Thermo‐plasmonics: using metallic nanostructures as nano‐sources of heat

Recent years have seen a growing interest in using metal nanostructures to control temperature on the nanoscale. Under illumination at its plasmonic resonance, a metal nanoparticle features enhanced light absorption, turning it into an ideal nano‐source of heat, remotely controllable using light. Such a powerful and flexible photothermal scheme is the basis of thermo‐plasmonics. Here, the recent progress of this emerging and fast‐growing field is reviewed. First, the physics of heat generation in metal nanoparticles is described, under both continuous and pulsed illumination. The second part is dedicated to numerical and experimental methods that have been developed to further understand and engineer plasmonic‐assisted heating processes on the nanoscale. Finally, some of the most recent applications based on the heat generated by gold nanoparticles are surveyed, namely photothermal cancer therapy, nano‐surgery, drug delivery, photothermal imaging, protein tracking, photoacoustic imaging, nano‐chemistry and optofluidics.     

Size,Shape, and Wavelength Effect on Photothermal Heat Elevation of Gold Nanoparticles: Absorption Coefficient Experimental Measurement

Complex-shaped nanoparticles as gold nanourchins (GNU) and nanorods (GNR) are very suitable agents in the case of photothermal therapy due to their photon-heat conversion ability in the red and near-infrared region (NIR). The quantification in heat generation of complex shaped nanostructures is an important key to predict the therapeutic effect of these nanoparticles. For that, the determination of the nanoparticles absorption cross section (σ_Abs) responsible for the heat generation is one of the important steps before any application. Although it is obvious to determine σ_Abs for spheres via Mie's theory, in the case of complex structures like GNU or GNR, this parameter is difficult to model. In this work, a new methodology is used to determine experimentally σ_Abs for both GNU and GNR. Experimental measurements of the photothermal properties of 100 nm size GNU and two different sizes of GNRs are studied regarding different parameters such as concentration, laser excitation wavelength, and exposure time. By using the heat transfer theory, the temperature elevation in the nanoparticles solutions is converted to temperature elevation at the nanoparticles surface and σ_Abs values are then calculated for both GNU and GNR in the NIR spectral region.     

Optimal design of gold nanoshells for optical imaging and photothermal therapy

Gold nanoshells are of great interest in optical imaging based on their light scattering properties and photothermal therapy due to their light absorption properties. Strong light scattering is essential for optical imaging, while effective photothermal therapy requires high light absorption. In this article, the optimal core radii and shell thicknesses of silica–gold and hollow gold nanoshells, possessing maximal light scattering and absorption at wavelengths between 700 and 1100 nm, are obtained using the Mie theory of a coated sphere. The results show that large-sized gold nanoshells of high aspect ratios (the aspect ratio is defined as the ratio of core radius to shell thickness) are the efficient contrast agents for optical imaging, while smaller gold nanoshells of high aspect ratios are the ideal therapeutic agents for photothermal therapy. From the comparison of the numerical results for silica–gold and hollow gold nanoshells, the latter are seen to offer a little superior light scattering and absorption at smaller particle size. Fitting expressions for the optimal core radii and shell thicknesses are also obtained, which can provide design guidelines for experimentalists to optimize the synthetic process of gold nanoshells.     

Gold Nanocages as Effective Photothermal Transducers in Killing Highly Tumorigenic Cancer Cells

Numerous gold nanostructures have the potential for photothermal therapy in cancers. Here, gold nanocages and gold nanoshells are synthesized, the sizes of which are fine‐tuned for a response at 750 nm wavelength. Their photothermal therapeutic efficiency is compared at gold concentration of 100 lg mL^?1 using a near‐infrared laser (750 nm). The biocompatibility for varying concentrations of gold (1 to 100 lg mL^?1) is performed in a normal cell line and laser‐mediated cell cytotoxicity for varying time intervals (7.5 and 10 min) is carried out in breast cancer cells. This study shows that when analyzed under similar conditions, the gold nanocages show better biocompatibility and are more efficient in near‐infrared absorption and photothermal conversion in comparison with conventional gold nanoshells. When subjected to photothermal laser ablation of breast cancer cell line for 7.5 min and 10 min, the nanocages are able to induce 62.92 ± 3.25% and 96.41 ± 3.04% reduction in cell viability, respectively, in comparison to nanoshells, in which a 43.35 ± 1.91% and 79.89 ± 4.74% reduction in cell viability is observed. The current study shows that the gold nanocages can outperform gold nanoshells and effectively kill cancer cells without any significant cytotoxic effect on normal cells.     

芯帽纳米颗粒的光热性质

贵金属纳米结构中的光热效应在肿瘤光热治疗、光热成像、纳米药物等领域具有重要的应用价值.各向异性的芯帽纳米结构以其丰富的可调结构参数和对激发光偏振态敏感的特性,可灵活地在近红外波段获得理想的光学吸收性质,从而可以实现温度的高效调节.本文基于有限元方法研究了颗粒物纳米结构参数对其光热效果的作用规律,数值结果表明:通过对结构参数的微量改变(包括金壳厚度、芯壳比、芯径、金属表面覆盖率等)可实现温度的显著调整;在偏振态的旋转范围(30?—70?)内可快速地产生大温变光热的准线性调整.其不弱于纳米芯壳和纳米棒结构的光热性能可为纳米光热生医研究提供一种新的选择.     

Control of the input efficiency of photons into solar cells with plasmonic nanoparticles

We study numerically the photon input efficiency of silicon solar cells due to gold plasmonic nanoparticles deposited on the cells. At low densities, when collective effects in light scattering by the nanoparticle ensemble are negligible, the absorption dependence increases linearly for a significant range of the solar spectrum. Collective effects lead to the input efficiency saturates, reaches its maximum and then decreases with nanoparticle density. The maximal input efficiency depends on the photon wavelength, nanoparticle shape and size, their distance to the cell, and the cell thickness, and can reach ~ 95% in thick solar cells. Finally, we show that aluminum nanoparticles improve the input efficiency in comparison with gold nanoparticles.     

Heat-generating property of a local plasmon resonator under illumination

We have investigated the heat generation from gold nanoparticles resulting from their local plasma resonance. We have demonstrated the self-assembly of Au nanoparticle arrays/dielectric layer/Ag mirror sandwiches, i.e., a local plasmon resonator, using a dynamic oblique deposition technique. The thicknesses of the Au and dielectric layers were changed combinatorially on a single substrate. As a result, local plasmon resonator chips were successfully fabricated. Because of strong interference, their optical absorption can be controlled between 0.0% and 97% in the near-IR region, depending on the thickness of the dielectric layer. We evaluated the heat generation from Au nanoparticles by measuring the temperature of water with which a cell prepared on a chip is filled under laser illumination. The change in the water temperature is proportional to the optical absorption of the local plasmon resonator chips. This suggests that the photothermal conversion efficiency can be controlled by interference. These features make the application of the local plasmon resonator to nanoheaters, which can spatiotemporally control heat generation, suitable.     

Size and Shape Effect of Gold Nanoparticles in “Far‐Field” Surface Plasmon Resonance

The “far‐field” surface plasmon resonance (FSPR) of metal nanoparticles, which have built a facile way to emission enhancement of red, green, blue, and white with nice reproducibility, has big potential application in solution‐processed organic light‐emitting diodes (OLEDs). According to the theory of the “far‐field” effect, the reflectivity of the metal surface and the phase shift at the reflection play an important role in enhancing ratio, which strongly relate to the size and shape of nanoparticles. In this work, gold nanospheres with different sizes and nanorods are synthesized in order to determine the size and shape effect of FSPR. The results demonstrate that the one with higher reflectivity in a certain range induces a better emission enhancement in the luminous efficiency and the maximum brightness. The nanoparticles with bigger sizes and shape of rods have higher reflectivity, which is consistent with the simulation based on FSPR effect. The phase shifts of different nanoparticles are optimized by the distance between gold nanoparticles and emitters. The metal NPs with a high reflectivity and the applicable phase shift will have big potential for the emission enhancement in OLEDs.     

Influence of the deposition parameters on the properties of SnS2 films prepared by PECVD method combined with solid sources

We report a simple and rapid biological approach to synthesize water-soluble and highly roughened “meatball”-like Au nanoparticles using green tea extract under microwave irradiation. The synthesized Au meatball-like nanoparticles possess excellent monodispersity and uniform size (250 nm in diameter). Raman measurements show that these tea-generated meatball-like gold nanostructures with high active surface areas exhibit a high enhancement of surface-enhanced Raman scattering. In addition, the Au meatball-like nanoparticles demonstrate good biocompatibility and remarkable in vitro stability at the biological temperature. Meanwhile, the factors that influence the Au meatball-like nanoparticles morphology are investigated, and the mechanisms behind the nonspherical shape evolution are discussed.     

Anisotropic Thermal Processing of Polymer Nanocomposites via the Photothermal Effect of Gold Nanorods

By embedding metal nanoparticles within polymeric materials, selective thermal polymer processing can be accomplished via irradiation with light resonant with the nanoparticle surface plasmon resonance due to the photothermal effect of the nanoparticles which efficiently transforms light into heat. The wavelength and polarization sensitivity of photothermal heating from embedded gold nanorods is used to selectively process a collection of polymeric nanofibers, completely melting those fibers lying along a chosen direction while leaving the remaining material largely unheated and unaffected. Fluorescence‐based temperature and viscosity sensing was employed to confirm the presence of heating and melting in selected fibers and its absence in counter‐aligned fibers. Such tunable specificity in processing a subset of a sample, while the remainder is unchanged, cannot easily be achieved through conventional heating techniques.     

Lock‐In Thermography to Analyze Plasmonic Nanoparticle Dispersions

The physicochemical properties of nanoparticles (NPs) strongly rely on their colloidal stability, and any given dispersion can display remarkably different features, depending on whether it contains single particles or clusters. Thus, developing efficient experimental methods that are able to provide accurate and reproducible measures of the NP properties is a considerable challenge for both research and industrial development. By analyzing different NPs, through size and concentration, it is demonstrated that lock‐in thermography, based on light absorption and heat generation, is able to detect and differentiate the distinct aggregation and re‐dispersion behavior of plasmonic NPs, e.g., gold and silver. Most importantly, the approach is nonintrusive and potentially highly cost‐effective compared to standard analytical techniques.     

Photothermally excited coherent lattice phonon oscillations in plasmonic nanoparticles

The photothermal property of (Ag and Au) plasmonic nanoparticles has brought about many important discoveries and applications in nanoscience and nanotechnology. In this review, we briefly summarize a photothermal effect, the coherent phonon oscillation, of plasmonic nanoparticles irradiated with ultrafast laser pulses of low power density. The coherent phonon oscillation is created in the nanoparticle by the ultrafast impulsive photothermal heating. The effects of size, shape, thickness, and interparticle interaction on the period of coherent phonon oscillations are discussed. The detection of the coherent lattice oscillation of metallic nanoparticles provides a powerful tool to characterize the mechanical and structural properties of nanostructures.     

Modeling of regular gold nanostructures arrays for SERS applications using a 3D FDTD method

We study the localized surface plasmon resonance (LSPR) and the surface-enhanced Raman scattering (SERS) of arrays of gold cylindrical and ellipsoidal nanoparticles with different diameters or major axes. The LSPR and SERS gains are calculated with the three dimensional Finite-Difference Time-Domain method using the Drude–Lorentz dispersion model. We find that the maximum of the extinction spectrum and the average SERS gain of each investigated nanostructures are shifted whatever their size and their shape. PACS 42.25.Fx; 71.45.Gm; 78.30.-j     

Photodegradation of PAMAM G5-stabilized aqueous suspensions of gold nanoparticles

Gold nanoparticles are produced in the form of colloidal suspensions in water by ps laser ablation of a metallic target. The fifth generation of ethylenediamine-core poly(amidoamine) (PAMAM G5) is used as a capping agent. Thanks to the ability of PAMAM to encapsulate and stabilize gold cations within its inner cavities, it is possible to evidence, by simple UV-visible spectroscopy, a photo-fragmentation process induced by the 532 nm radiation, which is resonant with the absorption plasmon band of gold nanoparticles. This effect, that can be also exploited to control the size and shape of gold nanoparticles obtained with different procedures, arises from electron photo-ejection and subsequent charging and disintegration of existing gold nanoparticles into smaller size products.     

银纳米链状材料的制备及近红外吸收性质

报道了利用水/油相界面反应,采用湿化学法合成银纳米链状材料的方法,并对这种材料的近红外吸收性质和光热转换性质进行了研究。TEM分析表明,银纳米材料为链状结构,直径约为50nm,长度分布范围较宽,从几十纳米至几百纳米。这种材料具有强的近红外吸收特性,随着还原剂加入量的增加,吸收带逐渐展宽(800～1300nm),而且平坦。这种材料具有优异光热转换性质,一经808nm激光照射,温度迅速提高。该材料优异的近红外吸收和光热转换性质,使其在红外断层成像和近红外热疗等领域具有广阔的应用前景。     

激光诱导玻璃内部金纳米颗粒的析出及光谱

使用钛宝石飞秒激光引发和热处理相结合，实现了在含有金离子的硅酸盐玻璃内部，有空间选择性地析出金纳米颗粒。对吸收光谱的研究表明，随着热处理温度的升高，吸收峰强度增大且红移；随着激光功率密度的增大，金纳米颗粒也增大。在特定的激光和热处理条件作用下，可以在玻璃内部有空间选择性的使金离子还原后聚集，形成金纳米颗粒，具有量子尺寸效应。改变激光功率和热处理温度可以控制所析出的金属纳米粒子的尺寸，从而实现多色显示，飞秒激光诱导金纳米颗粒具有稳定性，颜色具有持久性。     

Real-time SAXS and ultraviolet-visible spectral studies on size and shape evolution of gold nanoparticles in aqueous solution

Gold nanoparticles were synthesized with seed mediated wet growth method. A coexistent system with gold nanorods and nanospheres was prepared. In-situ real-time small angle X-ray scattering (SAXS) and ultraviolet-visible (UV-vis) absorption were used to monitor the growth process of Au nanoparticles in the aqueous solution. Combining SAXS measurement and UV-vis spectra, the contribution of gold nanorods was separated from that of gold nanospheres. The growth behavior of the gold nanorods and the gold nanospheres was studied. The size and shape evolution of both gold nanoparticles as well as their volume fractions were obtained. After adding the seed-solution into the growth solution to form a particle suspension, within the first 18 min, a mutual competitive growth occurred between the gold nanorods and nanospheres. And their average particle sizes always increased with growth time. 18-min later, the evolution of size and shape of gold nanoparticles was almost stopped. The results demonstrate that the aspect ratio of gold nanorods in the particle suspension follows an exponential decay change after the initial 5-min growth. The evolution process of size and shape of gold nanoparticles in the particle suspension has been discussed.     

纳秒脉冲激光特性对金纳米球光声响应的影响

由于局部表面等离激元共振现象,金纳米颗粒具有显著的光热效应,而近年来随着人们对精准医疗和非介入性组织成像的需要,作为纳米颗粒光热衍生效应的金纳米颗粒光声效应得到了人们的广泛关注.金纳米颗粒自身特性对其光声效应的影响目前已经得到一定的研究,而对于脉冲激光特性对其光声效应的影响尚缺乏深入探讨,因此,本文对金纳米球在不同脉冲...     

Cobalt Phosphide Nanoparticles Applied as a Theranostic Agent for Multimodal Imaging and Anticancer Photothermal Therapy

Biocompatible single‐component theranostic nanoagents instinctly affording multiple imaging modalities with satisfying therapeutic functions are highly desirable for anticancer treatments. Although cobalt‐based phosphides are well‐recognized as competent electrocatalysts, their potentials for biomedical applications remain unexplored. In this work, cobalt phosphide nanoparticles (CoP NPs) are developed to be a powerful theranostic agent for multimodal imaging and anticancer photothermal therapy. The uniform CoP NPs in a size of ≈21 nm are synthesized via a facile thermal decomposition method, followed by surface modification. The resultant CoP NPs exhibit excellent compatibility and stability in water as well as various physiological solutions. Supported by the good biocompatibility, strong near‐infrared absorption, and high photothermal conversion property, significant photothermal effect of the NPs is demonstrated, realizing efficient hyperthermia ablation on cancer cells. Importantly, the CoP NPs have shown considerable capabilities on high‐contrast in vitro and in vivo triple‐modal imaging, including infrared thermal (IRT), photoacoustic (PA), and T₂‐weighted magnetic resonance (MR) imaging. This work has unraveled the promising potentials of CoP‐based nanoagent for precise diagnosis and efficient therapy.     

Preparation of nanosized metal (oxides) by gas phase hydrolysis using mesoporous materials as nanoreactors

Immobilized nanosized metal (oxides) on carbonaceous carriers were prepared by hydrolysis under mild conditions by using the carrier pores as a kind of nanoreactor. Metal alkoxide vapor was adsorbed on the carrier and then formed the product upon exposure to water vapor. With this facile method, Titania, Vanadia, Rhodium (oxide), and Platinum (oxide) nanostructures were prepared at high yields, high loadings, and good dispersion in the carrier material. High number concentrations of spheroidal nanoparticles of uniform size (diameter ca. 5 nm) were obtained from less reactive precursors, whereas with highly reactive precursors, such nanoparticles occurred only after subsequent calcination. Nanoparticles appeared to be the thermodynamically stable form of the metal (oxide) produced in the pores. Highly reactive precursors formed metastable seeds, which nucleated and restructured into nanoparticles upon subsequent exposure to heat. The presented method allows for preparation of metal (oxide) nanostructures and effective control of their size and shape.