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Materials Chemistry and Physics 121 (2010) 349353

Contents lists available at ScienceDirect

Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

UVvisible light reshaping of gold nanorods

El-Sayed A.M. Al-Sherbini
Department of Measurements, Photochemistry and Agriculture, National Institute of Laser Enhanced Science (NILES), Cairo University, P.O. Box 12613, Al-Gamaa, Cairo, Egypt

a r t i c l e

i n f o

Article history:
Received 28 June 2009
Received in revised form 3 January 2010
Accepted 25 January 2010
Keywords:
Gold nanoparticles
Localized surface plasmon resonance (LSPR)
Photostability
Laser ablation
Micellar solutions

a b s t r a c t
The photostability of gold nanoparticles prepared via laser ablation in water or aqueous micellar solution and by wet chemical method was studied using irradiation from diode laser of wavelengths 620,
560, 520, 460 nm and UV-light sources. The results showed that gold nanoparticles prepared in micellar
solution were not affected by irradiation from all light sources, whereas aggregates were observed in
case of that prepared by laser ablation in distilled water. This may be attributed to the stabilizing role of
the capping micelles which prevent nanoparticles from aggregation during the irradiation time course.
Moreover, UV-irradiation of gold nanorods of aspect ratios 2.6, 3.1, 3.6, and 3.8 with absorption maxima
at 700, 730, 760 and 780 nm, respectively, leads to a change in particles morphology and shape as well as
photodecomposition of the rods. The rate of photodecomposition decreases with decreasing the aspect
ratio and the critical photodecomposition was found to be at aspect ratio 2.3 0.1. The decreasing was
explained by the dissolution of the surfactant around the gold nanorods.
2010 Elsevier B.V. All rights reserved.

1. Introduction
Gold nanoparticles have unique optical and chemical properties
that make them ideally suited for a number of applications in bionanotechnology, including optical probes, targeted drug delivery,
and programmed material synthesis. The optical response of gold
nanoparticles is often characterized by the presence of a strong
absorption band that is absent from the spectrum of the bulk. This
is attributed to a resonance in the collective motion of the conduction electrons in response to an incident electromagnetic eld and
is called the localized surface plasmon resonance (LSPR). LSPR is
dependent on the size, shape and degree of particleparticle coupling of the nanoparticles, dielectric properties of the metals from
which the nanoparticles are composed and dielectric properties of
the local environment in which the nanoparticles are immersed
[14].
Gold nanoparticles in different modications (e.g. spherical,
rods, shells) are the most promising candidates for photothermal
(PT) sensitizers, since they are strong absorbers, nontoxic, easily
conjugated to antibodies or protein and have adjustable optical
properties. It has been discovered that an accumulation of gold
nanoparticles on a cell membrane leads to an increase in bubble
formation efciency, resulting in more severe cancer cell damage
at relatively low laser uence of 6080 mJ cm2 , which is safe for
normal tissues [5,6].

Tel.: +20 235729499; fax: +20 235729499.

E-mail addresses: elsayed s2000@yahoo.com, elsayed@niles.edu.eg.
0254-0584/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2010.01.048

Nanophotothermolysis with pulsed lasers and absorbing

nanoparticles attached to specic targets has recently demonstrated great potential for selective damage to cancer cells, bacteria,
viruses and DNA. When nanoparticles are irradiated by short-laser
pulses, their temperature rises very quickly leading to irreversible
cell target damage, without damaging the surrounding healthy tissues.
The effect of temperature on the gold nanorods encapsulated in micelles [7] was investigated and the results showed
that the absorption maximum of the longitudinal band SPL of
the nanorods decreases and blue shifted with increasing the
temperature time courses while the average width remains approximately constant [810]. This might be due to the differential
thermal instability of rods or the capping micelles. The temperature could reshape the individual nanorods inside the micelles, or
the long micelles could dissolve as the exposure time of temperature increases. The later leads to precipitate of the longer gold
nanoparticles out of the solution being studied. The effect of shortlaser pulses on the stability of gold nanorods was studied. The
results showed that the nal products strongly depend on the
energy of the laser pulse as well as on its width. At high laser
uencies (1 J cm2 ) the gold nanorods was melted into spherical nanoparticles (nanodots). Upon decreasing the energy of the
excitation pulse, only partial melting of the nanorods takes place.
Shorter but wider nanorods are observed in the nal distribution
[1113].
In the present study the photostability of the gold nanoparticles
prepared via laser ablation in water or in aqueous micellar solution
and by wet chemical method was studied using different low power
laser sources and UV-light conventional lamps.

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E.-S.A.M. Al-Sherbini / Materials Chemistry and Physics 121 (2010) 349353

Fig. 1. Schematic diagram of the experimental set up.

2. Experimental section
Gold nanoparticles were prepared by laser ablation of a metal gold plate in
aqueous micellar solution of cetyltrimethylammonium bromide (CTAB) (Puress,
Fluka). Double distilled water was used. As shown in Fig. 1, the gold plate (>99.9%)
was placed on the wall of a glass tube lled with 3 mL of micellar solution. Laser
pulses ( = 8 ns at 10 Hz) from a Nd-YAG laser (continuum SLI-10) at  = 1064 nm
were focused onto the surface of a gold plate using a fused silica cylindrical lens
(p = 100 nm). The focused region on the gold plate has a rectangular shape of 6 nm
length and 0.5 nm wide. The position of the laser beam on the surface of the prepolished metal plate could be varied, to obtain a fresh surface and help to provide
homogeneous nanoparticles. The energy of Nd-YAG laser was 100 mJ pulse1
measured by power energy meter (molectron-EPM 2000:Tar5). The colored solution was measured by PerkinElmer Lmbda-40 spectrophotometer after irradiation
time courses. The samples prepared by laser ablation technique or by the chemical
method were irradiated under different diode laser sources of different wavelengths
of 620, 560, 520, 460 nm and or by using UV-light source (Analamp mod. 81-105-701, 230 nm, USA) 3 ml colloidal solution of the nanoparticles were put at 5 cm under
the UV-light source and were exposed at different irradiation times.
Gold nanospheres were prepared by borohydride reduction of the gold salt in
the presence of cetyltrimethylammonium bromide (CTAB) as capping agent [14].
Gold nanorods were prepared according to method reported by Nikoobakat et al.
[15]. Gold nanorods prepared by using seed-mediated method. Seed and growth
solutions were made as described below.

3. Seed solution
Cetyltrimethylammonium bromide (CTAB) solution (2.5 ml,
0.20 mol dm3 ) was mixed with 2.5 ml of 5 104 mol dm3
HAuCl4 . To the stirred solution, 0.3 ml of ice-cold 0.01 mol dm3
NaBH4 was added. The brownish yellow solution was vigorously
stirred for 2 min and was kept at 25 C.
4. Growth solution
CTAB (2.5 ml, 0.20 mol dm3 ) was added to specic amount of
4 103 mol dm3 AgNO3 solution at 25 C. To this solution, 2.5 ml
of 5 103 mol dm3 HAuCl4 was added, and after gentle mixing
of the solution 70 l of 0.0788 mol dm3 ascorbic acid (freshly prepared) added. Ascorbic acid as mild reducing agent changes the
growth solution from dark yellow to colorless. The nal step was the
addition of the seed to the growth solution at 2730 C. The color of
the solution gradually changed within 1020 min. For longer NRs,
the color changes takes place more slowly. The temperature of the
growth medium was kept constant at 2730 C in all the nanorods
preparations. By adjusting the amount of silver ions or gold seed
concentrations the different aspect ratios can be obtained.

Fig. 2. Shows the dependence of the absorption spectra of gold nanoparticles prepared by chemical method in micellar solution on UV-irradiation at 230 nm: interval
time (15) 20 min.

are characterized by two bands. The rst band is an intense band

at longer wavelength and it is corresponding to the longitudinal
resonance band and the other is a much weak transverse resonance
band at ca. max = 528 nm [1618]. The position of the longitudinal
band undergoes red shift with increasing the gold nanorods aspect
ratio. The mean transverse diameter of Au nanorods is typically
equal to ca. 10 nm, while its mean longitudinal lengths are variables
[14].
5.1. Effect of irradiation by diode laser sources and by UV-light
Nanoparticles such as gold when stimulated with the right frequency of laser light can act as tiny, precise and powerful heaters,
which potentially could be used in biomedical applications. The
problem is that the stability during irradiation by different laser
sources is a crucial parameter. Thus, the study of the photostability
is of a special interest to evaluate how the gold nanoparticles can
be applied in the eld of biotechnology.
By irradiation the spherical nanoparticles, that are previously
prepared by chemical method or by laser ablation technique
in micellar solution, using diode lasers (620, 560, 520, 460 nm;
150250 W m2 ) or UV lamp as a function of time, the optical density showed a slight decrease in the intensity without
any remarkable shifts in the corresponding wavelengths of each
nanoparticles, Figs. 2 and 3. This may be due that the capping
micelles prevent the nanoparticles from aggregation during the

5. Results and discussion

It is well known that, the optical absorption spectrum of gold
nanoparticles is due to the surface plasmon (SP) resonance(s) and
that the nanoparticles of sizes of 550 nm show a sharp band in the
520530 nm regions [14] where it is known a transverse band. With
increasing the length of the nanoparticles, the absorption spectra

Fig. 3. Shows the dependence of the absorption spectra of gold nanoparticles produced by laser ablation in micellar solution on UV-irradiation at 230 nm: interval
time (14) 20 min.

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Fig. 4. Dependence of the absorption spectra of gold nanoparticles on diode laser

at 620 nm: interval time 20 min.

351

Fig. 6. Dependence of the absorption spectra of gold nanoparticles on UV-irradiation

at 230 nm: interval time 20 min.

irradiation time courses. Also an aqueous solution of gold nanorods

with the absorption spectra of max. = 730 nm was irradiated under
the same conditions by using diode lasers at 620 nm, Fig. 4. The gure demonstrates insignicant decrease in the optical density with
increasing the exposure time. The same results were obtained when
the samples were irradiated at 560, 520, 460 nm, are not shown
here.
Fig. 5 shows the absorption spectra of the changes of gold
nanorods of (L/d = 3.1) before and after irradiation by UV-light
at 365 nm. The optical density at both longitudinal and transverse
plasmon bands decreases with increasing the irradiation time and
the absorption maxima was gradually shifted to shorter wavelengths (max. = 730691 nm). The optical density at max. = 533 nm
decreased without changes in the band width in the range
511550 nm.
When a new sample of the same aspect ratio (L/d = 3.1) irradiate by UV-light source at 230 nm, Fig. 6. The gure showed
that the rate of the photodegradation increases and it was also
blue shifted to max. = 677 nm. Therefore, the decreasing in the
absorbance and the blue shifts in SPL are caused by decreases in
the average length of the nanorods and the absorption spectra
changes in linear way, Fig. 9-5,6. This may be due to the regular reshaping of the nanorods inside the capping micelles. The
rod shape capping CTAB micelles is unstable, and they decompose
much faster than the short rod shape micelles. Accordingly, the
long gold nanorods decompose and precipitate out in the solution.

Structural transformation of gold nanorods is investigated by using

low-energy femtosecond and nanosecond laser pulses in colloidal
solution [13]. The observation results suggested that, short-laser
pulsed photothermal melting begins with the creation of defects
inside the nanorods followed by surface reconstruction and diffusion, in contrast with the thermal melting of the rods, where the
melting starts at the surface. The thermal stability of gold nanorods
in aqueous micellar solution and in binary glycerol/water micellar solutions was studied [9,10]. The results indicated that such
change in conguration requires the breaking of bond between
the micelles and the gold surface, which could lead to either the
breaking of the micelles around the long rods or the annealing
of the micelles around the shorter rods. At this point, the longer
rods break faster than the shorter one as the temperature increases.
With increasing the aspect ratios of gold nanorods, the rate of photodecomposition increases with increasing the length, Figs. 7 and 8.
Fig. 8 shows the TEM images of gold nanorods taken from solution
(a) at the start and (b) at the end of the experiment. Fig. 9 illustrates the normalized absorption spectra of the gold nanoparticles
at different aspect ratios and different irradiation time courses. The
gure shows that the rate of photodecomposition depends on the
aspect ratio. As observed from the gure, a slight decreasing in the
rate in case of nanosphere or with using the diode laser. When
UV-light was used the results shown high increases in the pho-

Fig. 5. Dependence of the absorption spectra of gold nanoparticles on UV-irradiation

at 365 nm: interval time (15) 20 min, 6 = 40 min.

Fig. 7. Dependence of the absorption spectra of gold nanorods on UV-irradiation at

230 nm: interval time 20 min.

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E.-S.A.M. Al-Sherbini / Materials Chemistry and Physics 121 (2010) 349353

Fig. 10. Rate of photodecomposition of gold nanparticles at different ratios L/d.

Fig. 8. Dependence of the absorption spectra of gold nanorods on UV-irradiation

at 230 nm. TEM images of gold nanorods taken from solution (a) at the start of the
experiment and (b) at the end of the experiment (scale bar 50 nm).

todecomposition in linear way with increasing the aspect ratios

(L/d). The effect of the aspect ratio on the photodecomposition
rate was calculated from the slope of different aspect ratios in
Fig. 9. In case of the aspect ratio of 2.6 the photodecomposition
rate was 6 105 absorbance s1 , while for 3.8 aspect ratio, the
photodecomposition rate was 2 104 absorbance s1 . The relation between the photodecomposition rates s1 versus the different
aspect ratios illustrated in Fig. 10, and could be calculated according
the following equation.
R=C +BX
R = 5 105 + 6.4e6 X

where R is the rate of photodecomposition s1 . C is the intersection

of the linear curve with the y axis, B is the slope of the linear curve
and X is the aspect ratio.
The critical aspect ratio given by intersection of the linear curve
with the x axis. The gure shows that at aspect ratio 2.3 0.1
the nanorods may be difcult to decompose by UVvisible light.
It also showed that, the rate of photodecomposition increases by
5.3e8 s1 with increasing the L/d by 0.1. Fig. 11a shows the
absorption spectra of gold nanoparticles prepared by laser ablation
technique in distilled water. By UV-irradiation the nanoparticles
as a function of time courses, the absorption maximum of the surface plasmon resonance (SP) shows a red shift and accompanied

(1)

Fig. 9. Normalized absorption spectra of gold nanparticles at different irradiation

times.

Fig. 11. (a) Dependence of the absorption spectra of gold nanoparticles prepared by
laser ablation technique in distilled water on UV-irradiation. (b) Gold nanoparticles
in H2 O before irradiation and (c) after irradiation.

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with a decreasing in the optical density and a broadening of the

absorption spectra within 600850 nm. The broadening might
be due to inhomogeneous in the size and shape distribution. The
observed red shifts from max. = 521 nm to max. = 540 nm with the
decreasing in the optical density of the absorption maximum can
be ascribed to the increasing in the particle sizes of the aggregated
gold nanoparticles. Fig. 11b showed the TEM of gold nanoparticles before (a) and after irradiation (b) where aggregation is clearly
observed. It is worthwhile to maintain that the capping micelles
prevent the spherical nanoparticles from aggregation during the
irradiation time courses.
Acknowledgment
The author gratefully acknowledge the help of Prof. M.A. ElSayed, the director of Laser Dynamics Lab. (LDL) at the School of
Chemistry and Biochemistry, Georgia Institute of Technology for his
many helpful discussions during the preparation of this manuscript.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.matchemphys.2010.01.048.

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