Synthesis and application of mesoporous molecular sieve for miniaturized matrix solid‐phase dispersion extraction of bioactive flavonoids from toothpaste,plant, and saliva

This article describes the use of the mesoporous molecular sieve KIT‐6 as a sorbent in miniaturized matrix solid‐phase dispersion (MSPD) in combination with ultra‐performance LC for the determination of bioactive flavonoids in toothpaste, Scutellariae Radix, and saliva. In this study, for the first time, KIT‐6 was used as a sorbent material for this mode of extraction. Compared with common silica‐based sorbents (C18 and activated silica gel), the proposed KIT‐6 dispersant with a three‐dimensional cubic Ia3d structure and highly ordered arrays of mesoporous channels exhibits excellent adsorption capability of the tested compounds. In addition, several experimental variables, such as the mass ratio of sample to dispersant, grinding time, and elution solvent, were optimized to maximize the extraction efficiency. The proposed analytical method is simple, fast, and entails low consumption of samples, dispersants and elution solvents, thereby meeting “green chemistry” requirements. Under the optimized conditions, the recoveries of three bioactive flavonoids obtained by analyzing the spiked samples were from 89.22 to 101.17%. Also, the LODs and LOQs for determining the analytes were in the range of 0.02–0.04 μg/mL and 0.07–0.13 μg/mL, respectively. Finally, the miniaturized matrix solid‐phase dispersion method was successfully applied to the analysis of target solutes in real samples, and satisfactory results were obtained.     

Mechanism of proteolysis in matrix metalloproteinase‐2 revealed by QM/MM modeling

The mechanism of enzymatic peptide hydrolysis in matrix metalloproteinase‐2 (MMP‐2) was studied at atomic resolution through quantum mechanics/molecular mechanics (QM/MM) simulations. An all‐atom three‐dimensional molecular model was constructed on the basis of a crystal structure from the Protein Data Bank (ID: 1QIB), and the oligopeptide Ace‐Gln‐Gly～Ile‐Ala‐Gly‐Nme was considered as the substrate. Two QM/MM software packages and several computational protocols were employed to calculate QM/MM energy profiles for a four‐step mechanism involving an initial nucleophilic attack followed by hydrogen bond rearrangement, proton transfer, and C? N bond cleavage. These QM/MM calculations consistently yield rather low overall barriers for the chemical steps, in the range of 5–10 kcal/mol, for diverse QM treatments (PBE0, B3LYP, and BB1K density functionals as well as local coupled cluster treatments) and two MM force fields (CHARMM and AMBER). It, thus, seems likely that product release is the rate‐limiting step in MMP‐2 catalysis. This is supported by an exploration of various release channels through QM/MM reaction path calculations and steered molecular dynamics simulations. © 2015 Wiley Periodicals, Inc.     

预裂化理论研究:基质表面酸性位类型及不同类型酸性位接触顺序对裂化过程小分子烯烃收率的影响

在区分氢负离子转移反应与氢转移反应、非选择性氢转移反应与总的氢转移反应的情况下,通过合成物性相近但酸性不同的氧化铝,用以作为裂化催化剂基质材料,在固定床反应器上考察了催化裂化过程,基质酸性位类型及基质表面Lewis及Brönsted酸性位接触顺序对小分子烯烃(丙烯、丁烯)收率的影响。结果表明,催化裂化生成小分子烯烃过程中,分子筛与基质所呈现出的反应特点存在较大的区别,前者活性虽高,但总的氢转移反应活性过强。基质材料裂化活性虽低但其表面以氢负离子转移反应为主,反应路径角度更有利于小分子烯烃收率的提高。另外,基质表面存在Brönsted酸性位,或原料油首先与基质表面Lewis酸性位相接触再与Brönsted酸性位反应的预裂化过程,会在促进裂化反应发生的同时抑制总的氢转移反应,更有利于小分子烯烃收率的提高。     

Environmental effects on fibre reinforced polymeric composites: Evolving reasons and remarks on interfacial strength and stability

The interface between fibre and matrix of fibrous polymeric composites is most critical and decisive in maintaining sustainability, durability and also reliability of this potential material, but unfortunately a comprehensive conclusion is yet to meet the label of confidence for the engineering viability. Fiber reinforced polymer (FRP) composites are being accepted and also utilized as better and reliable alternative materials for repairing and/or replacing conventional materials, starting from tiny objects to mega structure in various engineering applications. The promise and potential of these materials are sometimes threatened in speedy replacement of conventional materials because of their inhomogeneities and inherent susceptibility to degradation due to moist and thermal environments. Environmental conditioning is traditionally believed to be a physical phenomenon but present literature has revealed that the interdiffusion between fiber and polymer matrix resin comprises of physical, chemical, mechanical, physico-chemical and mechano-chemical phenomena. The failure and fracture behavior at ambient conditions itself is a complex phenomenon till at present. The service conditions which are mostly hygrothermal in nature, along with a variation of applied loads make the mechanical behavior nearly unpredictable, far off from conclusions in evaluating the short term as well as long term durability and reliability of FRPs. It is essential to accurately simulate the initial and subsequent evolution process of this kind of damage phenomena, in order to explore the full potential of the mechanical properties of composite laminates. The present review has emphasized the need of complying scattered as well as limited literature on this front, and has focused on creating the urgency to highlight the importance of judicious uses of these materials with minimum safety factors with an aim to achieving lighter weight in enhancing specific properties.     

Tutorial review on validation of liquid chromatography–mass spectrometry methods: Part I

This is the part I of a tutorial review intending to give an overview of the state of the art of method validation in liquid chromatography mass spectrometry (LC–MS) and discuss specific issues that arise with MS (and MS/MS) detection in LC (as opposed to the “conventional” detectors). The Part I briefly introduces the principles of operation of LC–MS (emphasizing the aspects important from the validation point of view, in particular the ionization process and ionization suppression/enhancement); reviews the main validation guideline documents and discusses in detail the following performance parameters: selectivity/specificity/identity, ruggedness/robustness, limit of detection, limit of quantification, decision limit and detection capability. With every method performance characteristic its essence and terminology are addressed, the current status of treating it is reviewed and recommendations are given, how to determine it, specifically in the case of LC–MS methods.     

Simultaneous determination of naphazoline and pyridoxine in eye drops using excitation–emission matrix fluorescence coupled with second-order calibration method based on alternating trilinear decomposition algorithm

A novel method is developed for the direct determination of naphazoline hydrochloride(NAP) and pyridoxine hydrochloride(VB6) in commercial eye drops. By using excitation–emission matrix(EEM)fluorescence coupled with second-order calibration method based on the alternating trilinear decomposition(ATLD) algorithm, the proposed approach can achieve quantitative analysis successfully even in the presence of unknown and uncalibrated interferences. The method shows good linearity for NAP and VB6 with correlation coefficients greater than 0.99. The results were in good agreement with the labeled contents. To further confirm the feasibility and reliability of the proposed method, the same batch samples were analyzed by multiple reaction monitoring(MRM) based on LC–MS/MS method.T-test demonstrated that there are no significant differences between the prediction results of the two methods. The satisfactory results obtained in this work indicate that the use of the second-order calibration method coupled with the EEM is a promising tool for industrial quality control and pharmaceutical analysis due to its advantages of high sensitivity, low-cost and simple implementation.     

超高效液相色谱-串联质谱法检测花生中36种农药及其代谢物残留

建立了花生中36种农药及其代谢物残留的超高效液相色谱-串联质谱(UHPLC-MS/MS)快速检测技术。采用乙腈提取,增强型脂质去除净化剂(EMR-Lipid)净化,正离子多反应监测(MRM)模式测定。结果表明,所有农药的线性相关系数均大于0.994,在0.005,0.01,0.10 mg/kg 3个加标水平下,36种农药的平均回收率为70.4%~119%,相对标准偏差(RSDs)为1.3%~19.4%,方法的定量下限为0.002 5~0.05 mg/kg。该方法简便、快速,灵敏度高、净化效果好,适用于花生中农药多残留的快速检测分析。     

固相萃取/液相色谱-串联质谱法测定食品中二甲基黄

建立了液相色谱-串联质谱(LC-MS/MS)测定食品中二甲基黄(DMY)的分析方法。样品经乙酸乙酯提取,二甲基黄专用固相萃取小柱(ProElut DMY SPE)净化,XDB-C18色谱柱(50 mm×4.6 mm,1.8μm)分离,并以5mmol/L乙酸铵水溶液(含0.1%(v/v)甲酸)-乙腈(含0.1%(v/v)甲酸)为流动相,梯度洗脱,电喷雾正离子模式(ESI~+)电离,多反应监测模式(MRM)检测,内标法定量。结果表明,DMY在0~50μg/L范围内线性关系良好,相关系数(r~2)均大于0.999。方法的检出限(LOD,S/N3)和定量限(LOQ,S/N10)分别为2μg/kg和10μg/kg。不同食品基质中,DMY在10、20和100μg/kg的添加水平下的平均加标回收率为93.3%~98.9%,相对标准偏差为1.6%~3.9%(n=6)。该方法有效补偿了液相色谱-串联质谱检测过程中的离子化抑制效应,灵敏度和准确度高,适用于腐乳、辣椒酱、禽蛋、豆干、糖果和火腿中DMY的测定。     

Synthesis,characterization, and hydrolytic degradation of polylactide/poly(ϵ-caprolactone)/nano-silica composites

Poly(lactic acid) (PLA)/poly(?-caprolactone) (PCL)/nano-silica composite degradable films were prepared by a solvent casting method. SEM results showed that the nano-silica particles were dispersed uniformly in the PLA/PCL matrix. TGA results indicated that the thermal decomposition temperature rose with the increase of nano-silica content. The tensile strength of the composites was enhanced with the increase of nano-silica content up to 2%. The tensile strength increased with the silica content and reached its maximum (22.51 Mpa). The improvement in the water uptake ratio in the PLA/PCL/silica nanocomposites may be attributable to the presence of silica nanoparticles in the PLA/PCL matrix. After 15 weeks total processing time for the solution of alkaline and phosphate buffer, the performances of 16.23% and 3.65% for degradation.     

基于严格α-双链对角占优矩阵的非奇H-矩阵的判定准则

研究了非奇H-矩阵的判定问题.先给出了几个判定严格α-双链对角占优矩阵的充要条件,进一步利用矩阵对角占优理论得到了判定非奇H-矩阵的一些充分条件,推广和改进了已有的相关结果,并用数值算例说明了这些判定方法的有效性.