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International Journal of Heat and Mass Transfer 89 (2015) 866–871

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International Journal of Heat and Mass Transfer


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

Photothermal response of hollow gold nanoshell to laser irradiation:


Continuous wave, short and ultrashort pulse
Ali Hatef a, Simon Fortin-Deschênes a, Etienne Boulais b, Frédéric Lesage c, Michel Meunier a,⇑
a
École Polytechnique de Montréal, Laser Processing and Plasmonics Laboratory, Engineering Physics Department, Montréal, Québec H3C 3A7, Canada
b
Department of Biological Engineering, Laboratory for Computational Biology & Biophysics, Massachusetts Institute of Technology, Cambridge, MA 02139, USA
c
École Polytechnique de Montréal, Department of Electrical Engineering, Montréal, Québec H3C 3A7, Canada

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

Article history: This paper is to investigate numerically the photothermal response of the most common size of gold
Received 2 October 2014 nanoshell (AuNS) in an aqueous medium for biomedical applications. Three types of laser light irradiate
Received in revised form 16 May 2015 the particle; a continuous-wave (CW), short (nanosecond) and ultrashort (femtosecond) pulse laser. The
Accepted 16 May 2015
spatiotemporal evolution of the temperature profile inside and around the AuNS is computed using a
numerical framework based on the finite element method (FEM). For CW and nanosecond (ns) pulse laser
where the AuNS’s electrons and lattice are at thermal equilibrium, the ordinary heat diffusion equation is
Keywords:
used to describe the heat transfer to the surrounding water. For femtosecond (fs) pulse laser, due to the
Modeling and numerical simulation
Finite element method
inexistence of the thermal equilibrium, a two-temperature model (TTM) is used to describe the heat
Continuous wave transfer processes occurring in the AuNS and the normal heat diffusion equation is used for the heat flux
Short and ultra-short pulse laser calculation at the particle/water interface. For each case, the influence of laser intensity on the maximum
Hollow gold nanoshell and plasmonic temperature reached at the particle/water interface is studied. The aim of this study is to provide a
photothermal therapy description for the fundamentals of heat release of AuNSs and useful insights for the development of
these particles for biomedical applications such as drug delivery, photothermal cancer therapy and opto-
poration of cells.
Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction temperature raises killing tumour cells that can be furfure


exploited for cancer therapy [9–13].
Gold nanoparticles (AuNPs) are well known for their capabili- Among all AuNPs, the ultra-thin hollow gold nanoshells (AuNSs)
ties to support localized surface plasmon resonance (LSPR) due to exhibits a unique combination of small size, strong, narrow and
collective and coherent oscillations of free electrons at the surface tunable absorption band in the near infrared (NIR) tissue window
of the particle. In resonance with an external electromagnetic (wavelength: 700–900 nm). These particles consist of a spherical
wave, occurring at a specific wavelength range, the AuNPs show gold shell filled with its embedding aqueous medium [14]. For
unique optical and thermal properties [1,2]. Illumination of the biomedical applications, smaller size (outer diameter, 30–50 nm)
AuNPs at or close to LSPR wavelength results in a near field allows prolonged blood circulation time and better chance in
enhancement, scattering and conversion of absorbed light energy crossing the tumour vessel wall. The strong and tunable absorption
to heat [3]. In addition, the surface of AuNPs can be routinely func- band in NIR regime enables a large penetration depth, even at low
tionalized with active ligands, monoclonal antibodies and thiolated laser intensities, that ranges from a few millimeters to several cen-
molecules due to the strong Au-S bond [4,5]. These novel proper- timeters depending on tissue type [15–17]. The hollow core allows
ties of AuNPs provide a highly localized functional and multifunc- higher drug loading capacity, easier synthesis, and the pure gold
tional platform in biomedical applications, particularly in composition reduces toxicity [18,19]. AuNSs are usually synthe-
photothermal therapy, optoporation of cells and selective or tar- sized using cobalt (Co) nanoparticles as sacrificial templates, the
geted drug delivery. At low temperatures, this process can be gold shells being grown via a galvanic reaction with Au ions
exploited for thermally induced release of drugs attached to [14,19–21].
AuNPs, which allows precise, on-demand delivery into the intracel- Photothermal response of AuNSs strongly depends on the irra-
lular environment [6–8]. However, at higher temperature, AuNPs diation regime (CW, ns and fs) that can be selected based on the
⇑ Corresponding author.
requirement of a specific biological application. For instance, irra-
E-mail address: michel.meunier@polymtl.ca (M. Meunier).
diation of AuNSs by a CW laser is best suited for applications that

http://dx.doi.org/10.1016/j.ijheatmasstransfer.2015.05.071
0017-9310/Ó 2015 Elsevier Ltd. All rights reserved.
A. Hatef et al. / International Journal of Heat and Mass Transfer 89 (2015) 866–871 867

require an enduring, moderate increase in temperature, such as surface of the AuNS. The absorption, scattering and extinction
hyperthermia and photothermal release of molecules. In this case, cross-section are defined as rabs ¼ Q abs =I0 , rscatt ¼ Q scatt =I0 and
AuNSs dissipate the absorbed energy into their surrounding envi- rext ¼ rabs þ rscatt , respectively. Here, I0 ¼ ð1=2Þe0 nw E20 represents
ronment without a substantial increase of their temperature the intensity of the incident laser beam of amplitude E0 in the sur-
[22,23]. Some applications such as photoacoustic imaging of cells rounding medium.
and gene silencing by transfection, necessitate a much higher
energy density in the vicinity of the AuNSs [24]. Further reducing 2.2. Thermal evolution
of the pulse width up to fs regime enables a very high-localized
temperature increase, more efficient energy deposition allowing The equation governs the thermal evolution of the AuNS and
the cleavage of bonds to link molecules to the AuNS surface [25]. surrounding water strongly depends on the irradiation
In recent years, there has been few research interests to time-regime. Comparison the pulse laser time width to the
advance fundamental understanding of plasmon-assisted pho- electron-lattice thermalization time 0.5–1 ps [32] plays a key role
tothermal phenomena around AuNS [26,27]. The main objective to choose thermal evolutional equations. For CW irradiation and ns
of this paper is to investigate the spatiotemporal photothermal pulses, the pulse width is much longer than electron-lattice ther-
response of the most common size of AuNS (40 nm diameter and malization time, therefore, the gold electrons and lattice are heated
3 nm shell thickness) for biomedical applications [28]. The particle in relative equilibrium. In this case the AuNS and water tempera-
is irradiated by CW, ns and fs laser pulses in water medium at a ture evolution are calculated from the usual heat diffusion equa-
wavelength of 800 nm where scattering in biological tissue is very tion [33]:
low. It has been found that such a AuNS around this size anneals
into solid particles within hours at 523 K [29], therefore, we @Tðr; tÞ
restrict the maximum temperature increase calculation to be in
qðrÞcðrÞ ¼ r  ðkðrÞrTðr; tÞÞ þ Q ðr; tÞ; ð3Þ
@t
the same range. For each irradiation regime we show the maxi-
in above equation, T(r, t) is the local temperature, r is the posi-
mum temperature increase dependency and rate to laser intensity.
tion with the origin fixed at the particle center and t is the
It is worth to mention here that although we performed the calcu-
time. Three material parameters: cðrÞ; qðrÞ and kðrÞ are the heat
lations for a particular sized AuNS, however, upon request the
capacity, mass density and thermal conductivity, respectively.
developed tools are capable of doing the same calculation for any
metallic configuration and shape. Q ðr; tÞ ¼ h~
jðr; tÞ  ~
Eðr; tÞi is the local heat generation density result-
t

ing from the electric current density ~ jðr; tÞ in the shell. In the case
2. Methods of pulse laser, the local field intensity calculated in Eq. (1) is modu-
lated by the Gaussian time profile of the incident laser pulse. The
The modeled system consists of AuNS with water core of radius intensity of the ns and fs pulse lasers are modeled by a Gaussian
of 17 nm and a gold layer with a thickness of 3 nm. The AuNS is curve, as following:
!
immersed in water since this medium has proven to be adequate
FL ½t  t 0 2
for the modeling of laser processes occurring in a cellular medium. IðtÞ ¼ pffiffiffiffiffiffiffi exp ð4Þ
2pt r 2t 2r
The time-dependent distribution of the electromagnetic field and
thermal response of the AuNS is modeled by a system of partial dif- pffiffiffiffiffiffiffiffiffiffiffiffi
in the above equation, t r ¼ t l =2 2 ln 2 is the pulse width, where tl is
ferential equations (PDE). The system is solved in three-dimensional
the laser pulse width defined as the full with at half maximum of
(3D) using the finite element method (FEM) provided by the com-
the Gaussian temporal profile, t0 is the position of the center of
mercial software COMSOL 4.3 (www.comsol.com).
the peak and FL is the incident laser energy density (fluence).
Absorption of radiation in the core and in the surrounding
2.1. Electromagnetic field distribution
medium is neglected. In our calculations, the following thermal
characteristics of water and gold are used: cw = 4182 J kg1 K1,
Assuming time-harmonic electric field, the electric field distri-
qw = 103 kg m3, kw = 0.6 W K1 m1, cAu = 130 J kg1 K1, qAu =
bution ~
Eðr; tÞ is computed using the Helmholtz equation [13]: 19.3  103 kg m3 and kAu = 300 W K1 m1.
  To study fs pulsed laser and AuNS interaction mechanisms, we
~ 2 r ~
r  ðl1
r r  EÞ  k0 er  j E¼0 ð1Þ consider the case where tl is much smaller than the characteristic
xe0
time constants of the transient non-equilibrium photothermal
where er is relative permittivity. For gold shell this quantity is a effects. These characters are electron–lattice interactions and pho-
complex, frequency dependant number and interpolated from non–phonon interactions at the surface of the particle. For this
Johnson and Christy [30]. For water er is set to be 1.77. The relative time regime the TTM can be used in which the electrons and lattice
permeability lr is taken as unity and k0 is the wave number. The remain at different temperatures (Te and Tl). This is due to the fact
other parameters in Eq. (1) are given in the reference [13]. This that the heat conduction in the lattice is small compared to that in
equation is solved in a spherical domain 10 times larger than the the electrons. Also the electron relaxation time is shorter than tens
AuNS with an outer perfectly matched layers (PML) shell and a scat- of fs for gold. In the water, considering laser fluences well below
tering type boundary condition that emulates an infinite domain. the optical breakdown, direct absorption is neglected and the usual
Assuming a non-dissipative host medium, the absorbed and one temperature heat diffusion equation applies. However,
scattered energies by the AuNS are obtained as [31]: because of the phonon mismatch factor, discontinuity between
ZZ  the water and shell temperature appears at the interface. We solve
1 ~ ~scat  ~
Q scat ¼ Re Escat  H nds ð2-aÞ the following set of thermal evolutional equations for the electrons
2 s
and the lattice for AuNS and water [34]:
ZZ 
1 ~ ~tot  ~
Q abs ¼ Re Etot  H nds ð2-bÞ
2 s
@T e ðr; tÞ
C e ðT e Þ ¼ r  ðke  rTðr; tÞÞ  G  ½T e ðr; tÞ  T l ðr; tÞ þ SðtÞ
@t
where ~E and H~ represent the electric and magnetic field vectors,
ð5-aÞ
respectively. ~
n is an outward-pointing unit vector normal to the
868 A. Hatef et al. / International Journal of Heat and Mass Transfer 89 (2015) 866–871

@T l ðr; tÞ 2
C l ðT l Þ ¼ r  ðkl  rT l ðr; tÞÞ þ G  ½T e ðr; tÞ  T l ðr; tÞ  F Absorption
@t 1.8 Scattering
ð5-bÞ Extiction
1.6

Cross section (nm2×104)


@T ðr; tÞ 1.4
qm ðrÞcm ðrÞ m ¼ r  ðkm  rT m ðr; tÞÞ þ F; ð5-cÞ
@t 1.2
in above equations, Te, Tl and Tm are the time dependent tempera- 1
tures of the electrons, lattice and surrounding medium, respec- 0.8
tively. c is the heat capacity (ce, electronic; cl, lattice and cm,
0.6
medium heat capacity) and k is the thermal conductivity. The
second term on the right hand side in (5-a) and (5-b) describes 0.4
the energy exchange from the electrons to the lattice via elec- 0.2
tron–phonon coupling with a coefficient G. The thermal conduc- 0
tance G = 2  1016 W/m3K [32] relates the temperature drop at an 600 650 700 750 800 850
interface to the heat flux crossing the interface and constitutes Wavelength (nm)
the coupling parameter between a particle and surrounding med-
ium energy equations. The term S(t) in Eq. (5-a) is the absorbed Fig. 1. FEM calculation of scattering, absorption and extinction cross sections for a
laser energy. Also, the F term in Eqs. (5-b) and (5-c) describes the 40 nm diameter AuNS with a 3 nm thick shell as a function of the incident laser
wavelength. The maximum energy absorption occurs at kmax = 715 nm. Inset shows
heat transfer across the interface between AuNS and surrounding
cross-section of the near-field enhancement distribution in and around an AuNS at
which is defined as [34]: off-resonance wavelength k = 800 nm. The color legend on the right shows the
3 magnitude of the field enhancement.
3hr 2
F¼ ½T l ðr; tÞ  T m ðr; tÞ ð6Þ
ðr32  r31 Þ
here, h is called interfacial thermal conductance and is the fitting
for Ti:sapphire femtosecond laser. The inset in Fig. 1 shows
parameter for the cooling process of AuNS in aqueous solutions.
near-field enhancement when a linearly polarized laser irradiates
Its value is 105  106 Wm2K1 [35]. Here kl = 0.001  kAu,
the particle. The color legend on the right shows the magnitude
ke = kAu, ce = 70  Te and cl = 3  106 J m3 K1 [36]. r2 and r1 are
of the field enhancement (|E|/|E0|). As shown in the inset, although
the outer and inner shell radius, respectively.
the incident laser field has an off-resonance wavelength, near-field
It is worth to mention that in the previous studies on fs
enhancement still occurs in a region 20 nm wide around the
laser-AuNP interaction [37], AuNP is treated as a point absorber
structure and a significant portion of the electromagnetic energy
by considering kl DTl  0 and ke DTe  0 in Eqs. (5-a) and (5-b).
is absorbed in the gold shell.
Neglecting these two terms causes a nonuniform temperature dis-
tribution at the surface of the AuNP. However, in our calculations,
we considered these two terms and removed this approximation.
This study focuses on irradiation conditions leading to moder- 3.1. Continuous wave laser illumination
ate temperature increase of the medium surrounding the particle.
This regime corresponds to temperature increases that lead to sig- The most trivial phenomenon occurs following the CW laser
nificant cell membrane damage (55 K) [38]. Being significantly irradiation is the heating of the AuNS and the subsequent heat
lower than the annealing temperature of AuNS into solid AuNPs transfer to the water by a simple conduction process at the surface.
(523 K [29]), evaporation or fragmentation of the AuNS is very For this case, the time taken by the system to reach equilibrium
unlikely and is neglected in the modeling. In addition, temperature depends on the thermal conductivity and the thermal capacity of
reached in the aqueous medium remains well below the water crit- the surrounding medium. However, for AuNS in water, the thermal
ical temperature (647 K). Hence cavitation resulting from phase energy generated inside the particle dissipates through the water
explosion or explosive boiling is neglected. within several nanoseconds [22].
We also performed calculations on the time evolution of the
3. Results and discussion temperature increase of the AuNS and the dependency of the evo-
lution on the incident CW laser beam intensity. The results show
Fig. 1 shows the AuNS absorption, extinction and scattering that for all intensities, the time required to reach 90% of maximum
cross-sections as a function of wavelength. Absorption is domi- temperature increase is about 100 ns. In Fig. 2 we show maximum
nant, with a maximum value (rabs = 1.53  104 nm2) occurring at temperature increase at the AuNS/water interface as a function of
the resonance wavelength of 715 nm (kmax). laser intensity. The rate of this maximum temperature increase is
The off resonant wavelength (k = 800 nm) lies on the middle of 32.5 K cm2/MW. The inset shows the steady-state radial tempera-
minimum absorption window in water where the penetration ture increase in and around the AuNS. Knowledge of the heat
depth of the incident laser field is at its maximum value. affected zone and space-dependent temperature increase is impor-
Therefore, our results can be more useful especially for biological tant because in practice the AuNSs are functionalized by chemical
application where one can consider the biological tissue and envi- or biochemical materials (e.g. antibody, antigen or ligand) and they
ronment as water [39]. Please note that for off resonant wave- may not be attached directly to the biological systems like cell
length the AuNS absorption cross section (rabs = 1.53  104 nm2) membrane, and temperature reached inside the AuNS alone might
is around 24 times less than the on resonant wavelength case not be relevant [40].
(rabs = 6.4  102 nm2 at k = 715 nm). In result irradiating the The temperature inside the AuNS is spatially uniform due to the
AuNS at this off resonant wavelength avoids overheating and dam- high thermal conductivity of gold and small shell volume. The
aging the particle. Also the thermal energy deposition in AuNS is a maximal temperature increase varies linearly with the field inten-
linear process, therefore one can easily use the results here in the sity. Typically, the temperature increase is shown to drop to 10%
case of off resonant wavelength as well. From practical point of of its maximum value at 200 nm from the AuNS center, enabling
view this wavelength is one of the most common and stable one possible long-range interactions inside biological systems.
A. Hatef et al. / International Journal of Heat and Mass Transfer 89 (2015) 866–871 869

300 temperature varies linearly with the fluence, with a slope of

Temperature Increase (K)


180
160 3.4 K cm2/mJ. The upper inset shows the time evolution of the tem-
140
120
perature increase on the shell’s outer surface when irradiated with
Max. temperature increase (K)

250 100 a single pulse with FL = 20 mJ/cm2. The laser peak intensity is
80
60
I = 3.75 MW/cm2. The maximum temperature increase
I = 5 MW/cm2
200
40 DTmax = 68 K is shown to occur 1 ns after the peak intensity.
20
0
0 50 100 150 200
Distance (nm)
3.3. Femtosecond pulse laser illumination
150

In this section we study the thermodynamic response of the


100 AuNS to a fs laser pulse. Fig. 4 illustrates the evolution of Te, Tl,
Slope=32.5 Kcm2/MW
and Tm, for a AuNS excited by a 100 fs laser pulse at a wavelength
of 800 nm and a laser fluence of 2 mJ/cm2. As mentioned in the
50 method section, the TTM is used to describe the thermal evolution
of the system, which neglects the initial nonthermal electron dis-
tribution. Due to the smaller electron heat capacity and electron–
0
electron scattering time, the conduction electrons in the shell first
0 1 2 3 4 5 6 7 8 9
Laser Intensity (MW/cm2) absorb the laser energy through the excitation of a plasmon that
decays rapidly, leading to a highly energetic electron population.
Fig. 2. Maximum temperatures increase at the surface of AuNS embedded in water Therefore, Te rises very rapidly and reaches a maximum value
versus CW incident laser intensity. Inset shows the steady-state distribution of
temperature increase as a function of the distance from the AuNS center for
intensity of I = 5 MW/cm2.
10000 2
(a)
1.8
Te (Electron temperature)
300 80 4 1000 1.6
Temperature increase (K)

Intensity (MW/cm2)

60 3
Temperature increase (K)

1.4

Intensity ×104 (MW/cm2)


250
Max. temperature increase (K)

40 2
100 1.2
20 1 Tl (Lattice temperature)
200 1
0 0
0 10 20 30 40 50 10 0.8
Time (ns)
70
150
Temperature increase (K)

60 0.6
50
40
1 Tm (Medium temperature) 0.4
100
30
0.2
20
8 ns 10 ns
50 10 0.1 0
0 0.1 1 10 100 1000 10000
Slope=3.4 Kcm2/mJ 0 10 20 30 40 50 60 70 80
Distance (nm) Time (ps)
0
0 20 40 60 80 100 350 6000
Laser fluence (mJ/cm2)
Maximum lattice & medium temperature increase (K)

(b)
Fig. 3. Maximum temperature increases variation on the surface of AuNS embed- 300
5000

Maximum electron temperature increase (K)


ded in water irradiated by a 5 ns laser pulse at 800 nm versus laser fluence. In upper
inset the solid and dashed line shows the temperature increase evolution and the
250 Te (Max. Electron temperature)
pulse intensity, respectively. In lower inset the solid and dashed line shows the 4000
Slope=1500 Kcm2/mJ
temperature increase profile as a function of the radial distance from the particle
center on the pulse peak time (8 ns) and 10 ns. For both insets the fluence is 20 mJ/ 200
cm2.
3000
Tl (Max. Lattice temperature)
150 Slope=113 Kcm2/mJ
3.2. Nanosecond pulse laser illumination 2000
100
In this case we study the AuNS thermodynamic response when
Tm (Max. Medium temperature)
the particle is irradiated by a Gaussian ns laser pulse with a dura- 1000
50 Slope=20 Kcm2/mJ
tion tl = 5 ns, centered at time t0 = 8 ns. This pulse width is much
longer than the characteristic time constants of the transient
0 0
non-equilibrium photothermal effects. To calculate the tempera- 0 0.5 1 1.5 2 2.5 3
ture evolution of the particle during and after the interaction with Laser fluence (mJ/cm2)
the laser pulse, we numerically solve the heat transfer Eq. (3)
[41,42]. Fig. 3 shows how the maximum temperature at the Fig. 4. (a) Time dependent temperature evolution of electrons, Te, lattice Tl and
AuNS/water interface varies with the fluence of the incident ns water temperature Tm, at the AuNS–water interface, for a laser pulse of 100 fs at
wavelength k = 800 nm with a fluence of 2 mJ/cm2. The dotted curve shows the
laser pulse. Increasing the energy density of the laser pulse is
Gaussian intensity profile of the pulse. (b) The maximum temperature increase of
shown to have no effect on the time required for the particle to (star markers) electrons (Te), (circle markers) lattice (Tl), and (square markers)
reach its maximum temperature. Interestingly, the maximum water (Tm) at the AuNS/water interface for different fluences.
870 A. Hatef et al. / International Journal of Heat and Mass Transfer 89 (2015) 866–871

Table 1 (GRSTB) and Unité de participation et d’initiation à la recherche


Comparison the rate of maximum temperature increase in AuNS for CW, ns and fs (UPIR) for financial support.
pulsed laser irradiance.

Laser irradiance Rate


CW 32.5 K cm2/MW References
Ns pulsed laser 3.4 K cm2/mJ
Fs pulsed laser 113 K cm2/mJ [1] E. Boulais, R. Lachaine, A. Hatef, M. Meunier, Plasmonics for pulsed-laser cell
nanosurgery: fundamentals and applications, J. Photochem. Photobiol., C 17
(2013) 26–49.
[2] M.I. Stockman, Nanoplasmonics: past, present, and glimpse into future, Opt.
4360 K that happens 325 fs after the pulse peak. Subsequently, the Express 19 (2011) 22029–22106.
[3] Z. Qin, J.C. Bischof, Thermophysical and biological responses of gold
energy deposited into the electronic system is transferred via elec- nanoparticle laser heating, Chem. Soc. Rev. 41 (2012) 1191–1217.
tron–lattice coupling to the lattice, increasing Tl up to 384 K within [4] R. Huschka, J. Zuloaga, M.W. Knight, L.V. Brown, P. Nordlander, N.J. Halas,
16 ps. Finally, by lattice–lattice interactions, the thermal energy is Light-induced release of dna from gold nanoparticles: nanoshells and
nanorods, J. Am. Chem. Soc. 133 (2011) 12247–12255.
transferred to the environment as the AuNS and medium reach [5] I.H. El-Sayed, X. Huang, M.A. El-Sayed, Selective laser photo-thermal therapy of
their equilibrium temperature. Here, Te and Tl reach thermal equi- epithelial carcinoma using anti-EGFR antibody conjugated gold nanoparticles,
librium within 20 ps and the AuNS transfers its energy to its sur- Cancer Lett. 239 (2006) 129–135.
[6] C.R. Patra, R. Bhattacharya, D. Mukhopadhyay, P. Mukherjee, Application of
rounding environment within several hundreds of picoseconds
gold nanoparticles for targeted therapy in cancer, J. Biomed. Nanotechnol. 4
(4 ns). (2008) 99–132.
Our results show that the time taken by the shell’s electrons [7] S. Yamashita, H. Fukushima, Y. Akiyama, Y. Niidome, T. Mori, Y. Katayama, T.
Niidome, Controlled-release system of single-stranded DNA triggered by the
and lattice to reach their respective maximal temperature is
photothermal effect of gold nanorods and its in vivo application, Bioorg. Med.
weakly dependent on the incident fluence, while it remain fixed Chem. 19 (2011) 2130–2135.
at Dt = 86 ps in the case of the surrounding water. Fig. 4(b) shows [8] G.B. Braun, A. Pallaoro, G. Wu, D. Missirlis, J.A. Zasadzinski, M. Tirrell, N.O.
the maximal lattice, electron and water temperature increase as a Reich, Laser-activated gene silencing via gold nanoshell-siRNA conjugates, ACS
Nano 3 (2009) 2007–2015.
function of laser fluence. As shown in this figure, the maximum [9] M. Paiva, D.J. Castro, M. Bublik, J. Sercarz, Laser-induced thermal therapy for
temperature increases linearly with the laser fluence, with slopes recurrent head and neck cancer: a comprehensive review: 50, J. Invest. Med. 54
Te,max, Tl,max and Tm,max being 1500, 113 and 20 K cm2/mJ, (2006) (S381-S382 310.2310/6650.2005.x0015).
[10] R.R. Letfullin, C. Joenathan, T.F. George, V.P. Zharov, Laser-induced explosion of
respectively. gold nanoparticles: potential role for nanophotothermolysis of cancer,
Note that Te, Tl and Tm reach thermal equilibrium after 4 ns. Nanomed. (Lond., England) 1 (2006) 473–480.
Here, the fluence required to reach a certain temperature is shown [11] X. Huang, P.K. Jain, I.H. El-Sayed, M.A. El-Sayed, Determination of the
minimum temperature required for selective photothermal destruction of
to be significantly lower for fs pulses than for ns laser irradiation. cancer cells with the use of immunotargeted gold nanoparticles, Photochem.
This can be of crucial importance in some biomedical applications, Photobiol. 82 (2006) 412–417.
where high laser power can damage living tissues. [12] F. Alali, I.H. Karampelas, Y.H. Kim, E.P. Furlani, Photonic and thermofluidic
analysis of colloidal plasmonic nanorings and nanotori for pulsed-laser
photothermal applications, J. Phys. Chem. C 117 (2013) 20178–20185.
[13] E.P. Furlani, I.H. Karampelas, Q. Xie, Analysis of pulsed laser plasmon-assisted
4. Conclusion photothermal heating and bubble generation at the nanoscale, Lab on a Chip –
Miniaturisation Chem. Biol. 12 (2012) 3707–3719.
[14] H.-N. Xie, I.A. Larmour, Y.-C. Chen, A.W. Wark, V. Tileli, D.W. McComb, K.
In this paper we presented a numerical framework to study
Faulds, D. Graham, Synthesis and NIR optical properties of hollow gold
thermodynamic response of hollow gold nanoshells (AuNSs) to a nanospheres with LSPR greater than one micrometer, Nanoscale 5 (2013) 765–
continuous wave (CW), short (ns) and ultra-short (fs) pulse laser 771.
irradiation. The AuNSs have a diameter of 40 nm with 3 nm shell [15] R. Bardhan, S. Lal, A. Joshi, N.J. Halas, Theranostic nanoshells: from probe
design to imaging and treatment of cancer, Acc. Chem. Res. 44 (2011) 936–
thicknesses that is the most common and appropriate size for 946.
biomedical applications [28]. Experimentally it has been shown [16] A. Shetty, A.M. Elliott, J.A. Schwartz, J. Wang, E. Esparza-Coss, S. Klumpp, B.
that for such a small size AuNS, if the gold lattice temperature Taylor, J.D. Hazle, R.J. Stafford, Use of gold nanoshells to mediate heating
induced perfusion changes in prostate tumors, in, 2008.
increase is more than 523 K, the particle most probably collapse [17] T.A. Erickson, J.W. Tunnell, Gold nanoshells in biomedical applications, in:
to a solid particle. Therefore, for all cases we restricted our param- Nanotechnologies for the Life Sciences, Wiley-VCH Verlag GmbH & Co. KGaA,
eters to avoid over heating the AuNP causing particle fragmenta- 2007.
[18] M.P. Melancon, M. Zhou, C. Li, Cancer theranostics with near-infrared light-
tion. In order to respect this restriction, we set an off resonance activatable multimodal nanoparticles, Acc. Chem. Res. 44 (2011) 947–956.
laser wavelengths for all cases at k = 800 nm. For all cases, we have [19] A.M. Schwartzberg, T.Y. Olson, C.E. Talley, J.Z. Zhang, Synthesis,
developed a computational platform based on finite element characterization, and tunable optical properties of hollow gold nanospheres 
, J. Phys. Chem. B 110 (2006) 19935–19944.
method for modeling transient and steady state temperature of
[20] H.-P. Liang, L.-J. Wan, C.-L. Bai, L. Jiang, Gold hollow nanospheres: tunable
the nanoshell-environment for different laser parameters. These surface plasmon resonance controlled by interior-cavity sizes, J. Phys. Chem. B
parameters were the intensity for CW laser and the laser fluence 109 (2005) 7795–7800.
[21] S. Preciado-Flores, D. Wang, D.A. Wheeler, R. Newhouse, J.K. Hensel, A.
in the case of ns and fs laser pulses. Table 1 compares the rate of
Schwartzberg, L. Wang, J. Zhu, M. Barboza-Flores, J.Z. Zhang, Highly
maximum temperature increase in AuNS for CW, ns and fs pulsed reproducible synthesis of hollow gold nanospheres with near infrared
laser irradiance. surface plasmon absorption using PVP as stabilizing agent, J. Mater. Chem.
21 (2011) 2344–2350.
[22] H.H. Richardson, Z.N. Hickman, A.O. Govorov, A.C. Thomas, W. Zhang, M.E.
Kordesch, Thermooptical properties of gold nanoparticles embedded in ice:
Conflict of interest characterization of heat generation and melting, Nano Lett. 6 (2006) 783–788.
[23] D.K. Roper, W. Ahn, M. Hoepfner, Microscale heat transfer transduced by
None declared. surface plasmon resonant gold nanoparticles, J. Phys. Chem. C 111 (2007)
3636–3641.
[24] L. Rouleau, R. Berti, V.W.K. Ng, C. Matteau-Pelletier, T. Lam, P. Saboural, A.K.
Kakkar, F. Lesage, E. Rhéaume, J.C. Tardif, VCAM-1-targeting gold nanoshell
Acknowledgment probe for photoacoustic imaging of atherosclerotic plaque in mice, Contrast
Media Mol. Imaging 8 (2013) 27–39.
The authors would like to thank Mrs. Alexandra [25] L. Guo, Y. Li, Z. Xiao, W. Lu, Photothermal properties of hollow gold
nanostructures for cancer theranostics, in: B. Bhushan, D. Luo, S.R. Schricker,
Thibeault-Eybalin for her insights and editing the manuscript, Le W. Sigmund, S. Zauscher (Eds.), Handbook of Nanomaterials Properties,
Groupe de recherche en sciences et technologies biomédicales Springer, Berlin Heidelberg, 2014, pp. 1199–1226.
A. Hatef et al. / International Journal of Heat and Mass Transfer 89 (2015) 866–871 871

[26] A.Y. Avetisyan, A.N. Yakunin, V.T. Valerii, On the problem of local tissue [35] O. Ekici, R.K. Harrison, N.J. Durr, D.S. Eversole, M. Lee, A. Ben-Yakar, Thermal
hyperthermia control: multiscale modelling of pulsed laser radiation action on analysis of gold nanorods heated with femtosecond laser pulses, J. Phys. D
a medium with embedded nanoparticles, Quantum Electron. 40 (2010) 1081. Appl. Phys. 41 (2008) 185501.
[27] N. Harris, M.J. Ford, M.B. Cortie, Optimization of plasmonic heating by gold [36] L. Guo, S.L. Hodson, T.S. Fisher, X. Xu, Heat transfer across metal-dielectric
nanospheres and nanoshells, J. Phys. Chem. B 110 (2006) 10701–10707. interfaces during ultrafast-laser heating, J. Heat Transfer 134 (2012) 042402.
[28] N. Koike, T. Ikuno, T. Okubo, A. Shimojima, Synthesis of monodisperse [37] D. Werner, S. Hashimoto, Improved working model for interpreting the
organosilica nanoparticles with hollow interiors and porous shells using excitation wavelength- and fluence-dependent response in pulsed laser-
silica nanospheres as templates, Chem. Commun. 49 (2013) 4998–5000. induced size reduction of aqueous gold nanoparticles, J. Phys. Chem. C 115
[29] G. Wu, A. Mikhailovsky, H.A. Khant, J.A. Zasadzinski, Chapter 14 synthesis, (2010) 5063–5072.
characterization, and optical response of gold nanoshells used to trigger [38] L. Huiyu, C. Dong, T. Fangqiong, D. Gangjun, L. Linlin, M. Xianwei, L. Wei, Z.
release from liposomes, in: D. Nejat (Ed.), Methods in Enzymology, Academic Yangde, T. Xu, L. Yi, Photothermal therapy of Lewis lung carcinoma in mice
Press, 2009, pp. 279–307. using gold nanoshells on carboxylated polystyrene spheres, Nanotechnology
[30] P.B. Johnson, R.W. Christy, Optical constants of the noble metals, Phys. Rev. B 6 19 (2008) 455101.
(1972) 4370–4379. [39] R. Weissleder, A clearer vision for in vivo imaging, Nat. Biotechnol. 19 (2001)
[31] L. Changhong, C.C. Mi, B.Q. Li, Energy absorption of gold nanoshells in 316–317.
hyperthermia therapy, IEEE Trans. NanoBiosci. 7 (2008) 206–214. [40] J.Z. Zhang, Biomedical applications of shape-controlled plasmonic
[32] A.-M. Dowgiallo, K.L. Knappenberger, Ultrafast electron-phonon coupling in nanostructures: a case study of hollow gold nanospheres for photothermal
hollow gold nanospheres, Phys. Chem. Chem. Phys. 13 (2011) 21585–21592. ablation therapy of cancer, J. Phys. Chem. Lett. 1 (2010) 686–695.
[33] A.O. Govorov, W. Zhang, T. Skeini, H. Richardson, J. Lee, N.A. Kotov, Gold [41] R.R. Letfullin, C.B. Iversen, T.F. George, Modeling nanophotothermal therapy:
nanoparticle ensembles as heaters and actuators: melting and collective kinetics of thermal ablation of healthy and cancerous cell organelles and gold
plasmon resonances, Nanoscale Res. Lett. 1 (2006) 84–90. nanoparticles, Nanomed.: Nanotechnol. Biol. Med. 7 (2011) 137–145.
[34] S. Hashimoto, D. Werner, T. Uwada, Studies on the interaction of pulsed lasers [42] A.N. Yakunin, Y.A. Avetisyan, V.V. Tuchin, Laser-induced thermal dynamics and
with plasmonic gold nanoparticles toward light manipulation, heat temperature localization phenomenon in tissues and cells doped with
management, and nanofabrication, J. Photochem. Photobiol., C 13 (2012) 28– nanoshells, in, 2012, pp. 82221F–82221F-82210.
54.

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