金纳米粒子表面自组装巯基十一烷醇单分子层体系的制备及其光散射特性研究

采用柠檬酸钠还原法制备了水相金纳米粒子, 通过巯基的自组装, 成功获得了巯基十一烷醇(MUN)单分子层保护的金纳米粒子. 用紫外可见光谱、透射电子显微镜、激光散射粒度分析、同步散射光谱和发射光谱等手段对组装前后的金纳米粒子的性质进行了研究. 结果表明: 制备的金纳米粒子最大吸收波长518 nm, 形状规则, 粒度均匀, 平均粒径为14.6 nm, 每个粒子含有约9.64×10⁴原子; 组装之后的金纳米粒子表面等离子体共振吸收峰红移17.0 nm, 平均粒径增大为20.2 nm, 组装层的平均厚度2.8 nm, 与MUN分子长度相当, 结合量实验证明每一个金纳米粒子可以结合约7.52×10³个MUN, 表面覆盖率为83.6%, 粒子分散均匀, 稳定性增强可长期保存; 同步散射光谱变化和发射光谱中分频、差频和倍频峰的存在证明, 金纳米粒子组装前后均具有非线性光学特性.     

自组装膜上细胞色素c的电化学石英晶体微天平实时表征和定量检测

采用电化学石英晶体微天平(EQCM)实时表征和定量检测细胞色素c(Cytc).在压电石英晶振表面上自组装巯基十一酸(MUA)单层膜,以盐酸1-乙基-3-(3-二甲基氨基丙基)碳二亚胺(EDC)和N-羟基琥珀酰亚胺(NHS)活化羧基,将Cytc共价固化到电极表面.EQCM实时监测了MUA的自组装和Cytc的固化过程,测定了二者在电极表面的覆盖度和Cytc的固化量.结果表明,Cytc在0.03～3.00μmol/L浓度范围内呈线性变化,检测限可达到1.19×10^-9mol/L.     

Macromolecular dimensions and mechanical properties of monolayer films of Sonorean mesquite gum

Mesquite gum sourced from Prosopis velutina trees and gum arabic (Acacia spp.) were characterized using light scattering and Langmuir isotherms. Both gum materials were fractionated by hydrophobic interaction chromatography, yielding four fractions for both gums: FI, FIIa, FIIb and FIII in mesquite gum and FI, FII, FIIIa and FIIIb in gum arabic. In mesquite gum, the obtained fractions had different protein content (7.18-38.60 wt.-%) and macromolecular dimensions (M approximately 3.89 x 10(5)-8.06 x 10(5) g.mol(-1), RG approximately 48.83-71.11 nm, RH approximately 9.61-24.06 nm) and architecture given by the structure factor (RG/RH ratio approximately 2.96-5.27). The mechanical properties of Langmuir monolayers at the air-water interface were very different on each gum and their fractions. For mesquite gum, the most active species at the interface were those comprised in Fractions IIa and IIb and III, while Fraction I the pi/A isotherm lied below that of the whole gum. In gum arabic only Fraction III developed greater surface pressure at the same surface per milligram of material than whole gum. This is rationalized in terms of structural differences in both materials. Mesquite gum tertiary structure seems to fit best with an elongated polydisperse macrocoil in agreement with the "twisted hairy rope" proposal for arabinogalactan proteoglycans.     

Flexible NO2-Functionalized N-Heterocyclic Carbene Monolayers on Au (111) Surface

The formation of flexible self-assembled monolayers (SAMs) in which an external trigger modifies the geometry of surface-anchored molecules is essential for the development of functional materials with tunable properties. In this work, it is demonstrated that NO₂-functionalized N-heterocyclic carbene molecules (NHCs), which were anchored on Au (111) surface, change their orientation from tilted into flat-lying position following trigger-induced reduction of their nitro groups. DFT calculations identified that the energetic driving force for reorientation was the lower steric hindrance and stronger interactions between the chemically reduced NHCs and the Au surface. The trigger-induced changes in the NHCs′ anchoring geometry and chemical functionality modified the work function and the hydrophobicity of the NHC-decorated Au surface, demonstrating the impact of a chemically tunable NHC-based SAM on the properties of the metal surface.     

Iron(II) complex of 2-(1H-pyrazol-1-yl)pyridine-4-carboxylic acid (ppCOOH) suitable for surface deposition

Abstract

The synthesis, structural and magnetic characterization of the tris iron(II) complex of 2-(1H-pyrazol-1-yl)pyridine-4-carboxylic acid (ppCOOH) ligand are reported in [Fe(ppCOOH)₃](ClO₄)₂·0.5H₂O·2EtOH. Single crystal structure and magnetic characterization of the bulk compound show that the low-spin state is dominant from 2 to 400 K. ESI-MS and UV–Vis spectroscopy experiments indicate that acetonitrile solutions of this complex are stable with time. ESI-MS confirms the presence of the tris complex in solution. This complex can be deposited onto SiO₂ surfaces due to the presence of carboxylic acid groups by immersing the substrates into acetonitrile solutions of the complex. XPS spectra of the deposited complex are similar to those of the bulk sample. AFM images show a slight increase in roughness with respect to the naked substrate and the absence of aggregates. These results are consistent with the formation of a monolayer of the complex on the surface.     

Platinum monolayers stabilized on dealloyed AuCu core-shell nanoparticles for improved activity and stability on methanol oxidation reaction

Deposition of platinum(Pt)monolayers(PtML)on Au substrate represents a robust strategy to maximally utilize the Pt atoms and meanwhile achieve high catalytic activity towards methanol oxidation reaction for direct methanol fuel cells owing to a substrate-induced tensile strain effect.However,recent studies showed that Pt(ML)on Au substrate are far from perfect smooth monoatomic layer,but actually exhibited three-dimensional nanoclusters.Moreover,the Pt(ML)suffered from severe structural instability and thus activity degradation during long-term electrocatalysis.To regulate the growth of Pt(ML)Au surface and also to improve its structural stability,we exploit dealloyed AuCu core-shell nanoparticles as a new substrate for depositing Pt(ML).By using high-resolution scanning transmission electron microscopy and energy dispersive X-ray elemental mapping combined with electrochemical characte rizations,we reveal that the dealloyed AuCu core-shell nanoparticles can effectively promote the deposition of Pt(ML)closer to a smooth monolayer structure,thus leading to a higher utilization efficiency of Pt and higher intrinsic activity towards methanol oxidation compared to those on pure Au nanoparticles.Moreover,the Pt(ML)deposited on the AuCu core-shell NPs showed substa ntially enhanced stability compared to those on pure Au NPs during long-term electrocatalysis over several hours,during which segregation of Cu to the Au/Pt interface was revealed and suggested to play an important role in stabilizing the Pt(ML)catalysts.     

A Robust Au−C≡C Functionalized Surface: Toward Real-Time Mapping and Accurate Quantification of Fe2+ in the Brains of Live AD Mouse Models

Described here is that Au−C≡C bonds showed the highest stability under biological conditions, with abundant thiols, and the best electrochemical performance compared to Au−S and Au−Se bonds. The new finding was also confirmed by theorical calculations. Based on this finding, a specific molecule for recognition of Fe²⁺ was designed and synthesized, and used to create a selective and accurate electrochemical sensor for the quantification of Fe²⁺. The present ratiometric strategy demonstrates high spatial resolution for real-time tracking of Fe²⁺ in a dynamic range of 0.2–120 μM. Finally, a microelectrode array with good biocompatibility was applied in imaging and biosensing of Fe²⁺ in the different regions of live mouse brains. Using this tool, it was discovered that the uptake of extracellular Fe²⁺ into the cortex and striatum was largely mediated by cyclic adenosine monophosphate (cAMP) through the CREB-related pathway in the brain of a mouse with Alzheimer's disease.