光辐照精确调控金纳米星枝杈长度及其光热性能探究

金纳米星是一种具有尖状结构的多分枝纳米颗粒.为了使金纳米星枝杈长度可控,利用HEPES作为体系的还原剂、稳定剂及形状诱导剂,在制备过程中进行光辐照,得到的金纳米星枝杈长度比无光辐照时的金纳米星枝杈长度短,而且不同波长光辐照得到的金纳米星枝杈长度有显著不同.在此基础上,分析了金纳米星枝杈长度变化的物理过程,提出光诱导金纳米星生长过程中枝杈长度变化的理论模型.测量了不同枝杈长度的金纳米星在光辐照下一定时间内的温度变化,计算了金纳米星的光热转换效率.实验结果表明,光辐照制备金纳米星能够精确控制金纳米星枝杈长度范围,从而调控金纳米星的光热转换效率.     

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.     

金纳米星/双锥的可控制备、光热转换及体外光热治疗

采用种子生长法,分别制备了金纳米星和金纳米双锥,利用透射电子显微镜、紫外-可见(UV-Vis)分光光度计等对样品进行了表征,并评价了金纳米星和金纳米双锥的光热转换性能、生物相容性以及体外光热治疗性能。结果表明,金纳米星和金纳米双锥的UV-Vis吸收峰位于808 nm和815 nm左右。在808 nm激光辐照下,光热转换效率分别为48.43%和53.68%。细胞实验表明,金纳米星和金纳米双锥具有良好的生物相容性。808 nm激光辐照5 min后,MCF-7细胞存活率分别降至22.54%和13.73%;且在同等条件下,金纳米双锥具有更加优异的光热治疗性能,是一种安全、高性能的肿瘤光热治疗用纳米探针材料。     

纳米尺度下光热治疗等离激元耦合影响分析

作为一种高效、 局域化且高度可控的纳米热源, 金纳米棒越来越多的应用于肿瘤的光热治疗之中。 为探讨微观尺度下金纳米棒的产热与传热机理, 以及颗粒之间耦合作用对体系光热效应的影响。 本文运用基于有限元的 COMSOL 软件, 建立了金纳米棒光热耦合的三维模型, 分析了排布方式和颗粒间距等因素对纳米棒光学性质和光热响应的影响。 研究表明, 不同排布方式下近距离耦合颗粒之间的耦合强度随间距的增大呈指数衰减, 在一定间距范围内这种衰减行为可以被等离子体尺度方程描述; 单体共振波长照射下, 颗粒间的聚集影响光热治疗的效果, 在颗粒耦合作用范围内, 分散性越高, 体系加热效果越好。 本文研究模型及所得结论可为金纳米棒的产热与传热机理及肿瘤的光热治疗提供参考与指导。     

近红外光热转换纳米晶研究进展

近红外光热转换纳米晶材料因其在近红外区(普遍位于780~1 400 nm)的高效光热转换性能,已广泛应用于光热杀死癌细胞、肿瘤治疗、海水淡化等领域。因其多样的液相制备方法和形貌控制、纳米结构复合、逐渐提高的光热转换效率以及表面易于药物修饰等优点,该材料在光热成像诊断、光热治疗等领域引起了学术界的广泛关注。本文综述了近红外光热转换纳米晶的研究进展,主要包括贵金属纳米晶、铜硫族半导体纳米晶、碳相关纳米晶以及这些纳米晶材料构成的复合结构,同时介绍了具有较高光热转换效率的表面等离子体共振(SPR)材料的研究进展,尤其是双模态SPR性质的耦合在光热转换领域的应用前景。基于其性能协同耦合的特性,双模态表面等离子体共振耦合的复合纳米晶将是近几年光热转换纳米晶发展的重要方向。     

一种金纳米球复合稀土Eu3+功能纳米材料的制备及光热监测应用

光热治疗基于光热药剂在激光照射下产生热量,进而高温杀死肿瘤细胞,因而实时监测光热过程中微观温度变化对于优化治疗效果具有十分重要的作用。稀土Eu~(3+)配合物的发光具有线谱、长荧光寿命以及对温度高度敏感的特点,利用Eu~(3+)配合物的温敏特性可检测光热过程中的温度变化,整合温度监测功能和光热特性的纳米体系在光热治疗领域具有很好的应用前景。本文制备了一种内部封装温度敏感探针Eu~(3+)配合物且表面复合金纳米球的功能纳米颗粒,将该功能纳米颗粒分散液置于不同的温度环境中,发现其荧光性能对温度具有高的响应灵敏度,即Eu~(3+)的特征发射峰(615 nm)强度随温度升高降低52.7%,表明该稀土荧光温度纳米传感器具有高的温度敏感性。在激光辐照下,功能纳米颗粒可以产生良好的光热现象,基于自身的温敏特性可实时对光热特性进行温度监控。     

Fe3O4@Au纳米星颗粒作为循环SERS基底用于农药残留物的检测

本文首先采用共沉淀的方法制备了Fe3O4纳米颗粒,随后经柠檬酸钠和对苯二酚还原氯金酸的方法在Fe3O4纳米颗粒的表面生成刺状Au纳米结构,进而获得Fe3O4@Au纳米星颗粒。该Fe3O4@Au纳米星颗粒作为SERS基底,用作农药残留物福美双和敌瘟磷的检测。由于高密度的Au纳米结构的尖端效应,该基底显示出高敏感的SERS活性。最后利用Fe3O4纳米颗粒的磁性,将其用于循环SERS测试,研究了其循环使用特性。     

光学相干层析成像色散补偿研究

针对通过增加光源谱宽度来提高光学相干层析成像系统分辨率时样品色散特性的限制作用,分析了色散与光学相干层析成像系统纵向光程分辨率的约束关系.根据物质色散特性,采用数值变换方法对光学相干层析成像相干成像信号进行了色散补偿.实验使用了中心波长1 550 nm 自激发辐射光源和光纤迈克尓逊干涉结构,对水和光学快速扫描延迟线引入的二阶和三阶色散进行了数值补偿并通过相位修正因子来改善补偿效果.确定了一种普适的、快速的数值色散补偿方法.在对水中盖玻片和生物组织和的光学相干层析成像图像的色散补偿实验中取得了良好的效果,证明了方法的可行性.     

光学相干层析成像色散补偿研究

针对通过增加光源谱宽度来提高光学相干层析成像系统分辨率时样品色散特性的限制作用,分析了色散与光学相干层析成像系统纵向光程分辨率的约束关系.根据物质色散特性,采用数值变换方法对光学相干层析成像相干成像信号进行了色散补偿.实验使用了中心波长1550nm自激发辐射光源和光纤迈克尓逊干涉结构,对水和光学快速扫描延迟线引入的二阶和三阶色散进行了数值补偿并通过相位修正因子来改善补偿效果.确定了一种普适的、快速的数值色散补偿方法.在对水中盖玻片和生物组织和的光学相干层析成像图像的色散补偿实验中取得了良好的效果,证明了方法的可行性.     

双光栅快速扫描光学延迟线的色散补偿

光学相干层析成像(OCT)系统的纵向分辨力不仅与光源的带宽有关,而且与系统中两干涉臂间的色散匹配有关。如果色散没有得到精确匹配,将使光学相干层析成像系统的纵向分辨力达不到所预期的理论值。色散问题在超高分辨光学相干层析成像系统中尤为突出。提出了一种基于双光栅快速扫描光学延迟线(RSOD),用于光学相干层析成像系统的色散补偿。该方法中新增的光栅引入了光栅间距这一独立变量,其与常规单光栅快速扫描光学延迟线机构中的光栅离焦量一起,可使光学相干层析成像系统中的群速度色散(GVD)和三阶色散(TOD)同时得到补偿。分析了双光栅快速扫描光学延迟线的色散特性和色散调节原则,并提供了一个典型光学相干层析成像系统中的色散补偿实例。     

聚吡咯修饰的金纳米棒对肿瘤的光学相干层析成像的影响

聚吡咯(PPy)制备简单、生物相容性好,且在近红外(NIR)光谱范围内有很强的吸收,可作为一种良好的光热治疗试剂;同时,其NIR光吸收性质也可用于增强光学相干层析成像(OCT)的对比效果。因此,采用PPy对传统的OCT对比试剂——金纳米棒(GNR)进行表面修饰,有望获得对比效果更好且生物毒性较小的新型OCT对比试剂。选用吡咯为起始原料,在GNR表面进行一步简单的氧化聚合反应即可制备得到PPy修饰的金纳米棒(GNR-PPy)。利用紫外-可见吸收光谱,拉曼光谱和透射电子显微镜对制备的样品进行了分析和表征。构建小鼠荷瘤模型,以研究GNR-PPy对肿瘤OCT图像对比度的增强效果。采用中心波长为840 nm的OCT系统对注射了纳米粒子的肿瘤区域进行OCT成像。结果表明,肿瘤组织注射了GNR-PPy后,OCT信号衰减非常明显;与注射了GNR的OCT图像相比,840 nm光在GNR-PPy的OCT图像中的穿透深度明显更低。从OCT图像中抽提出一维的衰减曲线对OCT图像进行定量分析,发现注射有GNR-PPy肿瘤组织的OCT信号衰减系数明显高于注射了GNR的组织。表明,相对于GNR,GNR-PPy具有更好的OCT信号对比效果,这在增强肿瘤成像效果方面具有潜在应用价值。     

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.     

Enhancing photothermal cancer therapy by clustering gold nanoparticles into spherical polymeric nanoconstructs

Gold nanoparticles (AuNPs) have been proposed as agents for enhancing photothermal therapy in cancer and cardiovascular diseases. Different geometrical configurations have been used, ranging from spheres to rods and more complex star shapes, to modulate optical and ablating properties. In this work, multiple, ultra-small 6 nm AuNPs are encapsulated into larger spherical polymeric nanoconstructs (SPNs), made out of a poly(lactic acid-co-glycol acid) (PLGA) core stabilized by a superficial lipid-PEG monolayer. The optical and photothermal properties of the resulting nanoconstructs (Au-SPNs) are modulated by varying the initial loading input of AuNPs, ranging between 25 and 150 μg_Au. Au-SPNs exhibit a hydrodynamic diameter varying from ~100 to 180 nm, growing with the gold content, and manifest up to 2-fold increase in thermal energy production per unit mass of gold for an initial input of 100 μg_Au. Au-SPNs are stable under physiological conditions up to 7 days and have direct cytotoxic effect on tumor cells. The superior photothermal performance of Au-SPNs is assessed in vitro on monolayers of breast cancer cells (SUM-159) and tumor spheroids of glioblastoma multiforme cells (U87-MG). The encapsulation of small AuNPs into larger spherical nanoconstructs enhances photothermal ablation and could favor tumor accumulation.     

Spectral characterization and intracellular detection of Surface‐Enhanced Raman Scattering (SERS)‐encoded plasmonic gold nanostars

Plasmonic gold nanostars offer a new platform for surface‐enhanced Raman scattering (SERS). However, due to the presence of organic surfactant on the nanoparticles, SERS characterization and application of nanostar ensembles in solution have been challenging. Here, we applied our newly developed surfactant‐free nanostars for SERS characterization and application. The SERS enhancement factors (EF) of silver spheres, gold spheres and nanostars of similar sizes and concentration were compared. Under 785 nm excitation, nanostars and silver spheres have similar EF, and both are much stronger than gold spheres. Having plasmon matching the incident energy and multiple ‘hot spots’ on the branches bring forth strong SERS response without the need to aggregate. Intracellular detection of silica‐coated SERS‐encoded nanostars was also demonstrated in breast cancer cells. The non‐aggregated field enhancement makes the gold nanostar ensemble a promising agent for SERS bioapplications. Copyright © 2012 John Wiley & Sons, Ltd.     

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。     

Multivalent Sorbitol Probes for Near-Infrared Photothermal Cancer Therapy

Photothermal therapy (PTT) is a targeted and non-invasive therapeutic strategy for effective cancer treatment. Image-guided PTT based on bifunctional near-infrared (NIR) fluorophores has received significant attention recently and the development of NIR fluorophores is advised for targeted imaging and precise cancer therapy. In this study, a multivalent sorbitol-conjugated NIR fluorophore (4Sorbitol-800) is used as a photothermal therapeutic agent for in vivo cancer imaging and therapy because of the high tumor-targetability of the sorbitol moieties and excellent photothermal properties of the NIR heptamethine cyanine core. This NIR fluorophore demonstrates an excellent photothermal effect, which increases the temperature of the tumor by 57.4 °C upon NIR laser irradiation (1.1 W cm⁻²) for 5 min. The volumes of HT-29 tumors targeted by 4Sorbitol-800 significantly decrease over 7 days after photothermal treatment. The 4Sorbitol-800 developed in this study exhibits good in vivo safety and a highly efficient antitumor capability. Therefore, 4Sorbitol-800 in combination with NIR laser irradiation has promising potential for future clinical applications with targeted photothermal cancer therapy.     

Synthesis of gold nanostars with fractal structure: application in surface-enhanced Raman scattering

Multi-branched gold nanostars with fractal feature were synthesized using the Triton X-100 participant seed-growth method. By increasing the amount of ascorbic acid, the branch length of gold nanostars could be greatly increased. It has been interesting to find that the secondary growth of new branches takes place from the elementary structure when the aspect ratio of the branches is greater than 8.0 and the corresponding plasmon absorption wavelength is greater than 900 nm. Raman activity of the gold nanostar films has been investigated by using the 4-mercaptobenzoic acid (4-MBA) as Raman active probe. Experimental results show that the surface-enhanced Raman scattering (SERS) ability of the gold nanostars could be efficiently improved when the fractal structure appears. The physical mechanism has been attributed to the intense increased secondary branch number and the increased “hot spots”. These unique multi-branched gold nanostars with fractal feature and great SERS activity should have great potential in sensing applications.     

In Vivo Targeted Cancer Theranostics by Core/Shell‐Structured Multifunctional Prussian Blue/PLGA “Nanococktails”

The construction of high‐performance nanotheranostic agent with Food and Drug Administration (FDA)‐approved materials for efficient treatment of breast cancer is still of great challenge. This work reports, for the first time, on the elaborate integration of two FDA‐approved materials together to construct a multifunctional core/shell‐structured “nanococktail” for cancer theranostics. The biocompatible Prussian blue nanoparticles with high photothermal‐conversion performance are coated by poly(lactic‐co‐glycolic acid) followed by further surface targeting engineering (folic acid conjugation). The anticancer drug paclitaxel is concurrently encapsulated into the nanocarrier with high efficiency and capacity. Especially, these “nanococktails” act as the desirable contrast agents for photoacoustic/magnetic resonance imaging dual‐mode diagnostic imaging, providing the potential for guidance and monitoring during the therapeutic process, which has been systematically demonstrated both in vitro and in vivo. Importantly, these “nanococktails” have demonstrated their high performance in synergistic in vivo photothermal therapy and chemotherapy against breast cancer tumor xenograft. This work not only provides a high‐performance theranostic “nanococktail” platform for efficient theranostic treatment of cancer but also paves a new way for the integration of various functional moieties together for realizing the specific diagnostic imaging‐guided and synergistic cancer therapy.