Fluorescence quenching study on the interaction of bases of nucleic acid with electron-accepting sensitizer and serum albumin containing electron-rich tryptophan residue

Static and dynamic fluorescence quenchings of electron-accepting sensitizers including positive charged heterocyclics and neutral cyanoaromatics by bases of nucleic acid (NB) have been investigated. It was found that NB could act as effective electron donors to quench the fluorescence of electron-accepting sensitizers. The quenchings by diffusion-controlled rate coincide well with the static and dynamic Stern-Volmer correlation. On the other hand, the diffusion-controlled fluorescence quenchings of the tryptophan (TRP) residue in the protein enzymes, HSA and BSA, by electron-accepting NB reveal that photochemical dual-damage of protein enzyme and thymine (THM) occur upon u.v.-irradiation, which is characteristic of excitation wavelength-dependence. Therefore, the results illustrate that the lesion interactions of NB with electron-deficient sensitizers or electron-rich TRP fluorophore-containing protein enzymes originate mainly from PET-initiated processes in both cases.     

Monitoring enzyme reaction and screening of inhibitors of acetylcholinesterase by quantitative matrix-assisted laser desorption/ionization fourier transform mass spectrometry

A matrix-assisted laser desorption/ionization Fourier transform mass spectrometry (MALDI-FTMS)-based assay was developed for kinetic measurements and inhibitor screening of acetylcholinesterase. Here, FTMS coupled to MALDI was applied to quantitative analysis of choline using the ratio of choline/acetylcholine without the use of additional internal standard, which simplified the experiment. The Michaelis constant (K _m) of acetylcholinesterase (AChE) was determined to be 73.9 μmol L⁻¹ by this approach. For Huperzine A, the linear mixed inhibition of AChE reflected the presence of competitive and noncompetitive components. The half maximal inhibitory concentration (IC₅₀) value of galantamine obtained for AChE was 2.39 μmol L⁻¹. Inhibitory potentials of Rhizoma Coptidis extracts were identified with the present method. In light of the results the referred extracts as a whole showed inhibitory action against AChE. The use of high-resolution FTMS largely eliminated the interference with the determination of ACh and Ch, produced by the low-mass compounds of chemical libraries for inhibitor screening. The excellent correlation with the reported kinetic parameters confirms that the MS-based assay is both accurate and precise for determining kinetic constants and for identifying enzyme inhibitors. The obvious advantages were demonstrated for quantitative analysis and also high-throughput characterization. This study offers a perspective into the utility of MALDI-FTMS as an alternate quantitative tool for inhibitor screening of AChE.     

DFT Study on Intermolecular Cleavage Reaction of N-（2-Hydroxyphenyl）-phthalamic Acid

The reaction mechanisms of intermolecular cleavage reaction of N-（2-hydroxyphenyl）-phthalamic acid were studied via the density functional theory（DFT）. All geometries of the reactant, transition states, and products were optimized at the B3LYP/6-31G（d, p） level. Vibration analysis was carried out to confirm its identity as transitions＇ structure, and the intrinsic reaction coordinate method（IRC） was used to search the minimum energy path. Two possible reaction channels are reported in this article. The calculated results indicate that O-cyclization reaction channel has the lower activation barrier, and therefore, it occurs more easier than the other.     

Sorption and desorption of phenanthrene onto iron, copper, and silicon dioxide nanoparticles

The sorption and desorption of phenanthrene by three engineered nanoparticles including nanosize zerovalent iron (NZVI), copper (NZVC), and silicon dioxide (NSiO2) were investigated. The sorption of phenanthrene onto NSiO2 was linear and reversible due to the hydrophilic properties of NSiO2. In comparison, sorption of phenanthrene onto NZVI and NZVC was nonlinear and irreversible, which was potentially due to the existence of significantly heterogeneous surface energy distribution patterns detected by a standard molecular probe technique. Naphthalene exerted significant competitive sorption with phenanthrene for NZVI and NZVC, and the isotherm of phenanthrene changed from being significantly nonlinear to nearly linear when naphthalene was simultaneously absorbed. A surface adsorption mechanism was proposed to explain the observed sorption and competition of phenanthrene on both NZVI and NZVC. In contrast, no competition was observed for sorption onto NSiO2. The sorption of phenanthrene on all three nanoparticles significantly decreased with increasing pH. The sorption irreversibility of phenanthrene on NZVI and NZVC were significantly enhanced with decreasing pH. A pH-dependent hydrophobic effect and dipole interactions between the charged surface (electron acceptors) and phenanthrene with electron-rich pi systems (electron donors) were proposed to explain the observed pH-dependent sorption.     

Syntheses and Crystal Structures of Two Chloro‐Bridged Coordination Polymers [Cd(BIM)Cl2]n and [Pb(BIM)Cl2]n

Two novel coordination polymers, [Cd(BIM)Cl₂]_n ( 1 ) and [Pb(BIM)Cl₂]_n ( 2 ) [wherein BIM = bis(imidazol‐1‐yl)methane], were synthesized by the reactions of the BIM ligand with CdCl₂ and PbCl₂, respectively. They were characterized by elemental analyses, IR, TGA and X‐ray single‐crystal diffraction techniques. Single‐crystal X‐ray structure analyses showed there is a pseudooctahedral arrangement around the cadmium atom in the complex 1 . It has a three‐dimensional network which contains one‐dimensional inorganic‐organic hybrid chains and μ₂‐bridging chloride ligands. A rare pentacoordinate square‐pyramidal arrangement was adopted for the lead(II) atom in the complex 2 , which has an unusual two‐dimensional layer structure of macrometallacycles crosslinked with the bridging Pb₂Cl₂ units. The metal atoms in both complexes were coordinated with two BIM ligands in cis arrangement and bridged by μ₂‐bridging chloride ligands.     

Preparative isolation of pseudolaric acids A and B,and their glucosides from the root bark of Pseudolarix kaempferi using high‐speed counter‐current chromatography

In order to provide the chemical markers for the quality control of herbal medicines, four diterpenoids, pseudolaric acids A and B (PAA and PAB), and their glucosides were isolated from the methanol extract of the Chinese herb Pseudolarix kaempferi using high‐speed counter‐current chromatography (HSCCC). The diphase solvent system was n‐hexane/EtOAc/MeOH/H₂O which was used at two ratios (5:5:5:5 and 1:9:4:6 by volume) in the separation of pseudolaric acids and their glycosides, respectively. As a result, PAA (14 mg), PAB (129 mg), PAA‐O‐β‐D ‐glucopyranoside (8 mg, PAAG), and PAB‐O‐β‐D ‐glucopyranoside (42 mg, PABG) were obtained from 0.5 g of the crude extract. Their purities were determined to be above 97% by HPLC analysis. Their chemical structures were confirmed by ¹H and ¹³C NMR analysis or HPLC comparison with the reference compounds.     

Synthesis and Mesomorphic Behavior of 3‐Alkyl‐2,5‐ bis[p‐(hexa‐2,4‐dienoyloxy)phenyl]‐Thiophene Derivatives

3‐Alkyl‐2,5‐bis[p‐(hexa‐2,4‐dienoyloxy)phenyl]‐thiophene derivatives were synthesized by using Kumada coupling and Suzuki coupling reactions as key steps. The thermotropic liquid crystalline behavior of these compounds was investigated by optical polarized microscopy, monotropic nematic mesophases were observed in such compounds.     

中空碳双面修饰的隔膜在高性能锂硫电池中的应用

为减少多硫化锂(LIPs)“穿梭效应”及锂枝晶对锂硫电池的影响,采用刮涂法制备中空碳材料修饰隔膜。接触角测试表明修饰隔膜对LIPs具有更强的吸引力,其对LIPs“穿梭”的有效抑制也可以通过渗透性实验进一步得到印证。在隔膜的正极对称电池测试中,电流响应显示中空碳材料的催化使LIPs快速转化为Li₂S。通过隔膜的负极对称电池测试发现修饰隔膜呈现出更稳定的电压-时间曲线。为证明隔膜修饰对锂硫电池性能改进的效果,分别采用聚丙烯(PP)隔膜、单面改性和双面改性的PP隔膜组装成纽扣电池并进行电化学测试,其中电极材料的硫负载量为1.8~2.0 mg·cm^-2。GITT(恒电流间歇滴定法)测试和锂离子扩散系数计算表明,改性隔膜的离子传输更快且阻抗较小。通过分析第1、5、10、50及100次的充放电循环阻抗谱图发现,中空碳材料的多通道能够为锂离子的传输提供更多的通道,因此能够使锂离子具有更加稳定的扩散行为。在电流密度为0.2C时,由双面改性隔膜组装的锂硫电池在首次充放电时有1 035 mAh·g^-1的可逆比容量,700圈后仍有500 mAh·g^-1的高比容量,并在高硫负载时表现出500 mAh·g^-1的可逆比容量。双面修饰隔膜赋予了锂硫电池优异的电化学性能,这是由于中空碳材料的修饰加速了LIPs的转化和吸附,有效缓解了LIPs的穿梭效应,且对锂枝晶有很好的抑制作用,提高了锂硫电池的安全性。     

Elution–extrusion counter-current chromatographic separation and theoretical mechanism of antioxidant from Robinia pseudoacacia flower

Robinia pseudoacacia flowers have attracted much attention because of numerous bioactivities. In this study, its extract showed the potential scavenging ability for 2,2′-azinobis-(3-ethylbenzthiazoline-6-sulphonate) and 1,1-diphenyl-2-picrylhydrazyl free radicals. Under the guidance of antioxidant activity, the antioxidant extract was enriched by liquid-liquid extraction. The partition coefficients of the two main components in antioxidant extracts differed greatly, so in this study, elution-extrusion counter-current chromatography with the solvent system of n-hexane-ethyl acetate-methanol-water (2.5:5:2.5:5, v/v) was used to enhance the separation efficiency, and the two main components were successfully obtained. Among them, kaempferol showed strong antioxidant activity, which can be responsible for the activity of the extract. In order to deeply understand the antioxidant mechanism of kaempferol, the thermodynamics, frontier molecular orbital, and kinetics of scavenging free radicals were investigated by density functional theory. The results showed that 4′-OH in kaempferol was the most active group, which can scavenge free radicals by hydrogen atom transfer in non-polar solvents and activate 3-OH to generate double hydrogen atom transfer in the gas phase. But in polar solvents, it was more inclined to clear radicals through single electron transfer and proton transfer. The kinetic result showed that kaempferol needed 9.17 kcal/mol of activation energy to scavenge free radicals.     

Exogenous Melatonin Activating Nuclear Factor E2-Related Factor 2 (Nrf2) Pathway via Melatonin Receptor to Reduce Oxidative Stress and Apoptosis in Antler Mesenchymal Stem Cells

Antler growth depends on the proliferation and differentiation of mesenchymal stem cells (MSCs), and this process may be adversely affected by oxidative stress. Melatonin (MLT) has antioxidant functions, but its role in Cervidae remains largely unknown. In this article, flow cytometry, reactive oxygen species (ROS) identification, qPCR, and other methods were used to investigate the protective mechanism of MLT in H₂O₂-induced oxidative stress of antler MSCs. The results showed that MLT significantly increases cell viability by relieving the oxidative stress of antler MSCs. MLT inhibits cell apoptosis by protecting mitochondrial function. We blocked the melatonin receptor with luzindole (Luz) and found that the receptor blockade significantly increases H₂O₂-induced hyperoxide levels and causes significant inhibition of mitochondrial function. MLT treatment activates the nuclear factor E2-related factor 2 (Nrf2) antioxidant signaling pathway, up-regulates the expression of NAD(P)H quinone oxidoreductase 1 (NQO1) and other genes and it could inhibit apoptosis. In contrast, the melatonin receptor blockade down-regulates the expression of Nrf2 pathway-related genes, but significantly up-regulates the expression of apoptotic genes. It was indicated that MLT activates the Nrf2 pathway through the melatonin receptor and alleviates H₂O₂-induced oxidative stress and apoptosis in antler MSCs. This study provides a theoretical basis for further studying the oxidative stress and antioxidant process of antler MSCs and, thereby, increasing antler yields.