纳米金粒子与R-藻红蛋白的相互作用

以NaBH4为还原剂, 采用化学还原法制备了纳米金溶胶, 发现以pH=7的金前驱液还原得到的纳米金粒子具有最强的紫外吸收(525 nm), 当以聚乙烯吡咯烷酮(PVP)为稳定剂时, 此吸收紫移到510 nm. TEM观察金粒子大小为5~8 nm. PVP、聚乙烯醇(PVA)和吐温-80等能较好地稳定纳米金粒子, 而十二烷基苯磺酸钠、PEG-1000和OP乳化剂等则没有稳定作用. 以紫外-可见光谱(UV-Vis)、X光荧光光谱(XRF)、透射电子显微镜(TEM)等研究了纳米金粒子与R-藻红蛋白的相互作用, 发现R-藻红蛋白本身对纳米金粒子具有良好的稳定作用. 当R-藻红蛋白与纳米金粒子共存时, R-藻红蛋白所具有的538 nm吸收带强度有所增强, 并发生紫移, 同时578 nm的荧光强度也明显减弱, 这表明R-藻红蛋白与纳米金粒子的相互作用对R-藻红蛋白的空间结构产生了影响, 导致位于R-藻红蛋白外缘藻红素发色团(PEB)的微环境发生了改变. 凝胶柱层析及分光光度分析结果进一步证实了金纳米粒子与藻红蛋白存在明显的相互作用, 这种相互作用可能与藻红蛋白分子中所包含的氨基基团有关.     

憎水性金纳米粒子的制备、表征与形貌控制

在十六烷基三甲基溴化铵(CTAB)或十八胺(C18NH2)/正庚烷/乙醇/HAuCl4.4H2O W/O型微乳液体系中,利用简单的加热手段通过乙醇还原法制备了具有不同形貌和尺寸的憎水性金纳米材料。由CTAB或C18NH2稳定的金纳米颗粒运用紫外可见光谱(UV-vis)、透射电镜(TEM)和X射线衍射(XRD)等分别进行了表征和分析。用混合表面活性剂(CTAB/C18NH2)替代单一表面活性剂(CTAB)可以削弱CTAB对金纳米晶体生长的导向作用并提高粒子的单分散性。     

金＠壳聚糖复合材料的合成、表征及其葡萄糖选择氧化性能

采用硼氢化钠化学还原氯金酸的碱性溶液制备了纳米金溶胶, 利用紫外-可见吸收光谱研究了金与壳聚糖的相互作用. 结果表明, 壳聚糖能够捕获金纳米粒子并易于形成金@壳聚糖复合材料. 利用X-光粉末衍射(XRD)、紫外-可见漫反射光谱(UV-vis DRS)、透射电镜(TEM)、红外光谱(IR)、微分热重及差热分析(DTG-DTA)等对这种复合材料进行了表征, 发现该材料具有较小的金纳米粒子, 壳聚糖的存在改变了金纳米粒子的等离子共振吸收, 二者之间存在一定的键合作用. 以分子氧为氧化剂, 在温和条件下, 该材料对葡萄糖选择氧化制葡萄糖酸反应具有良好的催化性能.     

反相微乳液中憎水性纳米金的原位还原法合成

利用十八胺(C18NH2)/正丁醇/正庚烷/HAuCl4(aq)W/O型微乳液体系,在常温的碱促进条件下由正丁醇原位还原氯金酸合成了具有高度单分散的憎水性金纳米粒子。由C18NH2稳定的金纳米颗粒运用紫外可见光谱(UV-vis)、透射电镜(TEM)和X射线衍射(XRD)等分别进行了表征和分析,并探讨了微乳液体系各组分对形成金纳米粒子形貌、尺寸和单分散性的影响。结果显示,随十八胺/氯金酸摩尔比的增加,金粒子的尺寸逐渐减小而单分散性逐渐提高。在正丁醇原位慢还原氯金酸的过程中,实验所选W/O型微乳液模板和表面活性剂十八胺分子对憎水性金纳米粒子的形貌和尺寸仍具有良好的控制作用。     

金纳米粒子与抗体蛋白相互作用的光谱研究

本文运用透射电镜(TEM)、Zeta电位测量、紫外-可见吸收光谱(UV-Vis)、荧光光谱以及衰减全反射傅立叶变换红外光谱(ATR-FTIR)等技术手段,研究了免疫球蛋白G(IgG)与金纳米粒子的相互作用。结果表明,所制备的金纳米粒子呈均一分散的球形,抗体蛋白能够与金纳米粒子形成稳定的复合物。内源荧光光谱表明金纳米粒子对抗体蛋白的内源荧光有显著的静态猝灭,猝灭常数KSV=4.25×109 L·mol-1,同时金纳米粒子与抗体蛋白间有较强的作用,结合常数K=1.95×1014,结合位点数n为1.49。外源荧光光谱表明金纳米粒子与抗体蛋白之间的作用力主要是疏水相互作用。ATR-FTIR分析抗体蛋白与金纳米粒子作用前后蛋白二级结构的变化,结果显示,抗体蛋白有序结构含量降低,构象朝着更加松散的状态变化。     

pH敏感的金纳米颗粒的制备及表征

利用立方硅氧烷(odaaps)作为保护剂合成了金纳米颗粒,利用紫外-可见(UV-vis)吸收光谱、透射电镜(TEM)对纳米颗粒进行了表征。通过改变纳米溶胶的pH值,从而改变立方硅氧烷上羧基的存在形式,控制纳米颗粒表面的电荷,实现金纳米颗粒的可逆聚集与分散;当将其pH值降低至2.5时,颗粒能够完全沉淀,加碱调节其pH与原始值(pH=9)一致时,聚集的颗粒会自动重新分散形成溶胶,其具有与起始一致的高分散性。     

一维金纳米粒子链的制备及其光学特性研究

在没有模板存在的条件下, 只用表面活性剂为稳定剂, 制备了一维的金纳米粒子链, 详细考察了链状结构形成时各种试剂浓度、种类及其它外部条件对纳米粒子链形成的影响. 实验发现, 在HAuCl₄ 浓度1～5 mmol•L^－1、十二烷基磺酸钠(SDS)浓度在2～8 mmol•L^－1 (小于其CMC)范围内, 温度由60 ℃ 0.5 h内升高到100 ℃, 并在升温时间内分次将还原剂加完, 反应完成后不老化立即冷却到室温, 可以获得一维金纳米粒子链. 采用紫外可见光谱(UV-Vis)、同步光散射光谱和发射光谱等手段对金纳米粒子链的光学特性进行了研究, 用高分辨透射电子显微镜(HRTEM)研究了金纳米粒子的外观和粒径分布, 结果表明制备的金纳米粒子链是错落有致的链状结构, 结节处可以观察到金原子的排列晶格, 说明金纳米粒子的链状连接不是外部分子作用的结果; 表面等离子体共振吸收峰出现红移现象, 且随着链长的增加红移越明显; 具有非常强的光散射特性, 散射光强度比浓度相同的金纳米粒子高8倍; 发射光谱中明显观察到其三级散射, 表明其具有很好的非线性光学特性. 对金纳米粒子链的形成机理进行了探讨, 认为表面活性剂烷基亲油作用和金原子的聚集作用相互竞争是链状结构形成的原因.     

乳液聚合法制备纳米金/聚苯乙烯复合粒子

以氯金酸为前驱体,十二烷基硫醇和硼氢化钠分别作为稳定剂和还原剂,采用相转移法制备了单分散的金纳米粒子.将金纳米粒子通过乳液聚合的方法制备了纳米金/聚苯乙烯复合粒子.通过紫外-可见吸收光谱(UV-Vis)研究了纳米金和纳米金/聚苯乙烯复合粒子的光吸收特性,使用傅立叶变换红外光谱(FT-IR)、X射线衍射(XRD)、透射电子显微镜(TEM)和动态光散射(DLS)对产物的组成、晶体结构、形貌、以及粒径进行了表征.结果表明,复合粒子为粒径分布较窄的球形,其中的金纳米粒子为面心立方结构.热失重分析(TGA)说明制备的纳米金/聚苯乙烯复合粒子具有很好的热稳定性.     

金核银壳纳米粒子薄膜的制备及SERS活性研究

采用柠檬酸化学还原法制备金溶胶, 通过自组装技术在石英片表面制备金纳米粒子薄膜, 在银增强剂混合溶液中反应获得金核银壳纳米粒子薄膜. 用紫外-可见吸收光谱仪和原子力显微镜(AFM)研究了不同条件下制备的金核银壳纳米粒子薄膜的光谱特性和表面形貌, 并以结晶紫为探针分子测量了金核银壳纳米粒子薄膜的表面增强拉曼光谱(SERS). 结果表明, 金纳米粒子薄膜的分布、银增强剂反应时间的长短对金核银壳纳米粒子薄膜的形成均有重要影响. 制备过程中, 可以通过控制反应条件获得一定粒径的、具有良好表面增强拉曼散射活性的金核银壳纳米粒子薄膜.     

纳米金免疫凝集比率光度法检测IgG

利用柠檬酸钠还原法制备了13nm胶体金,透射电子显微镜表征其具有良好的单分散性,通过它与牛血清蛋白(BSA)作用的紫外-可见光谱表明其对蛋白具有良好的生物亲和性。以羊抗人免疫球蛋白G(IgG)修饰的金纳米粒子作探针,基于金纳米粒子免疫聚集导致其消光系数和分散度的变化建立了人IgG的比率光度分析方法。结果表明所制备的纳米金标记探针在人IgG浓度100ng/mL～100μg/mL范围内有良好的线性响应,加标法测定结果表明该法具有良好的回收率和精密度。以细胞色素C(CytoC)和辣根过氧化物酶(HRP)两种蛋白质作对照实验,发现所制备的金纳米探针对IgG具有高度的特异性。     

Biosynthesis of Gold Nanoparticles by Streptomyces sp. ERI-3 Supernatant and Process Optimization for Enhanced Production

In this study, we present a simple and eco-friendly method for extracellular biosynthesis of gold nanoparticles by Streptomyces sp. ERI-3 cell-free supernatant. The research was also aimed to evaluate the effects of different reaction parameters including incubation temperature, reaction time, HAuCl₄ concentration and pH on gold nanoparticles production. The UV?CVis spectroscopy was used to monitor the formation of gold nanoparticles. The synthesized gold nanoparticles were characterized with XRD, TEM, and SEM. The average particle size ranged from 10 to 30?nm with spherical shape at optimum conditions.     

Water‐Soluble Gold Nanoparticles: From Catalytic Selective Nitroarene Reduction in Water to Refractive Index Sensing

Water‐soluble gold nanoparticles (Au NPs) stabilized by a nitrogen‐rich poly(ethylene glycol) (PEG)‐tagged substrate have been prepared by reduction of HAuCl₄ with NaBH₄ in water at room temperature. The morphology and size of the nanoparticles can be controlled by simply varying the gold/stabilizer ratio. The nanoparticles have been fully characterized by TEM, high‐resolution (HR) TEM, electron diffraction (ED), energy‐dispersive X‐ray spectroscopy (EDS), UV/Vis, powder XRD, and elemental analysis. The material is efficient as a recyclable catalyst for the selective reduction of nitroarenes with NaBH₄ to yield the corresponding anilines in water at room temperature. Furthermore, the potential ability of the Au NPs as a refractive index sensor owing to their localized surface plasmon resonance (LSPR) effect has also been assessed.     

High-yield Synthesis of Branched Gold Nanocrystals by a Sodium Diphenylamine-4-Sulfonate Reduction Process in Polyethylene Glycol Aqueous Solution

For developing new excellent electrocatalysts toward methanol and oxygen, branched Au nanocrystals have been prepared in high yield by the reaction of HAuCl₄ and sodium diphenylamine‐4‐sulfonate in the presence of PEG (polyethylene glycol) at room temperature. When the amount of PEG was in the range of 1–3 mL, branched Au nanocrystals were all obtained, and the amounts of sodium diphenylamine‐4‐sulfonate and HAuCl₄ had no obvious effect on the morphology of gold nanocrystals. PEG molecules play an important role in the formation of branched gold nanocrystals. The nanocrystals were characterized by transmission electron microscopy (TEM), selected area electron diffraction, high‐resolution transmission electron microscopy (HRTEM) and UV‐Vis absorption spectrum. HRTEM research suggests that the tips of gold nanocrystals grow selectively in the [111] directions. The UV‐Vis absorption spectrum displays two‐separated surface plasmon resonance peaks.     

Synthesis of Hollow Gold Nanospheres and Their Applications in Surface-enhanced Raman Scattering and DNA Biosensor

Hollow gold nanospheres (HGNs) with nanopinholes were prepared by chemical reduction of HAuCl₄ with aqueous KBH₄ in the presence of the Bu₄PBr template. The HGNs could be served as substrates for surface‐enhanced Raman scattering (SERS), which exhibited much higher surface enhancement than the solid gold nanoparticles in case of Rhodamine 6G as a molecule probe. Moreover, the HGNs could also be used in the modified electrode to detect DNA and superior to the solid counterpart of the similar size. Based on the detailed characterizations by transmission electron micrograph (TEM), field emission scanning electron micrograph (FESEM) and UV‐visible absorption spectroscopy, a plausible mechanism for forming HGNs was proposed. Meanwhile, the promoting effect of the hollow gold nanospheres on the SERS was discussed briefly.     

新型双链表面活性剂DDOBA的合成与高单分散性憎水纳米金的制备

自行设计合成了新颖的苄胺型双链表面活性剂3,4-双十二烷氧基苄胺(DDOBA). 利用DDOBA/正丁醇/正庚烷/甲酸/HAuCl₄·4H₂O自发形成的水/油(W/O)型微乳液作为微反应器, 通过微波辐射下的甲酸还原法成功制备了DDOBA保护的憎水性金纳米粒子, 并通过紫外-可见(UV-Vis)光谱、透射电镜(TEM)、高分辨透射电镜(HR-TEM)和X射线衍射(XRD)等方法进行了表征和分析. 结果显示, DDOBA既可参与形成稳定的W/O型(油包水型)微乳液, 又可作为金纳米粒子的良好保护剂. 在合适的微乳液体系组成范围内, 用本实验方法可以获得高单分散性的憎水性金纳米粒子, 并能在空气/水界面上自动形成大面积短程有序的纳米金二维自组装膜.     

Synthesis of Core-Shell (Pd-Au) Bimetallic Nanoparticles in Microemulsions

Palladium-gold core-shell nanoparticles were synthesized in the aqueous domains of water in oil microemulsions by the sequential reduction of H₂PdCl₄ and HAuCl₄. The nanoparticles were characterized by ultraviolet-visible (UV-vis) spectroscopy and transmission electron microscopy (TEM). The UV-vis spectra confirm the presence of palladium nanoparticles after reducing H₂PdCl₄. These particles have been used as seeds for the core-shell particles. UV-vis spectra show that, after reducing HAuCl₄, the surface plasmon absorption of the nanoparticles is dominated by gold, revealing the encapsulation of the palladium seeds. These results agree with crystallographic analysis performed with high-resolution TEM pictures, as well as with selected area electron diffraction. The TEM pictures show the core-shell nanoparticles with an average diameter of 9.1 nm, as compared with 5 nm for the palladium seeds, in good agreement with the used Pd:Au molar ratio.     

Colloidal Gold Nanoparticles Protected by Cationic Polyelectrolytes

Abstract

Several stable gold colloids were prepared by the in-situ reduction of hydrogen tetrachloroaurate (HAuCl₄) in the presence of various cationic polyelectrolytes. Several types of such polyelectrolytes were investigated for their ability to stabilize gold colloids, and UV – VIS spectroscopy was used to follow the in-situ reductions and to further characterize the colloids. The particle sizes and size distributions were determined by transmission electron microscopy (TEM). TEM micrographs and UV-VIS spectra were also used to characterize the stability of the colloids after storage for nine months in air at room temperature. Colloids protected by the cationic polyelectrolytes with ammonium side-groups along a hydrophobic polymer backbone frequently exhibited very good stability.     

One‐Step Synthesis of Collagen Hybrid Gold Nanoparticles and Formation on Egyptian‐like Gold‐Plated Archaeological Ivory

A one‐step method is reported to synthesize hybrid gold nanoparticles (AuNPs) by reduction of HAuCl₄ in acetic solution in the presence of collagen (Col), dicarboxylic acid‐terminated polyethylene glycol (PEG), and cetyltetrammonium bromide (CTAB) mixed with hydoxyapatite (HAP) as surfactants. Such formation process of AuNPs was shown to be responsible for purple stains naturally formed on Egyptianizing archaeological gilded ivories from 8th BC Syria. The understanding of this formation mechanism, which most likely involves a step with hybrid AuNPs, allows the establishing of an authenticity marker of ancient gold‐plated ivories.     

Room Temperature Synthesis of Gold Nanokites in Polyvinyl Alcohol‐Sodium Dodecyl Sulfate Aggregations Aqueous Solution

Controlled synthesis of asymmetrical gold nanokites was realized by reducing HAuCl₄ with polyvinyl alcohol (PVA) in PVA‐sodium dodecyl sulfate (SDS) aggregations aqueous solution at room temperature without any additional reducing agents. The crystal structures, optical property and growth process of the gold nanokites were investigated by X‐ray diffraction (XRD), Vis‐NIR spectrum and transmission electron microscope (TEM). HAuCl₄ concentration dramatically influenced the morphologies of the products. When HAuCl₄ concentration was increased from 0.5 mmol·L⁻¹ to 2.2 mmol·L⁻¹, the products changed from network‐like nanostructures to nanokites, nanoleaves and microplates. SDS was indispensable for the formation of gold nanokites and without SDS super‐branched structures became the dominant products.     

Gold clusters and nanoparticles in reverse micelles formed by tritons X-100, X-114, and X-45

The formation of gold nanoparticles and clusters in solutions of reverse micelles formed by Tritons X-45, X-114, and X-100 (polyoxyethylene isooctylphenyl ethers with degrees of polymerization n = 5, 7–8 and 9–10, respectively) in the presence of sodium sulfite is studied. The stability of these particles is shown to depend on the length of ethylene oxide chains in surfactant molecules, water content in micelles, and the presence of special additives. It is found that, on one hand, L-ascorbic acid favors a reduction of HAuCl₄ and, on the other hand, affects the stability of resultant particles.