Journal of Colloid and Interface Science 327 (2008) 224–232

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Journal of Colloid and Interface Science

www.elsevier.com/locate/jcis

Thermal hysteresis of some important physical properties of nanoparticles

Tapan Sarkar a , Shibsekhar Roy a , Jaydeep Bhattacharya a , Dhananjay Bhattacharya b , Chanchal K. Mitra c ,
Anjan Kr. Dasgupta a,∗
a
Department of Biochemistry, Calcutta University, 35 Ballygunge Circular Road, Calcutta 700019, India
b
Biophysics Division, Saha Institute of Nuclear Physics, 1/AF Bidhannagar, Calcutta 700064, India
c
Department of Biochemistry, University of Hyderabad, Hyderabad 500046, India

a r t i c l e i n f o a b s t r a c t

Article history: Gold nanoparticles show thermal hysteresis with properties such as surface plasmon absorption,
Received 15 April 2008 conductivity, and zeta potential. The direction of the incremental change in plasmon peak position and
Accepted 23 July 2008 its extinction depend on the nature of surface conjugation. The thermal profile of a surface plasmon
Available online 29 August 2008
resonance spectrum for nanoparticles may serve as a signature for the associated small molecule or
Keywords:
macromolecule on which it is seeded. The thermal responses of zeta potential and conductivity profile are
Gold nanoparticle found to be independent of the surface conjugation with the later being subjected to a phase transition
Surface plasmon phenomenon as revealed by a temperature criticality.
Hysteresis © 2008 Elsevier Inc. All rights reserved.
Phase transition

1. Introduction
The optical and optoelectronic characteristics of nanoparticle
colloids recently appear to be very useful in various plasmon
waveguides [1,2], spectroscopy [3], optical switches [4], and chem-
ical and biological sensors [5–10]. The free electrons in the con-
duction band of the metals show a strong absorption at a par-
ticular wavelength due to their collective oscillation known as
localized surface plasmon resonance (LSPR). Though detailed stud-
ies on the optical character of the plasmon are available in the
literature, the dependence of such thermal properties on the
nanoform composition is not reported. Normally, with increase of
temperature there is a gradual decrease in the plasmon inten-
sity [11].
The selective excitation of the localized vibration of the electron
plasma is known to depend on the substrate on which a nanopar-
ticle is prepared [12,13]. For a colloidal nanosuspension no sup-
porting substrate is needed. The plasmon excitation pattern may
depend on the interface between the colloidal particle and the im-
mediate environment embedding the same. This in turn depends
on the nature of the surface conjugation by chemical groups or
macromolecules. The specificity of plasmon pattern is reported for
functionalized gold nanoparticles. The typical plasmon spectra for
cysteine- and lysine-modified gold nanoparticles are already avail-
able in the literature. However, little is known about the thermal
* Corresponding author. Fax: +91 3324614849.
E-mail address: adgcal@gmail.com (A.Kr. Dasgupta).
behavior of the plasmon and how specific the thermal profile is to
the nature of functionalizing group. The approach may have a po-
tential in extracting a spectroscopic signature of small molecules
and macromolecules based on temperature-shift studies of plas-
mon intensity of their nano-conjugated forms.
Another important electrokinetic property that is subjected to
alteration by thermal intrusion is electrical (electronic) conduc-
tivity. Electrical conductivity is known to decrease exponentially
with increasing interparticle spacing. For gold nanoparticles, en-
hancement of the particle film electronic conductivity is found to
increase with increasing temperature [14]. For gold nanoparticles
protected by alkanethiols, the ohmic behavior with conductivity
shows several orders of magnitude smaller than that of the bulk
gold [15]. In another work, conductivity enhancement is reported
by specially modified SiO2 nanoparticles, where the nanoparti-
cle significantly increases the ion mobility [16]. Steady-state and
transient conductance measurements of gold nanobead solutions
showed that the application of a moderate electric field of value
between electrodes increases the value of the resulting steady-
state conductance significantly [17]. Interestingly, some periodic
features in the conductance are found in many gold nanoparticle–
biopolymer conjugates where both the threshold voltage and the
conductance features take place at voltages higher than expected
for the capacitance of the nanoparticles [18]. For the complex
metal oxide nanoparticle In2 O3 :Sn, conductance rises with increas-
ing annealing temperature more than threefold [19]. Our focus will
be to observe the thermal response of nanoparticle conductivity as
well as the associated zeta potential to assess the parallel surface
phenomena taking place.

0021-9797/$ – see front matter © 2008 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2008.07.050
 T. Sarkar et al. / Journal of Colloid and Interface Science 327 (2008) 224–232
2. Materials and methods
2.1. Preparation of nanoparticles
All glasswares were washed with aqua regia prior to use and
MilliQ water was used for the experiment. Gold nanoparticles
were prepared by standard borohydride reduction of correspond-
ing metal salt. For the preparation of gold nanoparticles (GNP) of
desired size, 0.4 mM auric chloride (Arora Matthey) was reduced
by 0.8 mM sodium borohydride (Merck) at room temperature. Af-
ter the reduction, 1 ml nanoparticle solution was centrifuged at
10,000 rpm for 1 h at 4 ◦ C to remove the excess reagents. The pre-
cipitate was resuspended in 600 μl MilliQ water.
2.2. Preparation of DNA-conjugated nanoparticles
DNA-conjugated nanoforms were prepared by growing the
nanoparticles in the presence of DNA. A stock 0.5 μM solution
was prepared by dissolving calf thymus DNA (Sigma) in autoclaved
water. The DNA solution was preserved at 4 ◦ C. For preparation
of nanocomposites, an aliquot from this solution was added while
preparing the nanoparticles. The centrifugation was carried out un-
der the same condition as described earlier.
2.3. Preparation of amino acid-capped gold nanoparticles
l-Cysteine and l-lysine (Sigma) were chosen as the capping
agents for the gold nanoparticles. The stock concentration used (for
both amino acids) was 10 mM and pH was maintained at physio-
logical range. Final concentrations of the amino acids were 0.1 mM
for AuCl3 and 0.8 and 0.4 mM sodium borohydride, respectively.
The capped nanoparticle solution was bluish violet in color and
the plasmon peak was at 533–535 nm.
2.4. Characterization of the prepared nanoparticles
2.4.1. Dynamic light scattering
Size distribution profiles of free nanoparticles and DNA-conju-
gated nanoparticles were measured by dynamic light scattering
(Zetasizer Nano-Malvern). The Nano-ZS (Malvern, UK) instrument
(5 mW He–Ne laser λ = 632 nm) was used for this purpose. The
sample was poured into a DTS0112 low-volume disposable sizing
cuvette of 1.5 ml (path length 1 cm). Typically, the gold nanoparti-
cles showed a diameter around 5 nm.
2.4.2. Transmission electron microscopy
Gold nanoparticles were also characterized by transmission
electron microscopy that showed the diameter of the particles
around 5 nm (see Fig. 1). Gold nanoparticles are prepared after
drying on carbon-coated copper grids and observed under a trans-
mission electron microscope FEI, Model STWIN, with an acceler-
ating potential of 200 kV, and analyzed with TECNAI G2 software
for their corresponding shape and size. The images were further
analyzed using a UTHSCSA imaging tool.
2.5. Spectroscopic measurements
Spectrophotometric measurements were made with a Perkin-
Elmer spectrophotometer (Lambda 32 UV spectrometer) with
(Peltier temperature programmer) a temperature-controlled sys-
tem. Wavelengths were scanned from 220 to 700 nm. For tem-
perature variation experiments temperature was changed at 1 ◦ C
intervals in the range 50–90 ◦ C.
225
2.6. Measurement of zeta potential and conductance by laser Doppler
velocimetry (LDV)
The Nano-ZS (Malvern) instrument we have used for our exper-
iment is equipped with a 4 mW He–Ne laser (λ = 632 nm) and
calculates the zeta potential. In an ionic solution, the development
of a net charge on the surface of a particle alters the ionic dis-
tribution in the interfacial region that results in the increase in
counterion concentration close to the surface. Thus an electrical
double layer exists surrounding each particle. The inner part of the
layer, i.e., the Stern layer, is characterized by strongly bound ions
and the outer layer consists of loosely bound diffusing ions. Within
this diffusive layer the ions as well as particles form a stable entity
confined by a boundary. With the gravity-induced particle move-
ment, ions within that boundary also move along it but not the
ions beyond this boundary. The potential existing in this boundary
is called the zeta potential.
It should be remembered that zeta potential is purely an elec-
trokinetic property of the electrical double layer surrounding the
subject but not the surface of the subject itself. This quantity is
measured by determining the electrophoretic mobility and then
applying the value in Henry’s equation. The velocity of a particle
in an electric field is known as electrophoretic mobility (U E ). Now,
applying this value to Henry’s equation we’ll obtain the value of
zeta potential (z).
3η U E
z= , (1)
2ε f ( K a )
where η = viscosity, ε = dielectric constant, and f ( K a ) = Henry’s
function.
A special capillary cell is used for this measurement with em-
bedded electrodes at either of the two ends. Particles move toward
the electrode of the opposite charge and their velocity is measured
and expressed in unit field strength as their mobility. Now, the
technique that is used for this measurement is laser Doppler ve-
locimetry. This technique efficiently measures the velocity of tiny
particles within the fluid streams moving at the velocity of the
fluid. The receiving optics is focused so as to relay the scattering
particles in the cell. After being scattered at an angle of 17◦ , the
beam is combined with the scattered beam and produces a fluctu-
ating signal, whose fluctuation rate is proportional to the particle
velocity. Then a signal processor extracts the characteristic fre-
quency of the scattered light. A temperature variation study was
performed by using the Peltier-based technology embedded with
the instrument.
3. Results and discussion
3.1. Transmission electron microscopic studies and image analysis
The sizes of the synthesized nanoforms (unconjugated gold
nanoparticles and DNA-conjugated gold nanoparticles) have been
analyzed under transmission electron microscopy (TEM). Figs. 1a
and 1b respectively represent the TEM images of gold nanoparti-
cles (NaBH4 reduced) and those conjugated with calf thymus DNA.
The figures indicate that the size and shape distribution of the gold
nanoparticles have changed markedly when they are formed in the
presence of DNA. These changes are seen in Figs. 1c and 1d. The
analyses of size and shape are provided in Figs. 1c and 1d. The
FERET diameter (the longest distance between two points in the
same nanoparticle; see Fig. 1c) exhibits an exponential distribu-
tion of particle size in the presence or in absence of DNA seeding.
In the later case, the distribution has a lower cutoff value of 5 nm.
The distribution is much wider for the unseeded nanoparticle, with
a cutoff value around 11 nm. Here, in addition to the role as a
template, DNA works as a stabilizer of the synthesized nanoform.
226 T. Sarkar et al. / Journal of Colloid and Interface Science 327 (2008) 224–232

(a) (b)

(c) (d)

Fig. 1. Transmission electron micrographs of free and DNA-conjugated gold nanoparticles and corresponding shape factors. (a) Bare gold nanoparticle, (b) calf thymus DNA-
seeded gold nanoparticle, (c) distribution of Ferret diameter of DNA-seeded gold nanoparticle (red) in comparison to the bare gold nanoparticle (black), (d) comparative
roundedness of bare gold nanoparticle and that seeded with DNA (roundedness closer to unity for spherical size). (For interpretation of the references to color in this figure
legend, the reader is referred to the web version of this article.)

The surface groups of DNA (e.g., –OH group) restrict the growth of
the nanoclusters and drive the conjugation to a smaller size distri-
bution that seems to fit with the diameter of the DNA (∼2 nm).
Seeding with DNA also changes the shape parameters. Fig. 1d il-
lustrates the shape variations of the nanoparticle in the absence
and in the presence of DNA seeding. Seeding with DNA leads to a
higher value of roundedness, indicating that they assume a more
spherical shape than their unseeded counterpart. The seeding also
improves the sharpness of the size distribution of the nanopar-
ticles. Hence, the upper cutoff size with DNA seeding is much
smaller than that of bare gold nanoparticles.
3.2. Thermally induced changes in plasmon intensity
Temperature variation induces differential changes in plasmon
intensity of the gold nanoparticles with different seeding condi-
tions under which gold nanoparticles are prepared. Normally heat-
ing leads to reduction in plasmon intensity. Conjugation with DNA
or lysine, however, induces the opposite effect, namely an increase
in plasmon intensity. Interestingly cooling does not always reverse
such changes. The heating normally induces a red shift of the plas-
mon maxima but cooling does not show any significant change of
the same. GNP shows that the λmax value of the nanoform can
increase from 3 to 8 nm in this thermal cycle. Interestingly the
plasmon shift referred in a related work [11] reported a much
lesser plasmonic shift as a result of similar thermal shifts but with
nanoparticles embedded in solid silica matrix unlike the colloidal
solution used by us.
Fig. 2a shows the plasmon intensity temperature profile of gold
nanoparticles synthesized under different seeding conditions. The
upper left panel represents the thermal profile of a bare gold
nanoparticle. The upper right, lower left, and lower right panel re-
spectively represent the plasmon behavior in presence of seeding
with DNA, cysteine, and lysine. The symbols (!) and (1) respec-
tively represent absorbance at the plasmon maxima under heating
and cooling conditions, respectively, the abscissa representing the
temperature (in ◦ C). The arrows in Fig. 2a represent the direction
of heating and cooling. It may be noted that in the case of ly-
sine seeding the hysteresis area is maximal, while it is minimal for
bare gold nanoparticles. The lesser hysteresis area evidently im-
plies higher thermal reversibility of the thermo-plasmonic effect.
The whole spectra of the thermal cycle for different nanoforms are
described in supplementary Figs. s2a and s2b.
Fig. 2b represents the corresponding (with respect to Fig. 2a)
profile for alteration in λmax of the plasmon resonance of gold
nanoparticle under heating and cooling conditions. The change in
λmax follows a pattern that is significantly different from plasmon
intensity. The hysteresis area is maximal for cysteine while it is
minimal for lysine, indicating minimum and maximum reversibil-
ity, respectively.
 T. Sarkar et al. / Journal of Colloid and Interface Science 327 (2008) 224–232 227

(a)

(b)

Fig. 2. Thermal hysteresis by optical properties of free and biomolecule-conjugated GNP. (a) Plasmon of bare and seeded gold nanoparticles at different temperatures. The
upper left represents bare gold nanoparticle, the panel in the upper right represents DNA-seeded gold nanoparticle, the panel in the lower left represents cysteine-seeded
gold nanoparticle, and that in the lower right represents lysine-seeded gold nanoparticle. Symbols (!) and (1) respectively denote the heating and the cooling pathway.
(b) Dynamics of maximum wavelength of bare and seeded gold nanoparticles at different temperatures. In relation to the panel (a), the corresponding λmax of bare and
seeded gold nanoparticles at different temperatures is shown here. Symbols (!) and (1) respectively denote the heating and the cooling pathway. (c) Thermal response of
the plasmon for DNA-seeded gold nanoparticle. Correlated hyperchromic shift and plasmon intensity for DNA-seeded gold nanoparticles are shown in the upper panel. The
lower left panel shows the corresponding thermal response of absorbance at 260 nm whereas the lower right panel shows the ratio of the plasmon and the absorbance at
260 nm plotted against absolute temperature shows a break near the melting point.
228 T. Sarkar et al. / Journal of Colloid and Interface Science 327 (2008) 224–232
(c)
Fig. 2. (continued)
The inferences that can be obtained from the two sets of data
(Figs. 2a and 2b) are that the seeding alters two independent at-
tributes of the gold nanoparticle: (a) the average size, i.e., the size
of a single stable nanoparticle, which determines the λmax ; and (b)
the surface topology of the nanoclusters, their porosity, and conju-
gate distribution, which determine the resultant plasmon intensity
at a given cluster size limit. However, the hydrodynamic size (i.e.,
size of the stable hydrated form) distribution remains almost un-
changed through the thermal cycle as shown in supplementary
Fig. s1.
Comparison of the upper left and right panels of Fig. 2c shows
how the plasmon intensity (520–530 nm) correlates with the hy-
perchromic shifts (260 nm). The fact that the ratio of the plasmon
absorbance and the absorbance at 260 nm (see lower right column
of Fig. 2c) shows a break near the melting temperature implies
that the intact double helix of the template dictated the seeding
and the loss of the same led to restructuring of the nanoclusters.
It is interesting to note that this correlation between plasmon and
hyperchromic shift is lost (data not shown) in the case of circular
DNA. The topological constrains in such DNA may lead to structural
distortions on binding with gold nanoparticles and as a result the
correlation may be lost. The melting of such plasmid DNA has a
completely different character (being a steep profile with higher
melting temperature) and this makes the analysis of the result dif-
ficult.
3.3. Congruence of thermal signature and its dependence of size
Functionalization of gold nanoparticles with different macro-
molecules leaves a distinct signature [20]. In some cases this sig-
nature may be similar. For example, the shift of the plasmon max-
ima to a higher wavelength seems to be a general trend. This can
be mediated by coalescence of gold nanoparticles, larger particles
yielding plasmon at higher wavelengths. However, the reverse of
this trend shown by lysine-seeded gold nanoparticles is not clearly
known.
Again the general trend, namely decrease of plasmon inten-
sity with temperature, is violated in both DNA-seeded and lysine-
seeded gold nanoparticles. A possible explanation may be that
there is a competition between two factors: first, the general de-
crease in plasmon intensity, and second the exposure or availabil-
ity of the nanoparticle in the light path. If the availability increases
with temperature, which may happen for DNA (due to, say, open-
ing of the helical chain) the dominance of the second factor may
explain the increase in plasmon intensity. However for lysine the
explanation is not straightforward. A thermally reversible opening
or closing of the matrix embedding gold and lysine may explain
the observation.
3.4. Behavior of conductivity and zeta potential as a function of
temperature
The electrokinetic behavior of the nanoparticle is certainly a
function of temperature. We have observed the thermal behavior
conductivity (K ) and the zeta potential of the nanoparticle. In this
study, we have taken bare gold nanoparticles and lysine-coated
and cysteine-coated gold nanoparticles. We have excluded the DNA
conjugation from this experiment for the associated melting prop-
erty of DNA that can significantly contribute to the alteration of
conductivity and zeta potential. We have studied the temperature
range of 40 to 80 ◦ C. At first we have increased the temperature
from 40 to 80 ◦ C and then cooled it down back to 40 ◦ C. The value
of conductivity increases with temperature for all the nanoparticles
as described in the upper panel of Fig. 3a. The direction of the tem-
perature change is denoted as T + (heating) and T − (cooling). It
is observed that the conductivity reaches a maximum and reverts
back to a lower value close to the initial (i.e., at 40 ◦ C) via a hys-
teresis loop. One important observation regarding this behavior is
the retention of a residual conductivity. Once, the maximum value
is reached and the solution is cooled, in the initial range of cool-
ing, i.e., in the 80 to 70 ◦ C range, the value of conductivity remains
constant. On further cooling, the conductivity decreases gradually.
However, the slope, i.e., the conductivity gradient (dK /dT ), re-
mains the same for both the increasing and the decreasing mode
of temperature. This retention is observed for all the nanoparticles,
irrespective of the ligand attached to the nanosurface and thus will
 T. Sarkar et al. / Journal of Colloid and Interface Science 327 (2008) 224–232 229

(a)

(b)

Fig. 3. Thermal hysteresis by electrokinetic properties of free and amino acid-conjugated GNP. (a) The upper panel shows the plot of temperature vs logarithm of conductance
(K ) for gold nanoparticle (circle), lysine-conjugated gold nanoparticle (square) and cysteine-conjugated gold nanoparticle (triangle). The lower panel shows the variation
of zeta potential with respect to the temperature for the said nanoparticles. (b) Plot of ( T − T c )2 vs log( K ), where T = temperature, T c = critical temperature, and K =
conductance.

be referred to as conductivity retentivity. As a result of the reten-
tion, when the temperature is decreased to the initial value, there
is a residual gain of conductivity.
However, for each of the nanoparticle used, it is observed that
the value of the specific conductivity gradient, i.e., [K −1 (dK /dT )],
remains constant for all types of the nanoparticles. Hence, we ob-
tained an empirical relation given below,
K = exp(α1 T + β1 ).
Then we have tested whether there is a temperature criticality
in this conductivity behavior. This is shown in Fig. 3b. We have
plotted log( K ) with the  T 2 , where  T = ( T − T c ) and T c is
the critical temperature taking the value of 80 ◦ C. The plot gives a
straight line for all types of nanoparticles. This leads to the deriva-
tion of the empirical relation given below,
 
(2)
K = exp α2 ( T )2 + β2 . (3)

Here α1 and β1 are two constants whose values are given in Ta- Here α2 and β2 are two constants whose values are given in Ta-
ble 1. ble 2.
230 T. Sarkar et al. / Journal of Colloid and Interface Science 327 (2008) 224–232
Table 1
Constants for the temperature dependence of the conductivity [K = exp(α1 T + β1 )];
here the subscripts H and C denote the heating and cooling process, respectively
Nanoparticle α1 β1
α1H α1C β1H
GNP 0.0081 0.0064 −2.533
Lys_GNP 0.0103 0.0067 −4.0055
Cys_GNP 0.0111 0.0063 −2.9468
Table 2
Constants for the critical temperature dependence of the conductivity [ K =
exp(α2 ( T 2 ) + β2 )]; here the subscripts H and C denote the heating and cooling
process, respectively
Nanoparticle α2 β2
α2H α2C β2H
GNP −1.723 × 10−4 −1.7066 × 10−4 0.268
Lys_GNP −2.1047 × 10−4 −1.78 × 10−4 −0.481
Cys_GNP −2.346 × 10−4 −1.66 × 10−4 0.9019
This also indicates a phase transition-type behavior. Hence, for
the gold nanoparticles there is a temperature-dependent perco-
lation of the nanosurface. Conductivity has emerged as a phase
transition property of the nanoparticle supporting the previously
noted coalescence property (Section 3.3) of the gold nanoparti-
cle.
For Eqs. (1) and (2), the values of the constants (α1 , β1 , α2 , and
β2 ) vary marginally between heating and cooling pathways. This
is described in Tables 1 and 2 as the constants (α1 , β1 , α2 , and
β2 ) have been calculated from both pathways and are described
as α1H , β1H , α2H , and β2H for the heating pathway and α1C , β1C ,
α2C , and β2C for the cooling one. The theoretically calculated val-
ues have been found to fit well with the experimentally observed
ones (see supplementary Fig. s3 as the error plot of theoretical
and experimental K values and Fig. s4 to show the linearity of the
log( K ) value with respect to  T 2 ).
The thermal behavior of the zeta potential is somewhat differ-
ent from that of the conductivity. We see very clearly (Fig. 3a)
that the thermal conductivity does not return to the original point
after a complete cycle but the zeta potential does. Differences
in zeta potential are most significant in the temperature range
of 50–60 ◦ C, but for the conductivity the T + and T − lines are
practically parallel. It is difficult to speculate, but one must re-
member that the zeta potential has its origin on the surface lay-
ers (the electrical double layer) that attains equilibrium relatively
rapidly (unless covalent interaction takes place). Hence, conduc-
tivity is a bulk phenomenon poorly affected by the surface pro-
cesses.
For the zeta potential, we note that the actual zeta potential
increases after the capping, but the amount of the hysteresis re-
mains approximately the same (<10 mV). This suggests that the
hysteresis is not affected by the capping process (we see a simi-
lar conclusion for the conductivity; see above). The change of the
zeta potential with temperature is observed in the lower panel of
Fig. 3a. Here also, the behavior is not dependent on the nature of
the ligand attached with the surface of the nanoparticle. However,
the initial rise of the temperature from 40 to 50 ◦ C showed a sharp
decrease of the zeta potential, which gradually gets saturated in
the higher temperature range. While cooling down, the zeta poten-
tial gradually reverts back to the initial. The pattern of hysteresis is
much different from that of conductivity. As the zeta potential de-
scribes the potential of the surface of the outermost double layer,
the hysteresis of the zeta potential indicates a dynamic equilibrium
of not only the surface charge but also the hydrodynamic assem-
bly property. We propose that the observed hysteresis is due to
the slow “reaction” at the surface. For the electrical conductivity,
we see that the conductivity increases, as expected from theory,
but during the cooling phase, the values for 60 and 70 are practi-
cally identical. For the zeta potential we do not see this effect, as
β1C the phenomenon is mostly due to the outer double layer, which is
−1.965 of a relatively faster time scale. Therefore the hysteresis is likely to
−2.721 be due to a slow process of adsorption on the inner layer. This also
−1.242 affects the spectrum, as expected.
For cycle multiplicity—memory of the physical pathway, the
marked difference between these two properties (zeta potential
and conductivity) has been more prominent when the thermal
cycle is repeated. We repeated the thermal cycle five times to
observe any effect of the number of cycles on the nature of hys-
teresis. The conductivity hysteresis remains unchanged throughout
the multiple cycling (Fig. 4a) whereas the zeta potential hystere-
β2C sis has changed markedly from cycle 1 to cycle 5 (Fig. 4b). Fig. 4,
0.301 as a whole, demonstrates the nature of the hysteresis as two-
−0.387 dimensional geometrical planes described by temperature and the
0.9544 related electrokinetic properties (conductivity for Fig. 4a and zeta
potential for Fig. 4b). The shapes of the five planes represent-
ing five cycles have clearly described the repetitive nature of the
conductivity cycle and the nonrepetitive nature of the zeta po-
tential one. As conductivity is a bulk scale property, the absence
of hysteresis in conductivity suggests that the observed effect is
caused by alterations in the surface interactions of the nanoparti-
cles.
4. Summary
One important issue raised in this work is the thermal response
of various important properties emerging at the nanoscale. Im-
portantly, these various properties respond with thermal intrusion
differently and in some cases they are strongly intertwined with
the nature of surface modification. Surface ligands play an im-
portant role in the nanoscale as the overall thermal response of
the nanobioconjugate is the summation of the thermal response
of both the nanosurface and bioconjugate. It certainly implies
that the thermal response of those attached biomolecules (amino
acid, nucleic acid) plays a determining role in driving the equilib-
rium of the nanobiocomposite in a solvent environment. A simple
utility of this approach can be the study of conformational be-
havior of macromolecule. Earlier studies from our laboratory [21]
showed that nanosurface attachment can probe the alteration of
the biomolecular conformation by altering its clustering properties
and thus can efficiently trace the thermal melting of the conju-
gated protein. Here also, the thermal melting of DNA is well re-
ported by the plasmonic response by the nanoparticle. The next
step should be the extrapolation of this technique to design a
probe to sense temperature of intercellular locations. As it ap-
pears from the results that the heating and cooling curves contain
a signature of the functional group or functional state of macro-
molecules with which the nanoparticle has been functionalized.
The importance of the finding of ligand-independent conductiv-
ity and zeta potential behavior may be attributed to the over-
all solution dynamics of the nanoforms coupled with the surface
charge distribution. Thus, the role of the local ionic environment
is also a very important factor governing the electronic properties
in nanoparticles. In a related work, Biancardo et al. [22] have re-
ported that in the case of 11-mercaptoundecanoic acid-coated gold
nanoparticles, it shows a temperature-dependent hysteresis occur-
ring due to ionic motion within the nanoparticle array, which is
likely due to the proton exchange between the carboxylic acid tail
groups. But, in our case, the hysteretic behavior being the same
for both bare and coated gold nanoparticles, we would like to
assign this phenomenon to be a more general property of the
nanosurface. Here, the interactions between the adjacent nanosur-
 T. Sarkar et al. / Journal of Colloid and Interface Science 327 (2008) 224–232 231

(a)

(b)

Fig. 4. Effect of multiple cycles on the nature of hysteresis. (a) Multiple cycles of conductivity shown in a three-dimensional space described by temperature (x-axis),
conductivity ( y-axis), and number of cycles (z-axis). (b) Multiple cycles of zeta potential shown in a three-dimensional space described by temperature (x-axis), zeta potential
( y-axis), and number of cycles (z-axis).

faces mainly by hydrophobic interaction and solution–nanosurface Supplementary material

interactions governed by hydrogen binding are the key players to
respond to the thermal intervention. Supplementary data for this article may be found in the online
version at DOI: 10.1016/j.jcis.2008.07.050.
Acknowledgments
References

We thank Dr. Pulak Ray of Saha Institute of Nuclear Physics for
assistance and help in transmission electron microscopy. We also
thank CSIR (Grant 37(1275)/06/EMR-II and 9/28(646)/2005-EMR-I)
for financial support. We thank UGC (Grant No. 348/Univ/Fellow/
May 06) for a fellowship. We thank Ms. Suryyani Deb, Mr. Santi
S. Singha, and Mr. Hirak K. Patra for miscellaneous help and sug-
gestions. We also thank an anonymous reviewer for valuable sug-
gestions. While writing this paper the first author expired and this
being his first and last work the rest of the authors and his lab-
mates dedicate the work in his memory.
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