A self-assembling protein template for constrained synthesis and patterning of nanoparticle arrays

Self-assembling biomolecules that form highly ordered structures have attracted interest as potential alternatives to conventional lithographic processes for patterning materials. Here, we introduce a general technique for patterning nanoparticle arrays using two-dimensional crystals of genetically modified hollow protein structures called chaperonins. Constrained chemical synthesis of transition metal nanoparticles is initiated using templates functionalized with polyhistidine sequences. These nanoparticles are ordered into arrays because the template-driven synthesis is constrained by the nanoscale structure of the crystallized protein. We anticipate that this system may be used to pattern different classes of nanoparticles based on the growing library of sequences shown to specifically bind or direct the growth of materials.     

π -Type and σ -type cation- π complexes of atomic cations

MP2/6-31+G* calculations were performed on the cation- complexes of ethylene, cyclobutadiene and benzene with a number of atomic cations. It was found that except B⁺ all the atomic cations form -type cation- complexes with ethylene. On the other hand, with cyclobutadiene Li⁺, N⁺, Na⁺, P⁺ and K⁺ form -type complexes, whereas H⁺, F⁺, and Cl⁺ form covalent -type complexes. With benzene Li⁺, B⁺, Na⁺, Al⁺, and K⁺ form -type complexes whereas H⁺, F⁺, and Cl⁺ form -type complexes. It was concluded that the driving force to form the -type complex is chemical bonding, and that for metal cations to form -type complexes is non-covalent interaction.     

Potential-dependent reorientation of thiocyanate on Au electrodes

Thiocyanate (SCN) adsorption on an Au electrode is examined using surface-enhanced Raman scattering (SERS) measurements, along with detailed density functional theory (DFT) calculations. Both the calculation and the spectroscopic measurements show that three different geometries are adopted by SCN adsorption in the potential region studied (0.0 V 相似文献   

Micranoic acids A and B: two new octanortriterpenoids from Schisandra micrantha

Two novel octanortriterpenoids, micranoic acids A (1) and B (2), along with three known compounds, kadsuric acid (3), 3beta-hydroxy-lanost-9(11),24(25)-dien-26-oic acid (4) and schizandronic acid (5), were isolated from the leaves and stems of Schisandra micrantha. The structures of 1 and 2 were determined by 1D and 2D NMR spectroscopic analysis. Micranoic acids A and B represent a new group of triterpenes in which the entire C-17 side chain has lost. This is the first report of octanortriterpenoids isolated from the family Schisandraceae.     

Synthesis of [1,2-3H2]-polystyrene

The synthesis of [1,2-³H₂]-polystyrene consisted of a two step reaction. First catalytic tritium gas addition to phenylacetylene was used to prepare [1,2-³H₂]-styrene and then it was polymerized to [1,2-³H₂]-polystyrene in the present of an initiator.     

Self-gelatinizable copolymer immobilized glucose biosensor based on prussian blue modified graphite electrode

A novel poly(vinyl alcohol) grafting 4-vinylpyridine self-gelatinizable copolymer was adapted to immobilize glucose oxidase. The reduction of hydrogen peroxide (H2O2) was detected at a Prussian Blue (PB) modified graphite electrode. A stable and sensitive glucose amperometric biosensor is described. The copolymer is a good biocompatible polymer in which the glucose oxidase retains high activity. Moreover, the copolymer can adhere firmly to the inorganic PB membrane. The sensor showed an apparent Michaelis-Menten constant of 18 +/- 0.2 mM and a maximum current density of 1.14 microA cm-2 mM-1. The linear range is from 5 microM to 4.5 mM glucose and the detection limit is 0.5 microM glucose. The catalytic efficiency of PB for the reduction of H2O2 is higher than that for the oxidation of H2O2. Glucose concentrations in serum samples from healthy persons and diabetic patients were determined using the sensor. The results compared well with those provided by the hospital using a spectroscopy method.     

Prediction of retention indexes. III. Silylated derivatives of polar compounds.

Polar compounds containing hydroxyl, amino and carboxyl groups, singly or in combination, can be chromatographed after the polar functional groups are silylated. The silylated derivatives of acids, alcohols, amines, diols, amino alcohols, amino acids are shown to behave chromatographically as hydrocarbons, and their retention indexes can be readily predicted from their base values. The column difference, namely, the difference between the retention indexes of the analyte on polar and non-polar columns is minimal for the silylated derivatives in comparison to that observed for the underivatized analytes. This minimal column difference is attributed to the hydrocarbon-like chromatographic characteristics of the silylated derivatives. The retention indexes of the silyl derivatives appear to correlate with the atom number Z of the analyte.     

Spectroscopy of hydrothermal reactions, 19: pH and salt dependence of decarboxylation of α‐alanine at 280–330°C in an FT‐IR spectroscopy flow reactor

The spontaneous decarboxylation of 0.5 m aqueous α‐alanine solutions as a function of pH (1–9 at 320°C, where neutrality is approximately 6) was determined with a flow reactor at 280–330°C and 275 bar by FT‐IR spectroscopy. The kinetics for the cationic and anionic forms have not been previously reported. The rate constants for the cationic form [CH₃(NH₃⁺)CHCO₂H], the anionic form [CH₃(NH₂)CHCO₂^?], and the zwitterion form [CH₃(NH₃⁺)CHCO₂^?] were obtained and followed the first‐order rate law. The rate of decarboxylation of the zwitterion is three times greater than that of the cationic and anionic forms in the temperature and pH ranges of study. The corresponding Arrhenius parameters were determined and compared with previously reported data. The addition of KCl (1 and 2 m) at the natural pH of α‐alanine resulted in a reduction of the decarboxylation rate, suggesting that the transition state is less polar than the zwitterion and/or that the activity of the zwitterion has been reduced. The α‐alanine solution is therefore somewhat more robust in solutions of high ionic strength, such as seawater, than it is in pure water. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 271–277, 2002     

The neomycin biosynthetic gene cluster of Streptomyces fradiae NCIMB 8233: characterisation of an aminotransferase involved in the formation of 2-deoxystreptamine

The biosynthetic gene cluster of the 2-deoxystreptamine (DOS)-containing aminoglycoside antibiotic neomycin has been cloned for the first time by screening of a cosmid library of Streptomyces fradiae NCIMB 8233. Sequence analysis has identified 21 putative open reading frames (ORFs) in the neomycin gene cluster (neo) with significant protein sequence similarity to gene products involved in the biosynthesis of other DOS-containing aminoglycosides, namely butirosin (btr), gentamycin (gnt), tobramycin (tbm) and kanamycin (kan). Located at the 5'-end of the neo gene cluster is the previously-characterised neomycin phosphotransferase gene (apH). Three genes unique to the neo and btr clusters have been revealed by comparison of the neo cluster to btr, gnt, tbm and kan clusters. This suggests that these three genes may be involved in the transfer of a ribose moiety to the DOS ring during the antibiotic biosynthesis. The product of the neo-6 gene is characterised here as the L-glutamine : 2-deoxy-scyllo-inosose aminotransferase responsible for the first transamination in DOS biosynthesis, which supports the assignment of the gene cluster.     

Effect of PEG on the crystallization of PPDO/PEG blends

A new biodegradable polymer system, poly(p-dioxanone) (PPDO)/poly(ethylene glycol) (PEG) blend was prepared by a solvent casting method using chloroform as a co-solvent. The PPDO/PEG blends have different weight ratios of 95/5, 90/10, 80/20 and 70/30. Crystallization of homopolymers and blends were investigated by differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD). When 5% of PEG was blended, the crystallization exothermal peaks (T_c) of PPDO increased sharply and the crystallization exothermal peaks (T_c) of PEG decreased slightly compared with the homopolymers. The crystallization rates of both components increased, and caused greater relative crystallization degree (X_t%). But when the content of PEG was more than 5%, the crystalline behaviors of blends had no more significant changes accordingly. The melting points of each sample varied little over the entire composition range in this study. The nonisothermal crystallization of PPDO homopolymer and blend (PPDO/PEG = 70/30) were also studied by DSC. The crystallization began at a higher temperature when the cooling rates were slower. The nonisothermal crystallization kinetics of blends was analyzed by Ozawa equation. The results showed that the Ozawa equation failed to describe the whole crystallization of the blend, but Mo equation could depict the nonisothermal crystallization perfectly.