental value 10,155 g/mol Au, calculated
on the basis of chemical analysis for Au. Stabilization of AuNPs is
achieved due to the spatial separation of their gold cores by the
shells that are composed of N(CH2 CH2 NH2 )3 , B(OH)3 and OC(CH3 )2
molecules and have a 3D spatial structure due to hydrogen bonds.
Furthermore, the charge stabilization by ions of Na+ and Cl
contained in the product is also possible.

3.4. Stability of colloidal solutions

The presence of a large number of proton-donor and protonaccepting centers provides the hydrophilic properties of AuNPs
powder. Due to this, the powder gets peptized with water and
water-miscible polar solvents like acetone, isopropanol, dimethylsulphoxide, as well as chloroform under US-processing with
the formation of transparent violet-colored colloidal solutions
in which AuNPs are present as aggregations. The hydrodynamic diameters of the aggregates, measured directly after
obtaining the colloidal solutions, increased along the solvent
sequence: acetone (dha 0 75 nm) < water (113 nm) < isopropanol
(125 nm) < DMSO (143 nm) chloroform (145 nm). Since the colloid solutions could be obtained by the peptization of AuNPs
powder in different solvents and the aggregates in the solutions
have different sizes, it can be argued, that the aggregation is

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the TEM data and h for the layer of NPs on the substrate surface
according to AFM data, we estimate the thickness of the protective shell as L = h d Au (5.1 3.2)/2 1 nm. This is in rather
good agreement with the fact that the shell is composed of TAEA
molecules, acetone and B(OH)3 . Among them, TAEA molecules
have the largest size, which is determined by the length of the
NCH2 CH2 NH2 fragment. Estimate of the maximum as the sum of
bond lengths N C (0.147 nm), C C (0.154 nm), N H (0.101 nm) and
Van der Waals radii of atoms N (0.15 nm) and H (0.12 nm), without taking into account the angles between bonds, gives the value
lmax = rN + 2lN C + lC C + lN H + rH 0.8 nm.
Fig. 9. AFM 3D image of the layer of AuNPs on mica.

not irreversible and is not accompanied by the agglomeration

of gold nuclei of NPs. Although the effect of the liquid medium
for the aggregates size is obvious, our attempts to identify any
one-parameter correlations of the hydrodynamic diameters of the
aggregates with the properties of the solvents (dielectric constant,
density, viscosity, empirical parameters of the solvents, dipole
moment of the molecules) have failed.
Spontaneous coagulation and sedimentation of AuNPs proceeded in the colloidal solutions. Spectral and aggregate size
changes during coagulation of AuNPs in the colloidal solutions
are presented at Fig. 8 and Fig. S2 on a different time scales. The
size of aggregates increased during coagulation, and the spectrum changed due to a decrease in the intensity of the major SPR
band in the region of 530 nm and an increase in the intensity in
the longer wavelength region  > 600 nm due to the second band,
related to the aggregates of AuNPs. The growth of the aggregates
in solution was limited by the critical dcr value. Aggregates growing to a size dha > dcr precipitated from the colloidal solution. With
the start of sedimentation, dha = dcr for the particles remaining in
the solution was almost unchanged, while the intensity of the
whole spectrum decreased monotonously with the conservation
of its shape. Sedimentation was a reversible process, and precipitates could be re-dispersed, therefore the cores of particles did not
agglomerate. Aqueous solutions conserved stability (the absence of
precipitate) for more than 7 days. In non-aqueous solutions, sedimentation of particles (or oatation in the case of chloroform)
started within 3050 min. The critical aggregate size for sedimentation depended on the solvent and was approximately equal to
dcr 170185 (water), 190195 (acetone), 220230 (isopropanol)
and 250275 nm (DMSO, chloroform).
Colloidal solutions are suitable for preparing AuNPs layers
on various surfaces, in particular with the help of electrophoresis or the drop method. The data obtained by means of
nonaqueous electrophoresis in chloroform showed that the
aggregates of AuNPs (dha 0 145 nm) has a positive charge, electrokinetic potential  = 134 8 mV and electrophoretic mobility
 = 66 4 1010 m2 /(V s).
The layer obtained through the natural evaporation of a drop
of the colloid aqueous solution of AuNPs on mica plate was continuous according to the AFM data and had a uniform surface with
the rare dome-like protrusions caused by large secondary particles. Though visually the distribution of large particles upon the
substrate surface looks as ordered distribution (Fig. 9), the prole of the thickness of the particles monolayer indicates that this
distribution has a random character (Fig. S3). The surface area
per one protrusion was approximately 4104 nm2 . The height of
domes varied from 0.7 to 2.5 nm, and their diameter at the bottom varied from 44 to 106 nm, the average value being 84 12 nm
(N = 132). The total thickness of the layer varied from 4.5 to 7.3 nm,
with the average value equal to h = 5.1 0.4 nm (N = 254). Using
the values of d Au for the cores of primary AuNPs according to

4. Conclusions
Investigation showed that TAEA is a good stabilizing reagent for
AuNPs. The synthesis proceeds by the reduction of HAuCl4 with
NaBH4 in a mixture of isopropanol and ethanol. The nal product is
a powder of AuNPs, violet-colored, containing 1.94% Au. The yield
of products with respect to Au is not less than 95%. AuNPs have gold
cores with a size 220 nm, and protective shells composed of TAEA
molecules, as well as acetone and B(OH)3 molecules bound with
TAEA through H-interactions. The AuNPs powder is stable in storage, it is hydrophilic and able to form colloidal solutions in water
and in polar solvents under ultrasonic re-dispersing. In colloidal
solutions, AuNPs is present as aggregates that get larger gradually
due to coagulation; no agglomeration of the cores of AuNPs occurs.
The solutions are most stable in water. The aggregates of AuNPs
have a charge, which is positive in chloroform medium, and possess
electrophoretic mobility. Colloidal solutions can be used to obtain
AuNPs layers on various surfaces.
Acknowledgment
This work was supported by the Russian Foundation for Basic
Research (project no. 12-03-00091-a).
Appendix A. Supplementary data
Supplementary data associated with this article can be
found, in the online version, at http://dx.doi.org/10.1016/j.colsurfa.
2013.10.015.
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