Supramolecular Hybrids from Cyanometallate Complexes and Diblock Copolypeptide Amphiphiles in Water

The self-assembly of discrete cyanometallates has attracted significant interest due to the potential of these materials to undergo soft metallophilic interactions as well as their optical properties. Diblock copolypeptide amphiphiles have also been investigated concerning their capacity for self-assembly into morphologies such as nanostructures. The present work combined these two concepts by examining supramolecular hybrids comprising cyanometallates with diblock copolypeptide amphiphiles in aqueous solutions. Discrete cyanometallates such as [Au(CN)₂]⁻, [Ag(CN)₂]⁻, and [Pt(CN)₄]²⁻ dispersed at the molecular level in water cannot interact with each other at low concentrations. However, the results of this work demonstrate that the addition of diblock copolypeptide amphiphiles such as poly-(L-lysine)-block-(L-cysteine) (Lys_m-b-Cys_n) to solutions of these complexes induces the supramolecular assembly of the discrete cyanometallates, resulting in photoluminescence originating from multinuclear complexes with metal-metal interactions. Electron microscopy images confirmed the formation of nanostructures of several hundred nanometers in size that grew to form advanced nanoarchitectures, including those resembling the original nanostructures. This concept of combining diblock copolypeptide amphiphiles with discrete cyanometallates allows the design of flexible and functional supramolecular hybrid systems in water.     

聚L-酪氨酸/半胱氨酸/纳米金修饰Pt电极固定血红蛋白测定H2O2

制备了聚L-酪氨酸/半胱氨酸/纳米金/血红蛋白修饰Pt电极,并用循环伏安法和交流阻抗法对制备过程进行了表征。还用循环伏安法和计时电流法研究了修饰电极与H2O2的相互作用。结果表明,该电极对H2O2有明显的催化作用,电流与H2O2浓度在3.5×10-7~2.0×10-3mol/L范围内呈线性关系,检出限为1.0×10-7mol/L。     

导电聚苯胺线膜修饰ZnO纳米棒阵列的可控制备及其紫外探测性能

基于p-n结的光生伏特效应可构筑性能优异的UV探测器,本文采用水热法可控制备竖直排列的氧化锌纳米棒阵列(n型ZnO-NRs),利用原位聚合法在ZnO-NRs表面上修饰p型聚苯胺线膜(PANI-NWs),再组装成ZnO-NRs与ZnO-NRs/PANI-NWs紫外探测器.通过扫描电镜(SEM)、X射线衍射仪(XRD)、紫...     

金催化乙炔氢氯化的密度泛函理论研究进展

乙炔氢氯化(AH)是生产氯乙烯的主要途径之一,传统上使用高毒性的汞催化剂,因此开发无汞催化剂迫在眉睫。金(Au)催化剂是最有潜力的替代催化剂之一,然而其活性Au物种、反应物的活化过程或反应过渡态结构等催化机理仍不够清晰。密度泛函理论（DFT）在研究由Au催化AH的反应机理中发挥了极其重要的作用。本文综述了DFT对金催化剂活性位点、反应物在催化剂上的吸附性质及反应机理的研究进展。重点讨论了DFT对阳离子金和金簇催化AH反应过程的模拟计算,包括Au电子状态、其它原子掺杂及金簇尺寸和形状对催化AH反应影响的模拟。结果表明DFT模拟计算在微观分子尺度上研究反应物的吸附、反应中间体及过渡态等方面发挥了关键作用,对理解Au催化AH反应机理做出了重要贡献。     

基于金纳米棒-壳聚糖复合膜的葡萄糖生物传感器

本文采用金纳米棒-壳聚糖复合膜固定葡萄糖氧化酶构建电流型葡萄糖生物传感器.通过电化学交流阻抗法和循环伏安法对酶膜状态进行了表征,得到了相应的等效电路和动力学参数.实验结果表明,金纳米棒-壳聚糖复合膜可以辅助电子传递,提高电极的电流响应,并使生物传感器的使用温度范围有很大的扩展.此传感器表现出对葡萄糖溶液浓度的优良响应,线性范围在2.78×10^-5mol/L—2.22×10^-3mol/L,响应灵敏度约为7.819μA·cm^-2(mmol/L)^-1,表观米氏常数为10mmol/L.本工作还研究了温度和溶液pH值对电极电流响应的影响.     

乙二醛诱导细胞凋亡的近红外表面增强拉曼光谱

将60 nm金纳米粒子导入到活的人骨肉瘤细胞中, 用近红外表面增强拉曼散射(SERS)技术获取细胞内化学成分的高分辨SERS信息. 对正常活性细胞和乙二醛诱导的凋亡细胞的比较研究表明, 对于正常活性的细胞, 金纳米探针主要分布在细胞质内(围绕细胞核), 而凋亡细胞内的金纳米探针的分布较为均匀, 在遍布凋亡细胞内的各个位置包括细胞表面均容易找到DNA片段的信息.     

Revisiting catechol derivatives as robust chromogenic hydrogen donors working in alkaline media for peroxidase mimetics

Colloidal noble metal-based nanoparticles are able to catalyze oxidation of chromogenic substrates by H₂O_2, similarly to peroxidases, even in basic media. However, lack of robust chromogens, which work in high pH impedes their real applications. Herein we demonstrate the applicability of selected catechol derivatives: bromopyrogallol red (BPR) and pyrogallol (PG) as chromogenic substrates for peroxidase-like activity assays, which are capable of working over wide range of pH, covering also basic values. Hyperbranched polyglycidol-stabilized gold nanoparticles (HBPG@AuNPs) were used as model enzyme mimetics. Efficiency of several methods of improving stability of substrates in alkaline media by means of selective suppression of their autoxidation by molecular oxygen was evaluated. In a framework of presented studies the impact of borate anion, applied as complexing agent for PG and BPR, on their stability and reactivity towards oxidation mediated by catalytic AuNPs was investigated. The key role of high concentration of hydrogen peroxide in elimination of non-catalytic oxidation of PG and improvement of optical properties of BPR in alkaline media containing borate was underlined. Described methods of peroxidase-like activity characterization with the use of BPR and PG can become universal tools for characterization of nanozymes, which gain various applications, among others, they are used as catalytic labels in bioassays and biosensors.     

Twist-grain boundary phase induced by Au nanoparticles in a chiral liquid crystal host

We report on the stabilisation of the liquid-crystalline, twist-grain boundary A (TGB_A) phase in mixtures of a chiral liquid crystal and surface-functionalised spherical Au nanoparticles (NPs) of 10 nm diameter. The results, obtained by calorimetric, optical, small-angle X-ray and plasmon resonance measurements, demonstrate that a TGB_A phase, which is metastable for the pure liquid crystal host, can be effectively stabilised for a 3 K range in the presence of NPs. Moreover, the role of NPs size on the TGB_A stabilisation is briefly discussed.     

Influence of Gold Nanoparticle Film Porosity on the Chemiresistive Sensing Performance

The porosity of 1‐hexanethiol‐functionalised gold nanoparticle films was assessed and utilised as chemiresistor sensors. Electrochemical capacitance measurements showed that the accessibility of electrolytes of different ionic strengths into the pores depended on the thickness of the electric double layer formed. A large variation in capacitance was measured in 0.01–1000 mM NaClO₄, implying a wide pore size distribution. The change in morphology of the nanoparticle films upon storage in air, water and ethanol for two weeks was investigated. There was a significant decrease in the electrochemical capacitance at high electrolyte concentrations for the ethanol‐stored films compared to the freshly‐prepared films suggesting a decrease in the number of small pores of radii in the range of 0.3–3 nm. This was further supported by optical topographical measurements where a decrease in the thickness of ethanol‐stored films was observed relative to the freshly‐prepared films. The porous nature of the nanoparticle films was found to have an effect on the chemical sensing behaviour. When used as chemiresistor sensors, for the detection of heptane in water, the ethanol‐stored films provided larger resistance changes and longer response times. This suggests that the more densely packed ethanol‐stored films provided more sites that enabled film swelling, and that diffusion of the analyte occurred through the narrower water‐filled pores. This demonstrates the effect of different storage conditions on film morphology and subsequently sensor response.