金纳米球和金纳米棒的制备及其光热催化性能

以氯金酸(HAuCl_4)为原料,硼氢化钠(NaBH_4)为还原剂,聚乙烯吡咯烷酮K30(PVP)为稳定剂制备了尺寸5 nm的金纳米球;以阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)为模板剂和油酸钠(NaOL)稳定剂,用种子生长法制备了不同长径比(R=2.5~4)的金纳米棒。在2 W·cm~(-2)的808 nm激光照射10 min条件下,C(0.4 mg·mL~(-1))浓度金纳米球溶液升温10.2℃,该溶液可催化血液中亚硝基硫醇释放NO,最大释放量可达1.42 nmol·L~(-1);相同光热及催化条件下,C(0.4 mg·mL~(-1))浓度金纳米棒(R=3.01)溶液升温41.3℃,该溶液催化血液中亚硝基硫醇释放NO最大释放量可达1.89 nmol·L~(-1)。金纳米球和金纳米棒的光热及催化性能随着浓度增加而增强,金纳米棒的光热及催化性能要优于金纳米球。     

聚乙二醇-金纳米棒介导的近红外光热抑菌作用

种子生长法合成纵向表面等离子体共振吸收峰为785 nm的金纳米棒,并对其表面进行聚乙二醇(PEG)修饰,研究了表面修饰PEG的金纳米棒(polyethylene glycol modified gold nanorods,PEG-GNR)的光热转化效应,并测试了其细胞毒性.以革兰氏阳性菌金黄色葡萄球菌、蜡状芽孢杆菌,革兰氏阴性菌大肠埃希氏菌及铜绿假单胞菌为细菌模型,详细研究了PEG-GNR在808 nm波长近红外激光照射下金纳米棒浓度和照射功率对抑菌效果的影响.结果表明,PEG-GNR对革兰氏阳性菌和革兰氏阴性菌在近红外照射下均有较好的抑菌效果,并且抑菌效果与金纳米棒的浓度和照射功率有着密切的关系;结合荧光显微镜和透射电子显微镜对细菌坏死状况的观察,初步证实细菌对PEG-GNR有效吸收是近红外光热杀菌的关键因素.     

聚乙二醇-金纳米棒介导的近红外光热抑菌作用

种子生长法合成纵向表面等离子体共振吸收峰为785 nm的金纳米棒,并对其表面进行聚乙二醇(PEG)修饰,研究了表面修饰PEG的金纳米棒(polyethylene glycol modified gold nanorods,PEG-GNR)的光热转化效应,并测试了其细胞毒性。以革兰氏阳性菌金黄色葡萄球菌、蜡状芽孢杆菌,革兰氏阴性菌大肠埃希氏菌及铜绿假单胞菌为细菌模型,详细研究了PEG-GNR在808nm波长近红外激光照射下金纳米棒浓度和照射功率对抑菌效果的影响。结果表明,PEG-GNR对革兰氏阳性菌和革兰氏阴性菌在近红外照射下均有较好的抑菌效果,并且抑菌效果与金纳米棒的浓度和照射功率有着密切的关系;结合荧光显微镜和透射电子显微镜对细菌坏死状况的观察,初步证实细菌对PEG-GNR有效吸收是近红外光热杀菌的关键因素。     

适体功能化的金纳米棒用于癌症靶向治疗的研究进展

金纳米棒(gold nanorods,GNRs)具有特殊的光学性质、较大的比表面积、出色的光热转换性能、表面易修饰等特点,在药物递送、光疗、生物成像和化学传感等领域应用十分广泛。适体是短的单链DNA或RNA片段,可特异性识别癌细胞或其表面的膜蛋白。近年来,适体功能化的GNRs在癌症靶向治疗领域显示出良好的应用前景。根据GNRs对癌症作用机制的差异,本文从光热疗法、光动力疗法、化疗和联合疗法4个方面总结了适体功能化的GNRs在癌症靶向治疗中的最新进展,并对该领域面临的主要挑战和发展趋势进行了探讨与展望。     

阴离子表面活性剂作为添加剂种子生长法制备尺寸可调的单分散金纳米棒

以不同阴离子表面活性剂作为添加剂种子生长法制备金纳米棒, 并考察阴离子表面活性剂种类对金纳米棒形貌及光学性质的影响。在十二烷基苯基磺酸钠(SDBS)存在下, 金纳米棒的产率明显高于使用十二烷基磺酸钠的反应体系。对添加SDBS的种子生长法制备金纳米棒的反应条件进行优化, 得到十六烷基三甲基溴化铵、SDBS、抗坏血酸和硝酸银的最佳浓度分别为0.04 mol·L^-1、2.4 mmol·L^-1、1.2 mmol·L^-1和0.08 mmol·L^-1。在此条件下, 金纳米棒的生长在30 min内完成, 所制备的金纳米棒表面等离子共振吸收峰位于823 nm, 其横纵比为(5±0.03)。当改变生长液中硝酸银浓度时, 金纳米棒的尺寸也随之发生改变。此外, 我们还探讨了SDBS的作用机理。相对于经典种子生长法, 新方法制备纳米金棒在尺寸可调性、单分散性和生物毒性方面明显改善, 可广泛应用于各种光学及生物分析。     

阴离子表面活性剂作为添加剂种子生长法制备尺寸可调的单分散金纳米棒

以不同阴离子表面活性剂作为添加剂种子生长法制备金纳米棒,并考察阴离子表面活性剂种类对金纳米棒形貌及光学性质的影响。在十二烷基苯基磺酸钠(SDBS)存在下,金纳米棒的产率明显高于使用十二烷基磺酸钠的反应体系。对添加SDBS的种子生长法制备金纳米棒的反应条件进行优化,得到十六烷基三甲基溴化铵、SDBS、抗坏血酸和硝酸银的最佳浓度分别为0.04 mol.L-1、2.4 mmol.L-1、1.2 mmol.L-1和0.08 mmol.L-1。在此条件下,金纳米棒的生长在30 min内完成,所制备的金纳米棒表面等离子共振吸收峰位于823 nm,其横纵比为(5±0.03)。当改变生长液中硝酸银浓度时,金纳米棒的尺寸也随之发生改变。此外,我们还探讨了SDBS的作用机理。相对于经典种子生长法,新方法制备纳米金棒在尺寸可调性、单分散性和生物毒性方面明显改善,可广泛应用于各种光学及生物分析。     

刺激响应性共聚物修饰金纳米棒的制备及其抗肿瘤性能

以1-叔丁氧基羰基-2-丙烯酰肼(Boc-AH)、N-(3,4-二羟基苯乙基)丙烯酰胺(DA)和聚乙二醇甲醚丙烯酸酯(mPEGA)为单体,利用可逆加成-断裂链转移聚合法制备了嵌段共聚物聚丙烯酰肼-聚N-(3,4-二羟基苯乙基)丙烯酰胺-聚单甲氧基聚乙二醇丙烯酸酯(PAH-b-PAD-b-PmPEGA,缩写为HDP),该...     

金纳米棒的表面改性及其在生物医学领域的应用

各向异性的金纳米棒由于具有独特的光学性质,在生物医学领域得到了日益广泛的应用。本文综述了金纳米棒的表面改性及其在生物标记与识别、生物成像、癌症诊断和光热治疗等领域中的应用。     

一种简易合成具有近红外吸收的纳米金壳球体方法

对经典的合成方法进行了详细的系统性的研究,通过改变合成过程中各反应物的参数,简易地得到了稳定的具有近红外吸收的纳米金壳球体。利用紫外可见光谱、动态光散射仪和透射电镜研究了制备过程中的各个参数对纳米金壳球体光学性质的影响。实验结果显示胺化试剂的用量以及先导试剂的预处理等在制备过程中都是重要影响因素。由改进方法所制备的纳米金壳球体具有很窄的粒径分布,并能在没有外加表面活性剂的条件下稳定地单分散于水溶液中。这些方法的改进提供了一种简易制备具有近红外吸收的纳米金壳球体的方法,从而有利于拓展此类纳米粒子在生物医学领域中的应用研究     

金纳米棒在超疏水表面的组装行为研究

采用了"烟囱效应"以及超疏水表面作为基底这两项外力作用来将金纳米棒进行组装。借用"烟囱"技术的侧面向心力所产生的向心空气气流,以及超疏水表面上液滴收缩产生的应力对纳米粒子的向心挤作用,得到了金纳米棒垂直于基片致密排列的特殊的组装花样以及金纳米棒水平短程有序的致密排列的组装花样。这种简便的组装方法不仅对纳米器件的应用有着重要的影响,而且可以广泛地适用于其他的纳米粒子的二维有序组装以得到不同的功能性的纳米组装体。     

小尺寸金纳米棒的快速制备及影响因素的研究

通过研究十六烷基三甲基溴化铵、抗坏血酸、NaBH4和AgNO3的用量,以及搅拌时间、反应时间对无种子生长法制备金纳米棒的影响,筛选出了最佳制备条件,以及各成分对金纳米棒生长过程中的作用.采用可见吸收光谱和透射电镜图对不同条件下所制备出的金纳米棒进行了表征.在室温为28℃,CTAB浓度为0.1 mol/L、AgNO3浓度为96μmol/L、AA浓度为0.97 mmol/L、NaBH4浓度为1.5μmol/L,搅拌25 s等最佳条件下,只需反应6h就能够成功制备出长径比为5且形貌均匀、分散性和稳定性良好、轴宽较小的金纳米棒,且有望应用于水环境中Hg2+的检测.     

Synthesis of Uniform Gold Nanorods with Large Width to Realize Ultralow SERS Detection

In this work, we successfully demonstrate high-yield synthesis of high-quality gold nanorods (Au NRs) with width ranging from 6.5 nm to 175 nm by introducing heptanol molecules as secondary templating agents during cetyltrimethylammonium bromide-templated, seeded growth method. The results show that an appropriate concentration of heptanol molecules not only alter the micellization behavior of CTAB in water, but also help silver ions impact the symmetry-breaking efficiency of additional Au−NP seeds in addition to enhancing the utilization of gold precursors. Moreover, the generality and versatility of the present strategy for synthesis of Au NRs with flexible controlled dimensions are further demonstrated by successful synthesis of Au NRs with the assistance of other fatty alcohols with properly long alkyl chains. Furthermore, when arrays of vertically aligned Au NRs with large width (AVA−Au_120×90 NRs) are used as SERS substrates, they can achieve the ultralow limit of detection for crystal violet (10⁻¹⁶ M) with good reliability and reproducibility, and the rapid detection and identification of residual harmful substances.     

Synthesis of 15P-Conjugated PPy-modified Gold Nanoparticles and Their Application to Photothermal Therapy of Ovarian Cancer

In this work, we synthesized the polypyrrole（PPy） modified gold nanoparticles and demonstrated their negligible cytotoxicity in vitro. These nanoparticles have also been demonstrated to efficiently ablate different kinds of tumor cells in vitro under the irradiation of the near-infrared laser. When the PPy modified gold nanoparticles were conjugated with the tumor-targeted molecule of 15P（sequence： SHSWHWLPNLRHYAS）, these conjugates displayed hyperthermia effects on the human ovarian cancer cell line SK-OV-3 cells in vitro under the irradiation of near-infrared laser, showing great tumor-targeted treatment efficiency. To determine the potential hyperthermia effect of PPy modified gold nanoparticles or 15P-conjugate on tumor cells in vivo, the SK-OV-3 cells were used to induce the subcutaneous tumor-bearing nude mice. The significant inhibition effects of near-infrared laser mediated PPy modified gold nanoparticles or 15P-conjugate on the tumor growth were observed. These composite results suggest that the 15P-conjugated PPy modified gold nanoparticles exhibit great biocompatibility, particularly tumor-targeted effect and the effective photothermal ablation of tumor cells, which warrants the potential therapeutic value of this conjugate for further application to the in vivo localized tumor therapy.     

基于AuCl(油胺)复合物合成形貌可控的金纳米结构

简要综述了使用一价金复合物AuCl(油胺)作为前驱物合成形貌可控的金纳米结构的相关工作. 通过改变有机溶剂、添加异质金属纳米粒子及控制反应温度等手段, 成功合成出球形的金纳米粒子(平均直径12.7 nm)、超细金纳米线(平均直径1.8 nm)及超细金纳米棒(平均直径2 nm); 并通过牺牲磁性纳米粒子模板的方法合成出枝状金纳米结构. 除了对合成方法和过程的介绍, 还简要讨论了每种纳米结构的形成机制.     

Controllable Preparation of Plasmonic Gold Nanostars for Enhanced Photothermal and SERS Effects

Gold nanostars(Au NSs) are asymmetric anisotropic nanomaterials with sharp edge structure. As a promising branched nanomaterial, Au NS has excellent plasmonic absorption and scattering properties. In order to tune the plasmonic photothermal and surface-enhanced Raman scattering(SERS) activity of Au NSs to obtain the desired characteristics, the effects of reagents on the local surface plasmon resonance(LSPR) bands of Au NSs were studied and the morphology and size were regulated. Nanoparticles with different sharp edges were synthesized to make their local plasmon resonance mode tunable in the visible and near-infrared region. The effects of the number and sharpness of different tips under the control of AgNO₃ on the photothermal response of Au NSs and the SERS activity and their mechanism were discussed in detail. The results show that as the length of the branch tip becomes longer and the sharpness increases, the plasmonic photothermal effect of Au NSs is strengthened, and the photothermal conversion efficiency is the highest up to 40% when the length of Au NSs is the longest. Au NSs with high SERS activity are used for the Raman detection substrate. Based on this property, the quantitative detection of the pesticide thiram is achieved.     

Chemical‐Bonding‐Directed Hierarchical Assembly of Nanoribbon‐Shaped Nanocomposites of Gold Nanorods and Poly(3‐hexylthiophene)

Nanoribbon‐shaped nanocomposites composed of conjugated polymer poly(3‐hexylthiophene) (P3HT) nanoribbons and plasmonic gold nanorods (AuNRs) were crafted by a co‐assembly of thiol‐terminated P3HT (P3HT‐SH) nanofibers with dodecanethiol‐coated AuNRs (AuNRs‐DDT). First, P3HT‐SH nanofibers were formed due to interchain π–π stacking. Upon the addition of AuNRs‐DDT, P3HT‐SH nanofibers were transformed into nanoribbons decorated with the aligned AuNRs on the surface (i.e., nanoribbon‐like P3HT/AuNRs nanocomposites). Depending on the surface coverage of the P3HT nanoribbons by AuNRs, these hierarchically assembled nanocomposites exhibited broadened and red‐shifted absorption bands of AuNRs in nIR region due to the plasmon coupling of adjacent aligned AuNRs and displayed quenched photoluminescence of P3HT. Such conjugated polymer/plasmonic nanorod nanocomposites may find applications in fields, such as building blocks for complex superstructures, optical biosensors, and optoelectronic devices.     

5-[2-(对苯偶氮苯氧基)丁氧基]苯基-10,15,20-三[(对甲氧基苯基)]卟啉及其金属配合物的合成

以5-[2-(4-溴丁氧基)苯基]-10,15,20-三(对甲氧基苯基)卟啉和对羟基偶氮苯为原料,经取代反应合成新化合物5-[2-(对苯偶氮苯氧基)丁氧基]苯基-10,15,20-三[(对甲氧基苯基)]卟啉(2),2经配位反应合成了金属铜,锌配合物(2a)和(2b),其结构经UV-Vis,1H NMR,IR和元素分析表征。     

Synthesis and Characterization of a Cobalt Complex with Maleate and Pyridine

A new polymeric cobalt complex [Co(u-male)(py)(H2O)]n (male=maleate; py =pyridine) 1 was prepared by cobalt chloride hexahydrate with disodium maleate and pyridine in an alcohol-aqueous solution. Single-crystal X-ray analysis has revealed that 1 crystallizes in the orthorhombic system, space group Pnma with a=18.001(1), b=7.6001(6), c=7.4731(6) A, V=1022.4(1)A3, Z=4, C9H9CoNO5, Mr=270.10, Dc= 1.755 g/cm3, F(000)=548, μ(MoKa)=1.683 mm-1, S =1.002, the final R=0.0280 and wR=0.0746 for 883 observed reflections with I ＞ 2σ(I). The structure analysis shows an approximate octahedral coordination environment of metal center. The Co(Ⅱ) ions are bridged by maleic anions in a rare tetradentate coordination fashion with a syn-anti coplanar conformation of the carboxyl group, forming a two-dimensional corrugated 2-D structure which is further attached into a three-dimensional framework via non-classical C-H…O interactions between adjacent layers.