金纳米棒核／二氧化硅壳纳米复合结构的可控制备及细胞成像

采用模板合成以及溶胶凝胶方法制备了金纳米棒核／二氧化硅壳（GNR@SiO2）纳米复合粒子,探讨了这种新型纳米复合结构的可控制备、光谱性质、细胞毒性和细胞成像。通过紫外可见分光光度计、透射电镜、共聚焦显微镜对样品进行表征,结果表明：通过对反应时间的调控,获得的纳米复合粒子的二氧化硅壳层厚度可以控制在20～30nm。由于二氧化硅壳层的存在,大大提高了金纳米棒的稳定性,同时降低了金纳米棒的细胞毒性;此外,由于二氧化硅壳层具有良好的化学修饰作用,因此可以将荧光探针分子标记在二氧化硅壳层表面,修饰后的纳米复合粒子可以通过细胞内吞作用进入细胞,从而实现细胞内的光学成像。因此,该纳米粒子复合材料在生物传感、细胞成像以及光热治疗等方面有着良好的应用前景。     

聚乙烯亚胺对氧化锌纳米阵列形貌的影响

采用化学沉淀法,以硝酸锌和六次亚甲基四胺的水溶液为生长溶液,在涂覆氧化锌晶种层的玻璃衬底上制备了定向生长的氧化锌纳米棒阵列,并研究了添加剂聚乙烯亚胺的浓度对氧化锌纳米棒形貌和结构的影响。X射线衍射和场发射扫描电镜的结果表明,合成的氧化锌纳米棒阵列较为均匀致密,具有六方纤锌矿结构,且有沿(002)晶面择优生长的特性;随着聚乙烯亚胺浓度的增加,氧化锌纳米棒的直径减小,直径分布趋于均匀,且氧化锌纳米棒的形貌也从锥状转变为柱状结构;另外,聚乙烯亚胺的加入对氧化锌的生长速度具有抑制作用,当聚乙烯亚胺的浓度增加至0.012 mol·L-1时,无氧化锌阵列生长。对氧化锌纳米棒阵列进行了拉曼光谱表征,结果表明,随着溶液中聚乙烯亚胺浓度的增加,氧化锌纳米棒的氧空位缺陷减少。最后,对聚乙烯亚胺浓度对氧化锌纳米阵列影响的机理进行了探讨。     

一种制备高纯度单分散金纳米棒的新方法

报道了一种温和的、低成本、有效制备高纯度单分散金纳米棒的新方法.采用种子生长法,在两种表面活性剂体系下液相合成金纳米棒,向粗产品中加入氯化钠溶液,通过提高反应液的离子强度,利用制备的金纳米棒与球形颗粒不同的静电作用将金纳米棒分离纯化.运用透射电子显微镜(TEM)和扫描电子显微镜(SEM)对金纳米棒的表面形貌进行表征.结果表明,在较短时间内可获得纯度达97％以上的金纳米棒,并初步探讨了提纯机理.     

半胱氨酸修饰金纳米棒光学性质的研究

采用种子生长法制备了不同长径比的金纳米棒,并通过金硫键的结合在其表面包覆半胱氨酸分子。利用紫外-可见吸收光谱仪,扫描电子显微镜以及拉曼光谱仪等对样品进行分析和表征。实验结果表明金纳米棒产率较高,且一致性较好。表面修饰后的金纳米棒的纵向吸收峰发生蓝移,表明半胱氨酸分子与金纳米棒的结合有助于溶液分散性的提升。以结晶紫为探针分子,随着金纳米棒长径比的增加其拉曼增强效果变强。进一步分析发现,修饰后的金纳米棒的表面增强拉曼光谱的增强效果并未受到影响。通过金纳米棒与半胱氨酸分子牢固的结合,一方面可以提高金纳米棒溶液的分散性与稳定性;另一方面半胱氨酸分子可为金纳米棒修饰其它有机官能团提供了一个牢固的桥梁,有效地拓展了金纳米棒的应用方向。     

金纳米棒二聚体结构的Fano共振

等离激元金属纳米结构中的Fano共振,由于其在超灵敏传感、超材料、光开关和非线性光学器件等方面的潜在应用而引起了广泛的关注。但在单颗粒尺度下单个金属纳米二聚体结构的Fano共振的实验研究仍然很少。本研究基于单颗粒光谱技术从实验上探讨了二聚体结构产生的Fano共振现象。利用种子生长法制备了等离激元共振峰分别在1 060 nm和700 nm的一长一短金纳米棒,通过L-半胱氨酸分子的静电吸附自组装构建首尾相连的金纳米棒二聚体结构,在暗场显微系统中表征了金纳米棒二聚体耦合前后的散射光谱。结果表明,短金纳米棒的明偶极模式与长金纳米棒的暗四极模式间的相消干涉在660 nm处产生了明显的Fano共振谷,同时基于有限差分时域（FDTD）方法的理论模拟散射光谱与实验结果能够较好地符合。这种自组装金纳米棒二聚体在等离激元传感和探测等方面具有广阔的应用前景。     

利用聚碳酸酯模板制备的金纳米棒的表面增强Raman散射效应研究

采用聚碳酸酯模板和电化学沉积法制备基于金纳米棒的Raman场增强衬底, 制备的金纳米棒直径大约36 nm, 长约1 μm, 测试结果显示其共振吸收峰的位置约为540 nm. 比较了谐振和非谐振条件下的场增强情况, 并确定了场增益系数, 结果显示谐振激光激发下的增益比非谐振情况下提高了7.36倍. 本研究相对于前人的工作取得了如下进展: 一是讨论了谐振模式与非谐振模式下的金纳米棒的场增益系数, 利用谐振波长的激光激发金纳米棒, 进一步提高了场增益; 二是消除了聚碳酸酯模板分子的荧光背底, 使其在表面增强 Raman 散射方面的应用进一步变得可行. 关键词： 金纳米棒 表面增强Raman散射 聚碳酸酯模板     

基于毛细管的金纳米棒与纳米哑铃组装结构SERS效应比较研究

本文介绍了基于毛细管的金纳米棒(Au nanorods, AuNRs)与金纳米哑铃(Au nanodumbbells, AuNDs)组装结构,并从灵敏性、均一性和重现性等角度对两种不同纳米单元构筑的基底进行了表面增强拉曼散射(surface-enhanced Raman scattering, SERS)效应比较研究。结果表明,合成前驱体和分散体系均相同基础上调控得到的两种纳米单元在表面配体交换处理与构筑工艺一致前提下的基于毛细管组装,AuNDs较AuNRs组装结构表现出更高的SERS活性,而两者的均一性和重现性相当。通过选择SERS效应相对显著的毛细管基AuNDs组装结构对实际水体中的孔雀石绿进行取样和SERS检测,检测能力达到2×10~(-3)μg/g量级,表明此策略对实际水体中微量孔雀石绿的快速高灵敏检测具有一定的可行性。     

金纳米棒核/贵金属壳杂化纳米结构的可控制备和性质调控

贵金属纳米颗粒由于其独特的光学及催化性能引起了人们的广泛关注,而这些性能与纳米颗粒的尺寸、形貌、结构组成等密切相关.目前如何有意识地控制晶体生长过程,以得到人们需要的纳米结构和组成,仍具有相当大的挑战性.文章重点介绍了利用具有特定形貌和晶面组成的金纳米棒(Au nanorods)作为种子,借助形成核/壳结构,诱导了Ag, Pd, Pt棒状纳米结构的形成,并实现了对杂化纳米结构光学和催化性能的调控,进一步扩展了贵金属纳米结构的应用范围.作者的研究结果表明,形成杂化纳米结构是性能调控的一种有效方式.     

金纳米棒表面等离子体共振瑞利散射能量转移光谱测定痕量硼

硼是一种生命体必需的微量元素,但过量的硼对人体以及动植物有害。建立一种高灵敏度,高选择性以及简便的硼检测方法,对于环境和人类健康都具有很重要的意义。本研究的目的是建立一种简便,灵敏,选择性测定硼的金纳米棒等离子体共振瑞利散射能量转移光谱新方法。直径为12 nm, 长度为37 nm的金纳米棒采用种子生长法制备。在pH 5.6的NH₄Ac-HAc的缓冲溶液中和甲亚胺-H存在下,金纳米棒在404 nm处产生较强的共振瑞利散射峰。当体系中存在硼酸时,硼酸与甲亚胺-H形成硼酸-甲亚胺-H配合物。作为散射受体的配合物与散射共振能量转移的给体纳金米棒靠近时,发生瑞利散射共振能量转移,导致瑞利散射信号猝灭。随着硼酸浓度的增加,形成的配合物增加,金纳米棒转移给黄色配合物的散射光能量增大,导致体系404 nm处的瑞利散射强度线性降低。其降低值ΔI_{404 nm}与硼的浓度在10～750 ng·mL-1范围内呈良好的线性关系。考察了共存物质对该法测定2.3×10-7 mol·L-1 B的干扰情况。结果表明该法具有较高的选择性,即4×10-4 mol·L-1的Mn2+,Cd2+,Zn2+,Bi3+,Na+,Al3+,葡萄糖,Hg2+,IO-₃,F-,SO2-₄,SiO2-₃,NO-₃,ClO-₄,过氧化氢等对硼的测定无干扰。据此建立了一个灵敏度高,选择性好,简便快速检测硼的瑞利散射共振能量转移新方法。     

金纳米棒核/贵金属壳杂化纳米结构的可控制备和性质调控

贵金属纳米颗粒由于其独特的光学及催化性能引起了人们的广泛关注,而这些性能与纳米颗粒的尺寸、形貌、结构组成等密切相关.目前如何有意识地控制晶体生长过程,以得到人们需要的纳米结构和组成,仍具有相当大的挑战性.文章重点介绍了利用具有特定形貌和晶面组成的金纳米棒（Au nanorods）作为种子,借助形成核/壳结构,诱导了Ag...     

Combined Facile Synthesis,Purification, and Surface Functionalization Approach Yields Monodispersed Gold Nanorods for Drug Delivery Applications

Synthesizing gold nanorods (AuNRs) by seed-mediated growth method results in the presence of undesired size and shape particles by-products occupying 10–90% of the population. In this study, AuNRs are synthesized by the seed-mediated growth method using cetyltrimethylammonium bromide (CTAB) as a surfactant. AuNRs with redshifted longitudinal localized surface plasmon resonance (LLSPR) peak, localized in the biological “transparency window” (650–1350 nm), are synthesized after optimizing seed solution, silver nitrate solution, and hydrochloric acid solution volumes, based on the published protocols. A two-step purification method, dialysis followed by centrifugation, is applied to remove excess CTAB and collect LLSPR-redshifted AuNRs with high rod purity (>90%). CTAB is subsequently exchanged with polyethylene glycol (PEG) to improve AuNRs biocompatibility. PEGylated AuNRs are confirmed innocuous to both SN4741 cells and B16F10 cells by the modified MTT assay and the modified lactate dehydrogenase (LDH) assay up to 1 nm and 24 h incubation. In this study, a combined facile synthesis, purification, and surface functionalization approach is proposed to obtain water-dispersible monodispersed AuNRs for drug delivery applications.     

Assembly of Gold Nanoparticles on Gold Nanorods Using Functionalized Poly(N‐isopropylacrylamide) as Polymeric “Glue”

A telechelic thermoresponsive polymer, α‐amino‐ω‐thiol‐poly(N‐isopropylacrylamide) (H₂N‐PNiPAM‐SH), is used as the polymeric glue to assemble gold nanoparticles (AuNPs) around gold nanorods (AuNRs) into a satellite structure. Prepared by reversible addition‐fragmentation chain transfer polymerization followed by hydrazinolysis, H₂N‐PNiPAM‐SH is able to interlink the two types of the gold building blocks with the thiol‐end grafting on AuNRs and the amine‐end coordinating on the AuNP surface. The density of the grafted AuNPs on AuNRs can be tuned by adjusting the molar ratio between AuNPs and AuNRs in the feed. The resulted satellite‐like assembly exhibits unique optical property that was responsive to temperature change.     

基于金纳米棒可饱和吸收体的被动调Q掺铒光纤激光器

利用种子诱导生长法制备了长径比为5的金纳米棒,测量了它的吸收谱,结果表明该纳米棒具有较宽的吸收带（800~1 600 nm）。进一步测量了它的非线性吸收性质,结果表明它在1.56 μm波长处具有可饱和吸收特性,有望被用于实现被动调Q脉冲激光的输出。将该可饱和吸收体置于掺铒光纤激光器腔内,当泵浦功率增至30 mW时开始有稳定的调Q脉冲激光输出,输出激光的工作波长为1.56 μm。当泵浦功率为205 mW时,可获得的最大输出功率约6.9 mW,脉冲能量达219 nJ。研究结果表明,这种新型可饱和吸收体在脉冲激光领域具有广阔的应用前景。     

Combinational Chemotherapy and Photothermal Therapy Using a Gold Nanorod Platform for Cancer Treatment

Multimodal approaches combined with various nanomaterials and advanced techniques have been developed for synergistic cancer treatment. Among various therapies, conventional chemotherapy (CHT) is a direct cancer treatment that can produce unintended side effects due to nonspecific action on both the tumor and normal cells; patient-friendly photothermal therapy (PTT) may be able to treat embedded tumors in vital regions with minimal invasion but does not guarantee complete removal of cancers. However, the combination of CHT-PTT may provide a promising tool for direct cancer treatment with minimal side effects. In this regard, nanostructured materials, such as gold nanorods with tuned size and surface characteristics, are key components designed to enhance the heating capacity and active or passive delivery of drugs to the tumor site. In this review, the pioneering work synergizing CHT and PTT is summarized, and the current state-of-the-art in the development of inorganic and organic nanocomposites for combinational therapy is described.     

Ligand Exchange on Gold Nanorods: Going Back to the Future

Ligand exchange on gold nanorods (NRs) is still too often dismissed or not given the importance it should deserve. The many applications of gold NRs, mainly in plasmonics, biological imaging, and sensing, are made possible by finely tuning not only the optical properties of the metallic core but also the tethered functional groups. Gold NRs are mainly synthesized by using CTAB as the morphology‐guiding surfactant, and an intimate relationship between the crystallographic facets of the rod and the CTAB bilayer exists. Because of this, it is imperative to fully understand the ligand exchange mechanisms that allow replacing CTAB with functional ligands, including the energetic contributions. Here, the major applications of gold NRs are briefly overviewed, and what is known about ligand exchange mechanisms is summarized, as well as why it is important to achieve complete removal of CTAB, including the techniques that are used to characterize the exchange reaction products. The concept of interface in gold NRs is briefly examined, and explained why the scientific community should focus more on understanding and characterizing it. Starting from the published literature, the reader is guided through the reasons why it is thought that ligand exchange on gold NRs is perhaps the next grand challenge in the nanoparticle field.     

Synergistic Effect of Photothermal Therapy and Chemotherapy Using Camptothecin‐Conjugated Gold Nanorods

A combinatorial treatment comprising thermal therapy and chemotherapy offers synergistic effects by inducing localized heat to targeted tumor sites and simultaneously delivering anticancer drugs to minimize systemic side effects and enhance the cytotoxic effect. In this study, a novel platform is developed for combining photothermal therapy and chemotherapy using drug‐conjugated gold nanorods (GNRs). Camptothecin (CPT), a model anticancer drug, is chemically conjugated onto GNRs through hydrolytic ester bonding. Upon near‐infrared (NIR) irradiation, localized heat from GNRs in target areas starts to destroy tissues and cells via photothermal therapy, and the elevated temperature accelerates hydrolysis of ester linkage, rapidly releasing drugs for chemotherapy. This combined NIR triggered thermal therapy and chemotherapy with CPT‐functionalized GNRs (CPT‐GNRs) presents a synergistic effect that has high efficacy in in vitro tests, thus providing a robust platform for efficient cancer treatments.     

The Cellular Interactions of PEGylated Gold Nanoparticles: Effect of PEGylation on Cellular Uptake and Cytotoxicity

Poly(ethylene glycol) (PEG) is frequently used to coat various medical nanoparticles (NPs). As PEG is known to minimize NP interactions with biological specimens, the question remains whether PEGylated NPs are intrinsically less toxic or whether this is caused by reduced NP uptake. In the present work, the effect of gold NP PEGylation on uptake by three cell types is compared and evaluated the effect on cell viability, oxidative stress, cell morphology, and functionality using a multiparametric methodology. The data reveal that PEGylation affects cellular NP uptake in a cell‐type‐dependent manner and influences toxicity by different mechanisms. At similar intracellular NP numbers, PEGylated NPs are found to yield higher levels of cell death, mostly by induction of oxidative stress. These findings reveal that PEGylation significantly reduces NP uptake, but that at similar functional (= cell‐associated) NP levels, non‐PEGylated NPs are better tolerated by the cells.     

Smart Therapeutic Strategy of pH-Responsive Gold Nanoparticles for Combating Multidrug Resistance

As several multi-target drug delivery approaches are successfully identified through preclinical screening, their clinical success is often hampered by challenges such as poor circulation stability, dissimilarities in the pharmacokinetics of different drugs, as well as targeting inefficiency. Gold nanoparticles (AuNPs) are adopted as promising nanocarriers in the co-delivery of multiple therapeutic drugs for combination therapy. The pH-responsive AuNPs are synthesized and incorporated with multiple chemotherapeutic drugs, such as doxorubicin and bleomycin. Such structures can work as drug carriers to treat cervical carcinoma by adopting a quality by design approach. The designed nanocarrier is characterized by adopting a range of physicochemical and morphological techniques. In vitro drug release and cytotoxicity of optimized nanocarriers are assessed to cervical tumor epithelial cells. The results highlight the notable advantages of colloidal AuNPs, including sustained drug release, therapeutic agent delivery with high stability, and biocompatibility for more effective treatment of cervical carcinoma. Furthermore, by improving the biodistribution and/or bioavailability profiles, it is believed that the two-in-one approach may therefore give evidence on the fate of co-loaded nanocarrier as a promising trajectory for successful clinical translation against ovarian carcinoma to achieve maximum therapeutic synergy for an individual patient.