Selective Immobilization of Gold Nanoparticles on the Surface of a Photoreactive Polymer

A photoreactive polymer containing thiocyanate (SCN) groups was employed for the immobilization of gold nanoparticles (AuNP). Upon UV illumination, isothiocyanate (NCS) groups are generated at the surface by photoisomerization. The illuminated areas of the polymer layer containing NCS were selectively modified with 2-aminoethanethiol to give SH terminated thiourea units at the surface. Gold nanoparticles were selectively immobilized in these areas by immersing the polymer surface in a colloidal solution of gold nanoparticles stabilized by citric acid. Depending on the time of immersion, different amounts of gold were deposited on the illuminated areas, while no immobilization of AuNP was observed in the non-illuminated areas. By using photolithographic masks, patterned gold structures (μm scale) were produced on the polymer surface.     

Synthesis and Characterization of Gold Nanoparticles with Surface Ligands Derived from a Primary Phosphine

Reduction of HAuCl₄ · 3H₂O with NaBH₄ in THF/H₂O in the presence of the primary phosphine PH₂Mes* (Mes* = 2,4,6-(t-Bu)₃C₆H₂) gave a mixture of ca. 1.3 nm diameter gold nanoparticles (1) and the known oligomers [Au(PHMes*)]_n (2). Nanoclusters 1 might contain phosphido (PHMes*) or phosphinidene (PMes*) surface ligands, or both; they were characterized by elemental analysis, TGA, XPS, TEM, NMR, IR, and UV–Vis spectroscopies, and by their reactions with dodecanethiol, which gave PH₂Mes*. Solid-state ³¹P-NMR cross-polarization studies of 1 and 1D (prepared using NaBD₄ and PD₂Mes* in THF/D₂O) were consistent with the presence of phosphinidene surface groups.     

金纳米粒子组装体系粒子密度与SERS强度的关系

利用纳米粒子组装技术制备出金基底／巯基苯胺自组装膜偶联层／金纳米粒子的“三明治”结构。实验结果显示,该结构对偶联层分子的喇曼光谱显示出很好的增强效应,增强因子可达１０＾５;在表面粒子密度（粒子覆盖度）较低时,表面增强喇曼散射（ＳＥＲＳ）强度与表面粒子密度近似呈线性关系;随着表面粒子密度的增加,这种线性关系出现负偏差并在表面粒子密度较高区域出现一个平台;在６０￣１１０ｎｍ范围内大粒径金粒子对喇曼光谱     

Fluorescent Property of Gold Nanoparticles with Different Surface Structures

"?Fluorescence spectra of naked gold nanoparticles, triphenylphosphine stabled gold nanoparticles, and 3-mercaptopropionic acid substituted gold nanoparticles were studied. It was found that fluorescence intensities of gold nanoparticles were highly sensitive to surface molecules. The fluorescence quenching effect of these gold nanoparticles on CdSe nanoparticles was also investigated. This quenching effect was related to the overlap degree between the absorption spectra of gold nanoparticles and the emission spectrum of CdSe nanoparticles, and was surface-dependent as well. "     

表面电荷对聚乙二醇修饰金纳米粒子生物行为的影响

利用硫-金键将末端修饰甲氧基、氨基或羧基的巯基化聚乙二醇(Thiolated polyethylene glycol,HS-PEG)分子分别组装到金纳米粒子表面, 合成了3种带有不同表面电荷的聚乙二醇修饰金纳米粒子(PEGylated gold nanoparticles,PEG-Au NP).细胞共培养和小鼠尾静脉注射实验结果表明,表面电荷能够显著影响PEG-Au NP的生物行为.细胞对PEG-Au NP的吞噬量遵循正电荷＞电中性＞负电荷的规律.尾静脉注射的PEG-Au NP能够随小鼠的血液循环由全器官分布逐渐向肝脾转移.表面带负电荷的PEG-Au NP较难被小鼠肝脾清除,带但正电荷的PEG-Au NP能够引起小鼠免疫系统较强的响应.     

Polymer Chain Conformation on Deuterated Polystyrene Nanoparticles Investigated by SANS

We previously reported that grafted polystyrene (PS) chains on silica nanoparticles at a low grafting density show similar conformations to free PS chains in the same solvent, THF (diameter ?50 nm, Colloid.poly.Sci. (2013), 291, 9, 2087–2099). As an extension of our previous study we choose an organic nanoparticle (deuterated polystyrene, dPS) instead of inorganic nanoparticle to see the impact of the substrate material on chain conformation. Additionally, a wider range of molecular weights were prepared to investigate the conformation feature of grafted PS chains more in detail. Small angle neutron scattering (SANS) experiments were performed to characterize PS grafted dPS particles in good solvent condition, with deuterated toluene and deuterated THF as solvent. To get insight into the conformation of the grafted PS layer we apply a scaling law describing the dimension of free PS polymer in good solvent condition to the obtained thickness of the grafted PS layer. We find an overall agreement with the scaling law where the thickness of the grafted PS layer is slightly larger than 2R_g of the free polymer chains in the respective solvent giving hint for semi dilute polymer brush (SDPB) situation.     

金纳米粒子在平整硅基表面上的组装

采用水相硅烷化方法,将３－氨基丙基－三甲氧基硅烷（ＡＰＳ）组装在湿化学法处理的单晶硅表面上。接触角、原子力显微镜（ＡＦＭ）、Ｘ射线光电子能谱（ＸＰＳ）表征结果显示得到了平整均匀的具有氨基表面的自组装膜。ＳＥＭ观察表明,１６ｎｍ的金纳米粒子可以在上述氨基表面上形成均匀的亚单层排布,得到了具有Ａｕ纳米粒子／ＡＰＳ／Ｓｉ形成的纳米复合结构,进一步的处理可以使金纳米粒子在表面上的排列由随机趋于有序化。     

基于纳米金与纳米银簇间表面等离子增强能量转移效应特异性检测microRNA

microRNAs(miRNAs)的灵敏检测对临床诊断具有十分重要的意义.本研究采用偶联DNA聚合酶和核酸内切酶介导的恒温扩增反应实现靶标循环再生的策略,利用纳米金(AuNPs)与纳米银簇(AgNCs)间表面等离子增强能量转移效应,开发了一种miRNA定量检测方法.在AuNPs表面组装两种探针(Probe a和Probe b)制备响应元件Probe b-Probe a-AuNP,其中Probe a通过3′端巯基共价偶联到AuNPs表面,此外具有靶标miRNA互补序列、核酸内切酶酶切序列和Probe b互补序列,Probe b为荧光AgNCs合成模板.靶标miRNA存在时,启动酶级联恒温扩增反应,导致Probe b脱离AuNPs表面,抑制了Probe b为模板合成的AgNCs与AuNPs间表面等离子增强能量转移效应,使得反应体系荧光信号增强.本方法的检出限为2.5×10-11 mol/L,与miRNAs商业化检测试剂盒相比,避免了逆转录反应,而且操作简单,检测成本低,可应用于生物样本中miRNAs分析.     

基于纳米金粒子可视化分析检测的研究进展

基于纳米金粒子表面等离子共振性质发展起来的可视化分析,由于具有灵敏度高、可设计性强、分析过程快速等优点已被广泛地应用于各类目标分析物的检测,成为一种极具潜力的分析手段。本文综述了基于纳米金粒子表面等离子共振可视化分析检测的研究进展,并对其发展趋势进行了展望。     

Block Copolymer Supported Gold Nanoparticles Assemblies with Exposed Gold Surface

Polymer-involved nanoparticles or nanoparticle assemblies are now facing a crossroad, where the exposure of nanoparticle and multiple nanoparticles cannot be obtained at the same time. Therefore, a new series of nanoparticle clusters is synthesized, where multiple gold nanoparticles assemble with amphiphilic block copolymers supporting inside. The exposure of gold nanoparticles of the structure is confirmed and increases the reduction rate of 4-nitrophenol by 60%. The assemblies can also be used as surface enhanced Raman scattering(SERS) probes with an enhancement factor(EF) as high as 3×10³.     

Diffusion of Nanoparticles in Semidilute Polymer Solutions: A Multiparticle Collision Dynamics Study

The diffusion of nanoparticles immersed in semidilute polymer solutions is investigated by a hybrid mesoscopic multiparticle collision dynamics method. Effects of polymer concentration and hydrodynamic interactions among polymer monomers are focused. Extensive simulations show that the dependence of diffusion coefficient D on the polymer concentration c agrees with Phillies equation D-exp (-αc^δ) with a scaling exponent δ≈0.97 which coincides with the experimental one in literature. For increasing nanoparticle size, the scaling prefactor α increases monotonically while the scaling exponent always keeps fixed. Moreover, we also study the diffusion of nanoparticle without hydrodynamic interactions and find that mobility of the nanoparticle slows down, and the scaling exponent is obviously different from the one in experiments, implying that hydrodynamic interactions play a crucial role in the diffusion of a nanoparticle in semidilute polymer solutions.     

金纳米颗粒掺杂PEDOT多孔导电聚合物的电化学合成及其亚硝酸盐传感应用

该文以聚苯乙烯微球为模板,利用电化学方法制备了金纳米颗粒(Au NPs)掺杂的三维多孔聚3,4-乙烯二氧噻吩(PEDOT)纳米材料,该材料对亚硝酸盐的氧化展现出优异的电催化活性,这是由于其独特的三维(3D)纳米多孔结构可以掺杂更多的Au NPs,从而提供大量的活性位点用于亚硝酸盐的催化。此外,3D孔状结构还可促进亚硝酸盐离子的扩散从而加快电子的传递。所构建的传感器用于亚硝酸盐的检测,其线性范围为0. 2~2 200μmol/L,检出限为70 nmol/L。该传感器展现出优异的选择性、长期的稳定性和良好的重现性,用于实际样品检测,与标准方法的测试结果一致。     

含寡聚腺嘌呤序列DNA探针在金纳米粒子上的固定及杂交性能

利用寡聚腺嘌呤序列(OAS)与金的强相互作用,在金纳米粒子(AuNPs)上固定不同密度DNA探针(DNAprobe),详细探究不同条件(OAS长度、AuNPs粒径、NaCl浓度等)下单链DNAprobe的固定效果,以及制备的纳米探针(Au-probe)与互补DNA目标分子(DNAtarget)的杂交性能.利用透射电子显微镜(TEM)、紫外可见分光光度计(UV-Vis)、激光粒度仪等对制备的AuNPs的形貌、粒径、表面DNAprobe固定及杂交性能等进行了研究.结果表明,随OAS碱基数量由10增加到30和50,Au-probe上固定的DNAprobe数量降低.对粒径为10.2和24.3 nm的AuNPs,杂交效果最佳的NaCl浓度分别为300和25 mmol/L.随着AuNPs粒径增大,AuNPs单位面积上的DNAprobe固定量及DNAtarget杂交量均呈下降趋势.     

Two-Dimensional Polymer Networks Locking on Inorganic Nanoparticles

Two-dimensional polymers (2DPs), single-layer networks of covalently linked monomers, show perspectives as membranes and in electronics. However, 2D polymerization of monomers in orthogonal directions limited the formation of 2DPs on nanoparticles (NPs) with high surface curvatures. Here we propose a high-curvature 2D polymerization to form a single-layer 2DP network as a non-contacting ligand on the surface of NPs for their stabilization and functionalization. The high-curvature 2D polymerization of amphiphilic Gemini monomers was conducted in situ on surfaces of NPs with various sizes, shapes, and materials, forming highly cross-linked 2DPs. Selective etching of core–shell NPs led to 2DPs as a non-contact ligand of yolk-shell structures with excellent shape retention and high NP-surface accessibility. In addition, by copolymerization, the 2DP ligands can covalently link to other functional molecules. This work promotes the development of 2DPs on NPs for their functional modification.     

Epinephrine Oxidation in the Presence of Interfering Molecules on Gold and Gold Electrodes modified with Gold Nanoparticles and Thiodipropionic Acid in Aqueous Solution. A Comparative Study

Thiodipropionoc acid (TDPA), cysteamine (CA) and gold nanoparticles (Au‐NPs) modified gold pure electrodes have been applied in voltammetric sensors for simultaneous detection of epinephrine (EP), ascorbic (AA) and uric (UA) acids. Modified electrodes with self assembled layers (SAMs) show high selectivity, sensitivity, reproducibility and stability. A linear relationship between the epinephrine concentration and the current response is obtained in the range of 0.1 μM to 0.65 μM with the detection limit ≤0.065 μM for the electrodes modified at 2D surface and in the range of 0.1 μM to 0.75 μM with the detection limit ≤0.082 μM for the electrodes modified at the 3D surface.     

Partial Reduction and Selective Transfer of Hydrogen Chloride on Catalytic Gold Nanoparticles

HCl in solution accepts electron density from Au NPs and partially reduces at room temperature, as occurs with other simple diatomic molecules, such as O₂ and H₂. The activation can be run catalytically in the presence of alkynes to give exclusively E-vinyl chlorides, after the regio- and stereoselective transfer of HCl. Based also on this method, vinyl chloride monomer (VCM) can be produced in a milder and greener way than current industrial processes.     

金纳米粒子通过形成Au-S键的组装

利用湿化学法以纳米粒子为基本单元构筑各种纳米复合结构,具有灵活简便、通用性强等特点,近年来受到了广泛的重视．Ｎａｔａｎ［１-４］等最先开展了在固体表面上制备金纳米粒子单层膜的研究,他们借助双官能团硅烷化试剂对硅氧化物基底（如玻璃、石英等）进行表面修饰?..     

Studies on Composites of Nanoparticles and Some Polymers

The metal oxide nanoparticle of Cr₂O₃ was made into a composite with the polymers, which is of novel functions. Surfactants solubilized agents were used to increase compatibility between the two phases. The. application of the new products is described.     

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。     

表面等离子体共振传感技术在高分子研究中的应用

介绍了表面等离子体共振 (SPR)的基本原理和SPR传感器技术的应用现状 ,综述了SPR传感器在高分子科学研究中的应用和发展前景。