Enzymatic reaction of the immobilized enzyme on porous silicon studied by matrix-assisted laser desorption/ionization-time of flight-mass spectrometry

Desorption/ionization on silicon mass spectrometry (DIOS-MS) is a matrix-free technique that allows for the direct desorption/ionization of low-molecular-weight compounds with little or no fragmentation of analytes. This technique has a relatively high tolerance for contaminants commonly found in biological samples. DIOS-MS has been applied to determine the activity of immobilized enzymes on the porous silicon surface. Enzyme activities were also monitored with the addition of a competitive inhibitor in the substrate solution. It is demonstrated that this method can be applied to the screening of enzyme inhibitors. Furthermore, a method for peptide mapping analysis by in situ digestion of proteins on the porous silicon surface modified by trypsin, combined with matrix-assisted laser desorption/ionization-time of flight-MS has been developed.     

Reversible formation of DNA G-quadruplex hairpin dimers from stilbenediether conjugates

Rapid and reversible G-quadruplex hairpin dimer formation is observed for bis(oligonucleotide) conjugates possessing stilbenediether (Sd) linkers connecting two short poly(G) sequences.     

Orientation control of fluorescence resonance energy transfer using DNA as a helical scaffold

The efficiency of fluorescence resonance energy transfer (FRET) between two chromophores positioned at opposite ends of DNA base pair domains has been investigated. The base pair domain serves as a helical scaffold which defines both the distance between chromophores and the dihedral angle between their electronic transition dipole moments, each incremental base pair increasing the distance and stepping the dihedral angle. Fluorescence quantum yields and lifetimes have been determined for both the donor and acceptor chromophores. The experimental data are found to be in excellent accord with an oriented dipole model, rather than with the averaged dipole model conventionally assumed for FRET.     

含1,2,3-三唑环的α,γ-二酮衍生物的合成研究

以对氯氯苄为原料,经取代、1,3-偶极环加成和缩合反应得到含1,2,3-三唑环的α,γ-二酮衍生物,其结构经1H NMR、13C NMR以及MS确证。研究表明,该α,γ-二酮化合物存在酮醇异构现象,在溶液中其酮醇异构体比例近似为1∶8。     

Surface modulated hierarchical graphene film via sulfur and phosphorus dual-doping for high performance flexible supercapacitors

The steam-assistant heteroatoms of sulfur and phosphorus dual-doped graphene film fabricated via an ice-template and thermal-activation approach demonstrates an excellent pseudocapacitive behavior in flexible electrochemical capacitors.     

LC‐MS/MS determination of 1‐O‐acetylbritannilactone in rat plasma and its application to a preclinical pharmacokinetic study

A novel, rapid and sensitive LC‐MS/MS method for the determination of 1‐O‐Acetylbritannilactone (ABL), a sesquiterpene lactone abundant in Inula britannica, was developed and validated using heteroclitin D as internal standard. Separation was achieved on a reversed phase Hypersil Gold C₁₈ column (50 × 4.6 mm, i.d., 3.0 µm) using isocratic elution with methanol–5 mM ammonium acetate buffer aqueous solution (80:20, v/v) at a flow rate of 0.4 mL/min. Calibration curve was linear (r > 0.99) in a concentration range of 1.60–800 ng/mL with the lower limit of quantification of 1.60 ng/mL. Intra‐ and inter‐day accuracy and precision were validated by relative error (RE) and relative standard deviation (RSD) values, respectively, which were both less than ±15%. The validated method has been successfully applied to a pharmacokinetic study of ABL in rats. The elimination half‐lives were 0.412 ± 0.068, 0.415 ± 0.092 and 0.453 ± 0.071 h after a single intravenous administration of 0.14, 0.42, and 1.26 mg/kg ABL, respectively. The area under the plasma concentration–time curve from time zero to the last quantifiable time point and from time zero to infinity and the plasma concentrations at 2 min were linearly related to the doses tested. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis of macrocyclic ligands incorporating sulfur and furan subunits

Abstract

Polyammonium macrocycles containing sulfur and furan units in the macrocyclic ring have been synthesized and studied for ATPase activity. The synthetic methodology involved using tosyl protection for the amines and the formation of macrocyclic Lactams, followed by reduction using borane in THF. Deprotection of the tosylated forms of the macrocycle was accomplished using sodium in butanol for the furan macrocycles, and HBr in HOAc for the sulfur containing macrocycle. The macrocycles were found to be poor catalysts for ATP hydrolysis compared to other similar polyammonium macrocycles.     

肉豆蔻酸单萜醇酯对布南色林经皮透过的影响

本文以环状单萜醇α-萜品醇、L-薄荷醇及链状单萜醇香叶醇、香茅醇为先导化合物,采用酰氯酯化法合成肉豆蔻酸α-萜品醇酯(TER-C14)、肉豆蔻酸-L-薄荷醇酯(MEN-C14)、肉豆蔻酸香叶醇酯(GER-C14)和肉豆蔻酸香茅醇酯(CIT-C14),并考察单萜醇及其肉豆蔻酯作为促透剂对布南色林(Blo)的促透效果。通过体外经皮渗透实验、体外释放实验和分子模拟技术初步探究单萜醇及其肉豆蔻酯的促透机制。结果显示,当GER-C14或CIT-C14为促透剂时,均有显著的促透效果(P<0.05),并且24h经皮累积透过量是空白组的4.84倍和4.45倍。促透机制为肉豆蔻酸单萜醇酯破坏药物与神经酰胺之间的氢键相互作用,增加脂质迁移率和药物的自由能,从而促进药物的渗透。肉豆蔻酸单萜醇酯有望作为新型促透剂在经皮给药系统中广泛应用。     

Conformational stability and vibrational study of phenylacetyl chloride

The Fourier transform infrared spectroscopy and Fourier transform Raman spectra of phenylacetyl chloride were recorded and analyzed in the range 3500–400 and 3500–200 cm^?1 at room temperature, respectively. In order to obtain the structural information and conformational stabilities, a potential energy surface scan for internal rotation was carried out at the B3LYP/6‐31G(d) level. The potential energy surface reveals that the title compound has two minimal conformers (A and B). The optimized geometries, structural parameters, stabilities, energies, thermodynamic parameters, vibrational wavenumbers, infrared intensities, and Raman activities for the two conformers (A and B) have been obtained by employing B3LYP and MP2 calculations with 6‐311++G (d, p) basis sets. The conformational energy difference between A and B is very small, indicating that the B conformer coexists with the A conformer. The detailed vibrational assignments of vibrational spectra of each conformer have been made on the basis of the potential energy distributions analysis. The highest occupied molecular orbital –lowest unoccupied molecular orbital energy gap and molecular electrostatic potential of the two conformers have been also calculated for comparison of their chemical activities. Copyright © 2015 John Wiley & Sons, Ltd.