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     

Optimization of the abnormal Beckmann rearrangement: application to steroid 17-oximes

A novel and practical procedure was developed for the abnormal Beckmann rearrangement of steroid 17-oximes. Treatment of the 17-oximes with TFA/CH(OMe)(3) in boiling THF for 2 h gives the corresponding 13,17-seco alkene nitrile products in unprecedented high yields (70-92%). Since the alkene nitriles can be subsequently converted into 18-norsteroids, this general method provides a highly efficient route to these biologically important compounds and, by extension, to other structurally related natural products.     

Synthesis and Characterization of Ag2S Nanocrystals in Hyperbranched Polyurethane at Room Temperature

Ag₂S nanoparticles in hyperbranched polyurethane matrix were prepared through the in situ reaction with thioacetamide as the sulfur source at room temperature. Transmission electron microscopic analysis revealed a uniform spherical shape for Ag₂S nanoparticles, with an average size of about 4-10 nm and a narrow size distribution. X-ray powder diffraction and UV-vis spectroscopy were also used to characterize the obtained nanoparticles     

Synthesis, crystal structure and magnetic property of the novel dinuclear nickel(II) complex with 4-(p-methoxyphenyl)-3,5-bis(pyridine-2-yl)-1,2,4-triazole

A novel dinuclear nickel(II) complex, [Ni₂(MOBPT)₂Cl₂(H₂O)₂]Cl₂ · 7H₂O (MOBPT = 4-(p-methoxyphenyl) −3,5-bis(pyridine-2-yl)-1,2,4-triazole), has been synthesized and characterized by elemental analysis, IR and single crystal X-ray diffraction methods. The crystal structure determination shows that the dinuclear Ni₂N₈ unit is almost planer in which each Ni^II ion is coordinated by four nitrogen atoms from MOBPT equatorially and a water molecule and a chloride ion axially in a distorted octahedral geometry. Magnetic measurements reveal a relatively weak antiferromagnetic exchange in the complex.     

氯化血红素催化新型荧光反应测定葡萄糖的研究

本文用流动注射分析了研究了过氧化物模拟酶催化过氧新型荧光底物（Ｎ，Ｎ－二氰甲基邻苯二胺，ＤＣＭＯＰＡ）的最优条件。结果表明，该系统可用于定量测定氧化氢及催化氯化血红素的浓度。     

High-voltage capillary zone electrophoresis of red blood cells

The high-voltage wide-bore capillary zone electrophoresis of red blood cells was investigated. The reproducibility of the retention time (electrophoretic mobility) is excellent and the differentiation among various species is good. The peaks in the electropherogram describe the distribution of the size and/or surface charge of the cells and are therefore broad. The relationship between the peak height and the number of cells injected is good, with linear correlation coefficients better than 0.98. Details of the preparation of cell suspensions and support electrolytes are given, which is essential for obtaining reproducible results. The inner surface of FEP capillary tubing is degraded by the application of high voltage and a pause is necessary between successive experiments if good and reproducible peak shapes are to be obtained. The length of the pause increases with the number of experiments made, and finally the tubing becomes useless. Inspection of the inner surface by X-ray photoelectron spectroscopy showed the breakdown of CHF bonds, but the actual mechanism is not known.     

Hydrodynamic simulation of cell docking in microfluidic channels with different dam structures

The immobilization of biological cells in micro-devices requires high efficiency and easy control while maintaining cell viability. One approach for cell immobilization is to utilize constriction structures such as dams to trap cells in microfluidics. In this paper, we present a comprehensive hydrodynamic analysis of two different types of constriction structures for cell immobilization: dams either in perpendicular or in parallel to the main flow route. Various structural models and experimental conditions were compared for cell docking and alignment, and the pressure and velocity profiles of the flow in the micro-channels and the hydrodynamic force and shear stress on the docked cells were calculated based on fluid dynamic theory and numerical simulation. The effects of the dam structures and cell docking on the flow properties, the transportation efficiency, and the induced stress on the docked cells were analyzed. Improved hydraulic pressure profiles in the auxiliary inlets were discussed for the modulation of the flow characteristics and attenuation of hydrodynamic forces exerted on the cells. Furthermore, a new design combining the advantages of perpendicular and parallel dam structures was proposed for cell-based microfluidics.     

Characteristic sequences for DNA primary sequence

A DNA sequence can be identified with a word over an alphabet N = [A, C, G, T]. Characteristic sequences of a DNA sequence are given in term of classifications of bases of nucleic acids. Using the characteristic sequences, we construct a set of 2 x 2 matrices to represent DNA primary sequences, which are based on counting of the frequency of occurrence of all (0,1) triplets of characteristic sequences. Furthermore, the leading eigenvalues of these matrices are computed and considered as invariants for the DNA primary sequences. Similarity and dissimilarity analysis based on the characteristic sequences are given for eight exon-1 genes of beta-globin about eight species.     

Porous nanocomposites of zirconium dioxide and silicate

Highly porous nanocomposites of zirconium dioxide and silicate are synthesised in an aqueous system from an inorganic salt of zirconium; the nanacomposites, with tailorable pore structures, exhibit superior performance as catalyst supports.     

DFT study on the geometric, electronic structure and Raman spectra of 5,15-diphenylporphine

The ground state geometric, electronic structure and Raman spectra of 5,15-diphenylporphine (H(2)DPP) have been studied using B3LYP/6-31G(d) method and compared with that of well-studied free base porphine (H(2)P) and meso-tetraphenylporphine (H(2)TPP). Calculation shows that 5,15-substitution causes remarkable in-plane distortion, whereas the resulting out-of-plane distortion is negligible. The calculated electronic structure of H(2)DPP is consistent with the absorption spectra compared with H(2)P and H(2)TPP. The calculated vibrational frequencies of H(2)DPP scaled with a single factor of 0.971 agree well with experimental data (the rms error is 8.0 cm(-1)). The assignment of experimental Raman bands of H(2)DPP was discussed on the basis of theoretical calculation and the comparison with that of H(2)P and H(2)TPP. The splitting of some vibrational modes involving the motion of C(m) atom, such as nu(1), nu(8), and nu(10), was observed and was attributed to the diversification of the environment around C(m) atoms. As the shift of absorption peaks, the shift of some structure-sensitive Raman bands of H(2)DPP form that of H(2)TPP and H(2)P was attributed to the in-plane nuclear reorganization (IPNR) induced by phenyl-substitution, though the contribution of nonplanarity mechanism could not be excluded completely.