Gold over Branched Palladium Nanostructures for Photothermal

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Gold over Branched Palladium Nanostructures for Photothermal Cancer Therapy Andrew J. McGrath, Yi-Hsin Chien, Soshan Cheong, David A. J. Herman, John Watt, Anna M. Henning, Lucy Gloag, Chen-Sheng Yeh, and Richard D. Tilley ACS Nano, Just Accepted Manuscript • DOI: 10.1021/acsnano.5b05563 • Publication Date (Web): 07 Nov 2015 Downloaded from http://pubs.acs.org on November 15, 2015

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Gold over Branched Palladium Nanostructures for Photothermal Cancer Therapy Andrew J. McGrath, Yi-Hsin Chien, Soshan Cheong, David A. J. Herman, John Watt, Anna M. Henning, Lucy Gloag, Chen-Sheng Yeh and Richard D. Tilley* A. J. McGrath, Dr. D. A. J. Herman, Dr. J. Watt School of Chemical and Physical Sciences and the MacDiarmid Institute for Advanced Materials and Nanotechnology, Victoria University of Wellington, Wellington 6012, New Zealand Dr. Y.-H. Chien, Prof. C.-S. Yeh Department of Chemistry, Center for Micro/Nano Science and Technology and Advanced Optoelectronic Technology Center, National Cheng Kung University, Tainan 701, Taiwan Dr. S. Cheong, L. Gloag, Prof. R. D. Tilley School of Chemistry and Australian Centre for NanoMedicine, University of New South Wales, Sydney, NSW 2052, Australia E-mail: [email protected] Dr. A. M. Henning Boutiq Science Ltd, Victoria University of Wellington, Wellington 6012, New Zealand Prof. R. D. Tilley

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Electron Microscope Unit, Mark Wainwright Analytical Centre, University of New South Wales, Sydney, NSW 2052, Australia

Keywords: palladium, gold, nanostructures, nanoparticles, hyperthermia.

ABSTRACT: Bimetallic nanostructures show exciting potential as materials for effective photothermal hyperthermia therapy. We report the seed-mediated synthesis of palladium-gold (Pd-Au) nanostructures containing multiple gold nanocrystals on highly-branched palladium seeds. The nanostructures were synthesized via the addition of gold precursor to a palladium seed solution, in the presence of oleylamine which acts as both a reducing and stabilizing agent. The interaction and the electronic coupling between gold nanocrystals and between palladium and gold broadened and red-shifted the localized surface plasmon resonance (LSPR) absorption maximum of the gold nanocrystals into the near-infrared (NIR) region, to give enhanced suitability for photothermal hyperthermia therapy. Pd-Au heterostructures irradiated with 808 nm laser light caused destruction of HeLa cancer cells in vitro, as well as complete destruction of tumor xenographs in mouse models in vivo for effective photothermal hyperthermia.


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An emerging strategy to selectively kill tumorous cell tissue is photothermal hyperthermia therapy. This form of cancer therapy is achieved by the conversion of light to thermal energy to heat up and kill cells with the use of light-absorbing nanomaterials.1 In order to maximize the photothermal response of the materials to laser irradiation, it is essential to maximize their absorption in the near-infrared (NIR) region, at 650-900 nm.2 Laser light of wavelengths above or below this range are significantly absorbed by water or hemoglobin respectively, and is unsuitable for photothermal therapeutic treatments. Gold nanostructures are one of the best candidate materials for photothermal cancer treatment, due to their high biocompatibility, ease of surface functionality and tunable localized surface plasmon resonance (LSPR) absorption band.3 The narrow LSPR absorption band of gold nanoparticles lies outside of the NIR region, with λmax typically at 450-520 nm.4 Red-shifting and broadening of this absorption band into the NIR region enables opportunities for the use of gold nanoparticles in photothermal therapeutic applications. Two of the most effective strategies for red-shifting the absorption band include (i) controlling the assembly and/or geometry of gold nanocrystals and (ii) incorporating a second metal in order to strategically exploit the synergistic effects between two metals, such as electronic coupling, to tune the optical properties. Various geometries of gold nanoparticles have been previously synthesized, including nanorods, nanoshells and nanocages, in order to shift the LSPR to the NIR region.5-8 Deliberatelyassembled aggregates or “vesicles” of gold nanoparticles have also been shown as effective transducers for NIR laser therapy,9-13 and in some cases with photothermal efficiencies superior to that of shape-engineered gold nanoparticles.14,15 These systems usually require several experimental steps post-synthesis that involve precise particle surface modification in order to maintain the aggregate structures that exhibit absorption in the critical NIR window. In this


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work, our approach is to use a highly-branched metallic nanostructure as a template because of the high surface area and reactive branch tips of the template structure can be used to form a network of gold nanoparticles over the branched template structure. For this purpose, multiply branched palladium nanostructures previously developed by our group were used.16 An important consideration when introducing a secondary metal component is to preserve the nontoxic properties of gold nanomaterials. Palladium is a logical choice, due to its proven low toxicity at concentrations required for hyperthermia, and is an emerging material of choice in the design of nanoparticle-based biological probes and therapeutics.17-19 The use of palladium as the template material also allows for tuning of the optical properties of colloidal gold due to the electronic interaction between the two metals.20-22 Such effects give rise to unique properties of bimetallic nanoparticles and have drawn considerable attention in the past decade.23-26 In particular, Xia and co-workers have shown that palladium-gold (Pd-Au) dimers displayed an LSPR band that was significantly red-shifted relative to that of gold nanocrystals.26-27 It was also shown that by increasing the size of the gold domain, the LSPR band can be further red-shifted as desired. Through controlling the gold nanocrystal size, and the Pd-Au composition thereby controlling the interaction between gold nanocrystals and interaction between gold and palladium, a clear opportunity presents itself towards controlled gold-based bimetallic nanostructures with tunable LSPR band. Such gold-based bimetallic nanostructures with tunable LSPR band when combined with low toxicity are highly suited to photothermal therapy. In this paper we use both a branched geometry and a Pd-Au bimetallic composition to design nanostructures with enhanced absorption within the NIR region for photothermal hyperthermia therapy. The synthetic strategy is to form a network of gold nanocrystals on the palladium seed template in which their surfaces come into


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close contact, which red-shifts the energy of the surface plasmons. The size of the gold nanocrystals and the red-shift of the LSPR band of the Pd-Au nanostructures were tuned by the amount of gold precursor added during the nanocrystal growth step. Our work demonstrates that the incorporation of a palladium core allows for red-shift of gold nanocrystals’ LSPR band with more relaxed restrictions with regard to shape control of the Au component. The hydrophobic surfactant molecules used in the synthesis were replaced with a hydrophilic poly(ethylene glycol) derivative to make the Pd-Au nanostructures water soluble. The Pd-Au nanostructures are shown to exhibit enhanced absorption within the NIR region to levels suitable for effective photothermal therapy. The absorption peak was shifted to 755 nm, which is well within the desired 650-900 nm region, and the Pd-Au nanostructures had a high absorption cross section at 808 nm. The Pd-Au nanostructures were found to have no observable cytotoxicity at the concentration required for hyperthermia applications. When applied for use as laser-induced photothermal hyperthermia agents, the Pd-Au nanostructures irradiated with 808 nm laser light caused destruction of HeLa cancer cells in vitro. In vivo studies showed the complete destruction of tumor xenographs in mouse models, paving the way for the use of templated gold-based bimetallic nanostructures for cancer treatments. Results and Discussion The Pd-Au nanostructures were prepared via a seeded growth process, using highly-branched palladium nanostructures (see Figure S1 in Supporting Information) as seeds or templates.16 In a typical synthesis, a solution of palladium nanostructures in chloroform was heated to reflux in the presence of oleylamine surfactant molecules. To this solution, 10 mM of HAuCl4 in 1/1 (v/v) chloroform/methanol mixture was added dropwise at a rate of 1.5 mL min-1, to a desired gold concentration. The oleylamine acts as both a stabilizer to the nanostructure and reducing agent to


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the gold precursor through the formation of gold-oleylamine complexes.28 The reaction solution was then left stirring while under reflux for 30 minutes, before removing from the heat source and cooling to room temperature. The product was retrieved by centrifugation, and washed twice in a mixture of methanol and toluene to remove excess surfactant. The synthesis was carried out using 0.2, 0.5, 1.0 and 2.0 mL of the HAuCl4 solution. As the nanostructures were stabilized by hydrophobic surfactants, ligand exchange process was performed in order to interface the Pd-Au nanostructures with physiological systems for in vitro and in vivo hyperthermia studies. For this purpose, a simple ligand exchange process was used to conjugate the nanostructures with poly(ethylene glycol) diamine (H2N-PEG-NH2).29 The PEG derivative was chosen as the capping ligand as it provides good steric stabilization for gold nanoparticles in aqueous solution and is highly biocompatible.30 Furthermore, the long amphiphilic polymer backbone is effective for imparting steric stability on the Pd-Au nanostructures,31 preventing aggregation of the nanostructures. Surface modification with PEG also ensures good tumor uptake of nanomaterials and minimizes immunological response, as previously shown for even large nanostructures (~150 nm) in vivo.32 TEM images of the Pd-Au nanostructures prepared by adding different volumes of HAuCl4 solution are shown in Figure 1. The average sizes of the nanostructures were measured to be 110, 114, 124 and 137 nm when the added gold precursor solution was 0.2, 0.5, 1.0 and 2.0 mL, respectively. Sizes were measured as the longest branch-to-branch distance across each nanostructure from TEM images. This size is on the order of several previous nanostructures utilized for photothermal therapy.32-34 The molar percentage ratio for each Pd-Au nanostructure was further investigated using inductively-coupled plasma atomic emission spectroscopy (ICPAES), and the Au molar content was determined as 7.8, 20.9, 29.3 and 44.2% for Pd-Au


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synthesized with 0.2, 0.5, 1.0 and 2.0 mL of 0.01 M HAuCl4 solution respectively. Growth of gold on the palladium nanostructures across each sample is uniform, as the relative monodispersity of each sample was maintained with a standard deviation of 99%, Sigma Aldrich). The ligand exchange was carried out via modification of literature methods.29 Briefly, 10 µmol of Pd-Au was dispersed in 5 mL CHCl3, along with 1 mmol (87 µL) of 3MPA, and the mixture was left to sonicate for 1 hr at room temperature. The hydrophilic Pd-Au nanostructures were recovered via centrifugation at 14,000 rpm, and washed three times in distilled H2O to remove excess ligand. The 3MPA-capped Pd-Au nanostructures were stabilised further via conjugation with bis(aminopropyl) polyethylene glycol (H2N-PEG3000-NH2) (Mw = 3,000 g mol-1), via a literature method. Briefly, 10 µmol of Pd-Au nanostructures was dispersed in 20 mL phosphate-buffered saline (PBS, pH = 5.5), and 1 mL of 10 mM solutions of N-(3-dimethylaminopropyl)-N’ethylcarbodiimide hydrochloride (EDC) (98%, Sigma Aldrich) and N-hydroxysuccinimide (NHS) (98%, Sigma Aldrich) in PBS were added. The solution was left to sonicate for 30 min at room temperature, at which point 1 mL of 10 mM H2N-PEG3000-NH2 (Sigma Aldrich) in PBS was added, and the solution left to sonicate for a further 6 hr. The Pd-Au nanostructures were recovered via centrifugation and washed three times with distilled H2O before being dispersed in PBS at pH = 7.4.


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Cytotoxicity assays: HeLa carcinoma cells were cultured in an incubation chamber in 5% CO2 at 37 oC in Dulbecco modified Eagle’s medium (DMEM) with 10% fetal bovine serum. Cells were collected by tripsinization, placed on a 10 cm tissue culture petri dish and allowed to grow for three days. Cells were seeded at a concentration of 5 x 103 per well in a 96-well plate, and incubated further overnight in a 5% CO2 chamber at 37 oC. The cell medium was then replaced with medium containing Pd-Au nanostructures and incubated for a further 24 hr. At this point, medium was again removed and replaced with medium containing MTT reagents, followed by incubation for 4 hr at 37 oC. The crystals formed were dissolved in DMSO, and the absorbance at 540 nm in each well measured. Temperature elevation tests: The Pd-Au nanostructures in DMEM at a concentration of 50 ug (Pd) mL-1 were added to 96-well plates in 200 µL aliquots. An 808 nm continuous-watt diode laser was focused on these solutions (laser beam spot size of 16 mm2), at 0.51 mW beam power, for a beam density of 3 W cm-2. The temperature increase over time was measured using a digital thermometer (TES 1319A-K type). In vitro photothermal therapy: Cells were cultured using identical methods as those prepared for cytotoxicity assays. Cells were seeded at a concentration of 5 x 103 per well in a 96-well plate and cultured overnight. After 24 hr, the cell medium was replaced with medium containing PdAu-PEG-NH2 in concentrations up to 1 mM Pd-Au. Cell cultures subjected to laser illumination were exposed to an 808 nm CW laser at 3 W cm-2 beam density (spot size 16 mm2). After laser exposure, the plates containing cell cultures were incubated for 24 hr in a 5% CO2 chamber at 37 o

C. Cell viability was counted via MTT assay, as per methods used for cytotoxicity assays.


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In vivo photothermal therapy HeLa cervical cancer cells were incubated in DMEM supplemented with 10% fetal bovine serum. Cells were cultured and tripsinized as per those for in vitro cell culture tests, and suspended in PBS after tripsinization. Male B9 mice (6 weeks old) were provided by National Cheng Kung University of Taiwan. HeLa tumor xenographs were established through injecting 106 cells in 100 µL of saline. Pd-Au was injected at a concentration of 1 mM in PBS directly to the tumor site, and left for 30 min to allow PBS to drain from the tumor. Control group mice received a 100 µL PBS injection. Visible tumors received 808 nm CW laser illumination for 30 min, at laser density of 3 W cm-2 (beam area 16 mm2). Tumor width, height and length were measured at 2-day intervals for up to 8 days, after which the mice were sacrificed.


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Figure 1. (A-D) Lower- and (E-H) higher-magnification TEM images of Pd-Au nanostructures synthesized by adding different volumes of 10 mM HAuCl4: (A,E) 0.2, (B,F) 0.5, (C,G) 1.0 and (D,H) 2.0 mL.


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Figure 2. (A) XRD patterns of Pd-Au nanostructures synthesized via addition of different volumes of 0.01 M HAuCl4 solution. Reference peaks taken from JCPDS-00-004-0784 (Au) and JCPDS-00-005-0681 (Pd). (B) Au nanocrystal size versus volume of Au solution added during synthesis. Red line represents a linear fit to the data (R2 = 0.9965).


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Figure 3. (A) High-resolution TEM image of the interface between a Pd branch and an Au nanocrystal nucleated on the tip of the branch. (B) A close-up image of the Au nanocrystal, showing the (200) and (111) lattice planes (top) and corresponding fast Fourier transform (FFT) pattern (bottom). (C) Close-up of the interface between Au nanocrystal and Pd branch, showing the parallel (200) lattice planes (top) and matching FFT (bottom). (D) Close-up of a Pd branch showing the (200) and (111) lattice planes (top) and matching FFT pattern (bottom).


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Figure 4. A) UV-visible spectra of Pd-Au nanostructures obtained with the addition of different volumes of 0.01 M HAuCl4 solution to branched palladium nanostructures. Spectra are vertically offset for clarity. B) Temperature measurements of Pd-Au nanostructures under laser irradiation, in comparison with those of palladium nanostructures and the suspended medium (DMEM) Palladium concentration was fixed at 50 µg mL-1 for Pd-Au and Pd, to ensure identical nanostructure concentration. C) Viability of HeLa cells incubated with increasing concentration of Pd seeds and Pd-Au nanostructures using MTT assays. D) Comparison of HeLa cell viability with and without treatments of Pd-Au nanostructures and laser irradiation (n = 4 for each group; ** p < 0.01).


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Figure 5. A) In vivo photothermal hyperthermia efficacy of Pd-Au, as compared to laser treatment with PBS only. 100 µL of either PBS, Pd or Pd-Au (at 50 µg mL-1 Pd concentration) in PBS was injected into HeLa xenographs in mice (n = 3 for each group; * p < 0.05). B) Representative images taken of the mice immediately before and 8 days after laser irradiation of the tumor site for 30 minutes at 3 W cm-2. The dashed white circles indicate the tumor regions.

ASSOCIATED CONTENT Supporting Information. TEM image of Pd seeds, size histograms of Pd-Au nanostructures, EDX data, XRD data, UV-vis spectrum of Pd seeds, further temperature profile data for Pd-Au nanostructures, and methods and equations used to calculate absorption cross-section are provided as Supporting Information. This material is available free of charge via the Internet at http://pubs.acs.org. AUTHOR INFORMATION Corresponding Author *[email protected] Author Contributions


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The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.

ACKNOWLEDGMENT A.J.M. and R.D.T. thank the Royal Society of New Zealand for funding under the New ZealandTaiwan Nanotechnology Research Programme, and the Ministry of Business, Innovation and Enterprise for funding.

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Synopsis Optimizing materials for photothermal therapy requires ease of synthesis and high absorption cross-section values in the near-infrared (NIR) region. The surface plasmon resonance of gold nanostructures can be tuned to this end, via networking of gold nanocrystals and by using a bimetallic structure. Palladium-gold nanostructures were synthesized via a seed-mediated method, which formed Au nanocrystals on the Pd branches with high NIR absorption, and showed tumor cell destruction in vivo.


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Gold over Branched Palladium Nanostructures for Photothermal

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