Mild and Efficient Procedure for Michael Addition of N-Heterocycles to α,β-Unsaturated Compounds Using Anhydrous K3PO4 as Catalyst

Imidazole, 1,2,4-triazole, indole, and benzotriazole undergo conjugate additions with α, β-unsaturated carbonyl compounds in the presence of anhydrous potassium phosphate at ambient temperature to afford the corresponding Michael adducts in excellent yields.     

Robust self-assembled octadecylphosphonic acid monolayers on a mica substrate

As determined by scratch tests, self-assembled monolayers (SAMs) of octadecylphosphonic acid (OPA) on a muscovite mica substrate were found to be mechanically robust and to serve as a lubricant to protect the underlying mica substrate. For comparison purposes, three polymer films were subjected to scratch tests under the same conditions. The scratch tests were conducted using a diamond-tipped stylus, and the resultant scratches were examined using atomic force microscopy. The excellent mechanical strength of OPA SAMs is supported by analysis with time-of-flight secondary ion mass spectrometry, which suggests that the headgroup of the OPA is strongly bonded to the substrate atoms. The molecular lubrication provided by OPA SAMs suggests that the interaction between the headgroup and the substrate is sufficiently strong to endure significant shear force and that the hydrocarbon chains are able to dissipate shear energy.     

Electroreduction of α-glucose on CNT/graphite electrode modified by Zn and Zn–Fe alloy

Electroreduction of -glucose to form sorbitol on Zn/CNTs and Zn alloy/CNTs electrodes has been investigated in this paper. Carbon nanotubes (CNTs) used in this paper are grown directly on graphite disks by chemical vapor deposition. Zn and Zn alloy are electrodeposited on the activated CNTs/graphite electrode by pulse galvanostatic method. The micrographs of Zn/CNTs and Zn alloy/CNTs electrodes are characterized by scanning electron microscopy. The results show that the current efficiency of -glucose reduction on CNTs electrodes is much better than that on flat Zn electrodes. The order of the current efficiency on different electrodes is as follows: Zn/CNT (0.58) Zn–Fe/CNT (0.57)>Zn–Ni/CNT (0.43) Zn/graphite (0.42)>Zn (0.40). It indicates that CNTs have good potential application in electrosynthesis. Additionally, effects of some operating parameters, such as pH, temperature and -glucose concentration, on the current efficiency of -glucose reduction are also discussed.     

De novo sequencing of tryptic peptides sulfonated by 4-sulfophenyl isothiocyanate for unambiguous protein identification using post-source decay matrix-assisted laser desorption/ionization mass spectrometry

A simple method of solid-phase derivatization and sequencing of tryptic peptides has been developed for rapid and unambiguous identification of spots on two-dimensional gels using post-source decay (PSD) matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. The proteolytic digests of proteins are chemically modified by 4-sulfophenyl isothiocyanate. The derivatization reaction introduces a negative sulfonic acid group at the N-terminus of a peptide, which can increase the efficiency of PSD fragmentation and enable the selective detection of only a single series of fragment ions (y-ions). This chemically assisted method avoids the limitation of high background normally observed in MALDI-PSD spectra, and makes the spectra easier to interpret and facilitates de novo sequencing of internal fragment. The modification reaction is conducted in C(18) microZipTips to decrease the background and to enhance the signal/noise. Derivatization procedures were optimized for MALDI-PSD to increase the structural information and to obtain a complete peptide sequence even in critical cases. The MALDI-PSD mass spectra of two model peptides and their sulfonated derivatives are compared. For some proteins unambiguous identification could be achieved by MALDI-PSD sequencing of derivatized peptides obtained from in-gel digests of phosphorylase B and proteins of hepatic satellite cells (HSC).     

Biomass Composition, Lipid Characterization, and Metabolic Profile Analysis of the Fed-Batch Fermentation Process of Two Different Docosahexanoic Acid Producing Schizochytrium sp. Strains

Growth and fermentation characteristics, biomass composition, lipid characterization and metabolic profiling analysis of two different Schizochytrium sp. strains, the original strain and the industrial adaptive strain, were investigated in the fed-batch fermentation process. The final cell biomass, total lipids content, docosahexanoic acid (DHA) content and DHA productivity of the adaptive strain were much higher than those of the original strain. The metabolic distinctions which extensively existed between these two strains were revealed by the score plot of principal component analysis. In addition, potential biomarkers responsible for discriminating different strains were identified as myo-inositol, histidine, alanine, asparagine, cysteine, and oxalic acid. These findings provided new insights into the industrial strain screening and further improvement of DHA production by Schizochytrium sp.     

Removal of uranium(VI) from aqueous solutions by carboxyl-rich hydrothermal carbon spheres through low-temperature heat treatment in air

Carboxyl-rich hydrothermal carbon spheres were prepared by simply heating pristine hydrothermal carbon spheres (HCSs) at lower temperature in air, and the textural properties were characterized using Boehm titrations, scanning electron microscopy, Fourier transform infrared spectrometer (FT-IR) and elemental-analysis. The result of Boehm titrations indicated that the content of carboxyl groups on HCSs increased significantly from 0.53 to 3.81 mmol/g after heat-treatment at 300 °C, which was also confirmed by FT-IR and EA qualitatively. The ability of heat-treated HCSs has been explored for the removal and recovery of uranium from aqueous solutions, and the influences of different experimental parameters, such as heat-treatment temperature, contact time and ionic strength, on adsorption were investigated. The U(VI) sorption capacity of HCSs increased from 55.0 to 179.95 mg/g after heat-treatment at 300 °C for 5 h. Selective adsorption studies showed that the heat-treated HCSs could selectively remove U(VI), and the selectivity coefficients were improved after heat-treatment in the presence of co-existing ions, Na(I), Ni(II), Sr(II), Mn(II), Mg(II) and Zn(II). The adsorbent HCSs could be effectively regenerated by 0.05 mol/L HCl solution for the removal and recovery of U(VI). Complete removal (99.0 %) of U(VI) from 1.0 L industry wastewater containing 15.0 mg U(VI) ions was possible with 5.0 g heat-treated HCSs. In addition, a reaction mechanism for newly generating carboxyl groups on pristine HCSs surface during heat-treatment process and uranyl ion interaction with carboxyl-rich hydrothermal carbon spheres were also supposed.     

Synthesis of New Spiropyrans With a Polyaromatic or Heteroaromatic Pendant and Their Photochromic Bedhaviors

A series of spiropyrans with a polyaromatic or heteroaromatic pendant was synthesized conveniently.Their photochromic behaviors were investigated with the aid of absorption spectral measurements.The results indicated that the compounds with the same parent spiropyran but different aromatic pendant show significantly different photochromic properties.This may be due to the π-π orbital interaction between the polyaromatic pendant and the open photomerocyanine form of spiropyran.The results obtained are very useful in the molecule design area.     

Flow-injection analysis based on a membrane separation module and a bulk acoustic wave impedance sensor – determination of the volatile acidity of fermentation products

A novel flow-injection analysis (FIA) system has been developed for the rapid determination of the volatile acidity of some fermentation products like vinegars and juices. The proposed method is based on the diffusion of volatile acids, mainly acetic acid, across a PTFE gas-permeable membrane from an acid stream into an alkaline stream, and the acids trapped in the acceptor solution are determined online by a bulk acoustic wave impedance sensor based on changes in the conductivity of the solution. It exhibited a linear frequency response up to 10 mmol · L^–1 acetic acid with a detection limit of 50 μmol · L^–1, and the precision was better than 1% (RSD) at a through-put of 72 h^–1. The effects of operating voltage for the detector, cell constant of the electrode, composition of acceptor stream, flow rates and temperature on the FIA performance were also investigated. Received: 2 June 1997 / Revised: 7 July 1997 / Accepted: 12 July 1997     

Chemical analysis and cellular imaging with quantum dots

Quantum dots are tiny light-emitting particles on the nanometer scale. They are emerging as a new class of biological labels with properties and applications that are not available with traditional organic dyes and fluorescent proteins. Their novel properties such as improved brightness, resistance against photobleaching, and multicolor light emission, have opened new possibilities for ultrasensitive chemical analysis and cellular imaging. In this Research Highlight article , we discuss the unique optical properties of semiconductor quantum dots, surface chemistry and bioconjugation, current applications in bioanalytical chemistry and cell biology, and future research directions.