Bridging photochemistry and photomechanics with NMR crystallography: the molecular basis for the macroscopic expansion of an anthracene ester nanorod

Crystals composed of photoreactive molecules represent a new class of photomechanical materials with the potential to generate large forces on fast timescales. An example is the photodimerization of 9-tert-butyl-anthracene ester (9TBAE) in molecular crystal nanorods that leads to an average elongation of 8%. Previous work showed that this expansion results from the formation of a metastable crystalline product. In this article, it is shown how a novel combination of ensemble oriented-crystal solid-state NMR, X-ray diffraction, and first principles computational modeling can be used to establish the absolute unit cell orientations relative to the shape change, revealing the atomic-resolution mechanism for the photomechanical response and enabling the construction of a model that predicts an elongation of 7.4%, in good agreement with the experimental value. According to this model, the nanorod expansion does not result from an overall change in the volume of the unit cell, but rather from an anisotropic rearrangement of the molecular contents. The ability to understand quantitatively how molecular-level photochemistry generates mechanical displacements allows us to predict that the expansion could be tuned from +9% to −9.5% by controlling the initial orientation of the unit cell with respect to the nanorod axis. This application of NMR-assisted crystallography provides a new tool capable of tying the atomic-level structural rearrangement of the reacting molecular species to the mechanical response of a nanostructured sample.

NMR crystallography establishes absolute unit-cell orientations relative to the shape change, revealing the atomic-resolution mechanism for the nanorod''s photomechanical response.     

Protein adsorption on oligo(ethylene glycol)-terminated alkanethiolate self-assembled monolayers: The molecular basis for nonfouling behavior

A study of protein resistance of oligo(ethylene glycol) (OEG), HS(CH2)11(OCH2CH2)nOH (n = 2, 4, and 6), self-assembled monolayers (SAMs) on Au(111) surfaces is presented here. Hydroxyl-terminated OEG-SAMs are chosen to avoid the hydrophobic effect observed with methyl-terminated OEG-SAMs, particularly at high packing densities. The structure of the OEG-SAM surfaces is controlled by adjusting the assembly solvent. These SAMs were characterized by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Protein adsorption on these surfaces was investigated by surface plasmon resonance (SPR). OEG-SAMs assembled from mixed ethanol and water solutions show higher packing density on gold than those from pure ethanol solution. For EG2OH- and EG4OH-SAMs, proteins (i.e., fibrinogen and lysozyme) adsorb more on the densely packed SAMs prepared from mixed ethanol and water solutions, while EG6OH-SAMs generally resist protein adsorption regardless of the assembly solvent used.     

基于静电吸附甲苯胺蓝和纳米金固定过氧化物酶生物传感器的研究

以玻碳电极为基底,电聚合邻氨基苯甲酸(ABA),使其形成带负电的界面,通过分子间静电作用力,自组装一层带正电荷的电子媒介体甲苯胺蓝(TB),再通过媒介体的氨基吸附纳米金,最后静电吸附固定辣根过氧化物酶制备出H2O2传感器。探讨了膜聚合时间、媒介体组装时间、pH、温度、工作电位对电极响应的影响。在优化的实验条件下,该传感器对H2O2电流响应与其浓度为1.5×10-5~1.3×10-3mol/L范围内呈线性关系;检出限为5.6×10-6mol/L。此外,该传感器具有较低的工作电位,能有效地消除抗坏血酸等的干扰。     

Insulin-positive ductal cells do not migrate into preexisting islets during pregnancy

The adult pancreatic ductal system was suggested to harbor facultative beta-cell progenitors similar to the embryonic pancreas, and the appearance of insulin-positive duct cells has been used as evidence for natural duct-to-beta-cell reprogramming. Nevertheless, the phenotype and fate of these insulin-positive cells in ducts have not been determined. Here, we used a cell-tagging dye, CFDA-SE, to permanently label pancreatic duct cells through an intraductal infusion technique. Representing a time when significant increases in beta-cell mass occur, pregnancy was later induced in these CFDA-SE-treated mice to assess the phenotype and fate of the insulin-positive cells in ducts. We found that a small portion of CFDA-SE-labeled duct cells became insulin-positive, but they were not fully functional beta-cells based on the in vitro glucose response and the expression levels of key beta-cell genes. Moreover, these insulin-positive cells in ducts expressed significantly lower levels of genes associated with extracellular matrix degradation and cell migration, which may thus prevent their budding and migration into preexisting islets. A similar conclusion was reached through analysis of the Gene Expression Omnibus database for both mice and humans. Together, our data suggest that the contribution of duct cells to normal beta-cells in adult islets is minimal at best.Subject terms: Transdifferentiation, Gestational diabetes     

Characterization of carbon-supported AuPt nanoparticles for electrocatalytic methanol oxidation reaction

In view of the recent finding that the bimetallic AuPt nanoparticles prepared by molecular-capping-based colloidal synthesis and subsequent assembly on carbon black support and thermal activation treatment exhibit alloy properties, which is in sharp contrast to the bimetallic miscibility gap known for the bulk counterparts in a wide composition range, there is a clear need to assess the electrocatalytic properties of the catalysts prepared with different bimetallic composition and different thermal treatment temperatures. This paper reports recent results of such an investigation of the electrocatalytic methanol oxidation reaction (MOR) activities of the carbon-supported AuPt nanoparticle catalysts with different bimetallic composition and thermal treatment temperatures. Au(m)Pt(100)(-)(m) nanoparticles of 2-3 nm core sizes with different atomic compositions ranging from 10% to 90% Au (m = 10 approximately 90) have been synthesized by controlling the feeding of the metal precursors used in the synthesis. The electrocatalytic MOR activities of the carbon-supported AuPt bimetallic catalysts were characterized in alkaline electrolytes. The catalysts with 65% to 85% Au and treated at 500 degrees C were found to exhibit maximum electrocatalytic activities in the alkaline electrolytes. The findings, together with a comparison with some well-documented catalysts as well as recent experimental and theoretical modeling results, have revealed important insights into the participation of CO(ad) and OH(ad) on Au sites in the catalytic reaction of Pt in the AuPt alloys with approximately 75% Au. The insights are useful for understanding the correlation of the bifunctional electrocatalytic activity of the bimetallic nanoparticle catalysts with the bimetallic composition and the thermal treatment temperatures.     

Grafting of nanoporous alumina membranes and films with organic acids

In this study, direct surface grafting of nanoporous alumina membranes and glass‐supported alumina films was carried out with three different fluorinated organic acids: trifluoroacetic acid, perfluoropentanoic acid and 2,3,4,5,6‐pentafluorobenzoic acid. Elemental surface composition and chemical environment of alumina were investigated using X‐ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). Alumina surfaces grafted with fluoro‐organic acids exhibited increased hydrophobic properties compared to ungrafted surfaces when measured using goniometry and atomic force microscopy (AFM). This work describes the evidence for surface chemical modification of alumina using direct reaction with organic acids. An AFM study of the adsorption of the immunoglobulin G (IgG) molecules on the fluoro‐organic‐acid‐grafted surfaces is reported. The results show that an ordered arrangement of immunoglobulin G structures with in‐filling of pores could be achieved only on the more hydrophobic fluoro‐organic‐acid‐grafted alumina membranes. Copyright © 2007 John Wiley & Sons, Ltd.     

A new label-free amperometric immunosenor for rubella vaccine

A novel label-free amperometric immunosensor for the detection of rubella vaccine was developed by immobilizing anti-rubella serum on bilayer nano-Au/polymerized o-phenylenediamine film with electrodeposited Prussian Blue (PB) as an electrode transfer mediator on the platinum electrode. The redox reactions of PB as a probe on the platinum surface were blocked due to the binding of the antibody to the antigen, which was investigated by cyclic voltammetry. Therefore, the interaction of the antibody with various concentrations of antigen could be detected by measurements of amperometric response in PBS, and the amperometric response on the surface of the modified electrode was inversely proportional to the concentration of rubella vaccine in the sample. The immunosensor showed a specific response to rubella vaccine in the range 8.1×10^–8–8.0×10^–6 lgCCID₅₀/ml (cell culture infectious dose) and a detection limit of 4.010^–8 lgCCID₅₀/ml at a signal-to-noise ratio of 3. To summarize, the present work provides a low-cost, fast response time, highly sensitive and easy-to-prepare method for the determination of antigen in biological products.     

Monodispersed core-shell Fe3O4@Au nanoparticles

The ability to synthesize and assemble monodispersed core-shell nanoparticles is important for exploring the unique properties of nanoscale core, shell, or their combinations in technological applications. This paper describes findings of an investigation of the synthesis and assembly of core (Fe(3)O(4))-shell (Au) nanoparticles with high monodispersity. Fe(3)O(4) nanoparticles of selected sizes were used as seeding materials for the reduction of gold precursors to produce gold-coated Fe(3)O(4) nanoparticles (Fe(3)O(4)@Au). Experimental data from both physical and chemical determinations of the changes in particle size, surface plasmon resonance optical band, core-shell composition, surface reactivity, and magnetic properties have confirmed the formation of the core-shell nanostructure. The interfacial reactivity of a combination of ligand-exchanging and interparticle cross-linking was exploited for molecularly mediated thin film assembly of the core-shell nanoparticles. The SQUID data reveal a decrease in magnetization and blocking temperature and an increase in coercivity for Fe(3)O(4)@Au, reflecting the decreased coupling of the magnetic moments as a result of the increased interparticle spacing by both gold and capping shells. Implications of the findings to the design of interfacial reactivities via core-shell nanocomposites for magnetic, catalytic, and biological applications are also briefly discussed.     

亚波长介质光栅导模共振研究

从平板波导的本征值方程出发,导出弱调制介质光栅共振位置的表达式,其预测结果与利用严格的耦合波理论所得值一致.对正入射时导模共振产生双反射峰现象进行解释,并就导模共振对入射角和光栅周期敏感性的成因进行了探讨.从薄膜的特征矩阵方程出发,在理论上分析了利用导模共振获得性能良好的反射滤光片的途径.