聚砜酰胺超滤膜的制备和性能

本文研究了聚砜酰胺超滤膜制备的工艺条件和膜分离性能之间的关系。求得膜的分离性能随预压时间、蒸发时间、沉淀浴温度和溶剂种类而变化的规律。     

铜在鱼体中的积累规律研究

采用实验室模拟对鱼所生存的人工水环境中投Cu的方式,通过鱼对Cu的吸收富集研究了鱼体中Cu的积累规律及其Cu对部分鱼内脏的毒性影响。揭示不同质量浓度下,单一重金属离子在鲫鱼体内积累的动态变化规律以及铜对鲫鱼属于剧毒重金属。结果表明,在较低的质量浓度下Cu在鲫鱼各组织器官中的积累量随质量浓度的增加而增加、随时间的延长而增加,达到一定时间后积累趋于平衡;在高质量浓度环境下Cu在鲫鱼各组织器官中的积累量有时随时间的延长反而有所下降,但针对不同组织来说其积累能力由大到小顺序一般为:内脏,鱼鳃,肌肉。采用主要的分析方法是微波溶样消解法和火焰原子吸收分光光度法。     

对羟基苯甲酸的溶剂浮选研究

研究了对羟基苯甲酸溶剂浮选的浮选条件优化和回收动力学规律。考察了溶液的pH、通气速度、溶液离子强度、浮选时间、相比以及浮选溶剂等因素对对羟基苯甲酸浮选效率的影响，优选了浮选条件。研究表明对羟基苯甲酸的溶剂浮选过程符合一级动力学方程，表观速率常数随空气流速的增加而增大。     

温度和相结构对镧扩散动力学的影响

研究了等离了体渗氮过程中La在密排六方ε－Fe-3N(ε）和面心立方γ′－Fe4N(γ′)双相中的扩散动力学规律,与γ′相或ε＋γ′双相比较,发现ε相对La的扩散具有阻碍作用,一定温度下,随着渗氮时间的延长,ε相不断分解出γ′相,La在单相（如γ′相）和双相ε γ′中的扩散深度分别呈抛物线和近似指数规律增加,提高渗氮温度,La扩散的深度增加,但其扩散动力学规律并未因此而改变,温度从520度升高至560度使La扩散深度的增量较因相结构由ε转变为γ′相而引起的层深增加要小。     

脂肪酸的色谱保留时间规律与质谱特征研究及其在食品分析中的应用

用石油醚提取食品中的脂肪,经甲酯化反应后,采用HP-88(100m×0.25mm,0.33μm)弹性石英毛细管柱分离脂肪酸甲酯的同系物及异构体,GC/MS法测定。研究了不同链长脂肪酸的同系物及异构体的气相色谱出峰顺序,得到其保留时间规律;研究了不同脂肪酸的质谱断裂规律,选择3个特征离子来鉴定脂肪酸成分。建立了3个特征离子确定脂肪酸碳数及双键数目,色谱保留时间规律确定脂肪酸顺反异构体及双键位置异构体的方法。本法无需标准品即可快速测定脂肪酸同系物及异构体的含量,适用于脂肪酸组成的研究;及油脂、食品中脂肪酸,特别是反式脂肪酸的测定。     

基质辅助激光解吸电离飞行时间质谱对环状芳香多硫寡聚物的研究

采用基质辅助激光解吸电离飞行时间质谱(MALDI TOF-MS)对环状芳香硫醚的寡聚产物进行了测定和分析,首次确定了这类采用其它传统方法难以分析的难溶多硫环状芳香硫醚寡聚物的结构;研究了芳香烃部分随聚合度不同的分布规律和芳香烃部分相同的条件下S原子数目不同而引起的组分变化的规律;讨论了4种基质的辅助解吸电离效果和离子化试剂对测定结果的影响,探索出测定这类寡聚物的最佳条件.     

非线性和时变参数时间序列模型及其在水质分析中的应用

时间序列分析是根据观测值建立数学模型，研究数据的内在规律，现有文献主要是介绍线性时间序列模型。研究表明化学分析数据很多涉及非线性时间序列，且具有时变参数特性。本文在研究线性、非线性时间序列模型基础上，提出一种具有时变参数特性的非线性时间序列模型。该模型用于加酸调ｐＨ的循环冷却水系统进行预报，可使ｐＨ值极差降低３～６倍，对保证水质稳定具有重要意义。     

芎汤活血有效部位在大鼠体内整体吸收规律的HPLC指纹图谱研究

研究芎汤活血有效部位给药大鼠体内的整体吸收规律。将活血有效部位给大鼠灌胃后,测绘不同时间点血浆的HPLC指纹图谱,通过比较计算特征峰欧式距离,研究该复方药对的吸收规律。芎汤活血有效部位大鼠给药后,45 min药物吸收最高,1.5 h之内体内药物浓度保持在较高水平,随后变化较小。采用指纹图谱技术测定复方给药后的血浆成分,能更好地反映中药多成分在体内的吸收规律。     

n-InP/Fe3+, Fe2+界面在小信号电流阶跃下的暂态行为

应用小信号电流阶跃法研究了光照下n-InP/Fe~(3+), Fe~(2+)界面, 此时电位变化符合双指数规律, 这和理论推导是一致的。在时间很短时, 电位与时间成线性关系, 从直线斜率可求出空间电荷区电容。     

以高锰酸钾引发丙烯腈与木质纤维素接枝共聚的研究

研究了以高锰酸钾为引发剂羟丙基马尾松磨木浆粕与丙烯腈接枝共聚的基本反应规律。结果表明,所研究的体系具有较高单体转化率、高接枝效率和低均聚的特点。当高锰酸钾予处理时间大于10分钟,温度高于50℃,浓度达0.057N时,接枝增量趋于稳定;但当高锰酸钾浓度高于0.99N,温度在65℃以上时,接枝增量反而下降,这可能是由于高锰酸钾氧化接枝底物造成。在50℃,硫酸浓度为0.021M时,接枝增量有一最大值。接枝增量和均聚率随聚合时间的延长而增加,120分钟后基本趋于稳定,接枝增量随单体浓度的提高而明显增加,但均聚率却无明显变化。     

Kinetic Isotope Effects in Asymmetric Reactions

Kinetic isotope effects are exquisitely sensitive probes of transition structure. As such, kinetic isotope effects offer a uniquely useful probe for the symmetry‐breaking process that is inherent to stereoselective reactions. In this Concept article, we explore the role of steric and electronic effects in stereocontrol, and we relate these concepts to recent studies carried out in our laboratory. We also explore the way in which kinetic isotope effects serve as useful points of contact with computational models of transition structures. Finally, we discuss future opportunities for kinetic isotope effects to play a role in asymmetric catalyst development.     

河水中兽药多残留分析时亲水亲脂平衡柱的基质效应和保留效果

基质效应是液相色谱-质谱联用(LC-MS)定量分析中的重要干扰因素。以反渗透水为空白对照进行LC-MS/MS检测,在500倍浓缩条件下考察了33种兽药分别经Waters、Supelco和CNW等3种亲水亲脂平衡(hydrophilic-lipophilic balance, HLB)固相萃取柱富集后的基质效应及其保留效果。结果表明,以反渗透水为基质时3种HLB柱均表现出外源性基质效应,对大部分喹诺酮类和四环素类兽药呈现促进效应,有两种HLB柱对雌激素类兽药等呈现抑制效应,对磺胺类兽药的基质效应不显著,有一种HLB柱对氯霉素类兽药呈现抑制效应;以河水为基质时,由于外源性杂质与内源性杂质共同作用,对大部分喹诺酮类和四环素类兽药呈现促进效应,对氯霉素类和雌激素类兽药呈现抑制效应,对磺胺类兽药基质效应不显著。与外标法相比较,基质匹配标准校正法可有效消除基质效应对检测结果的影响。在50 ng/L和200 ng/L两个加标水平下,Waters、Supelco和CNW 3种HLB柱对河水中33种目标兽药的校正后的回收率分别为40.3%~146.0%、37.8%~104.2%和52.9%~150.1%; RSD(n=4)为0.2%~14.6%。相同实验条件下3种HLB柱的外源性基质效应不容忽视。而采用基质匹配标准校正法克服目标物基质效应,保留效果无显著差异,富集效果良好,为河水样品中兽药多残留分析方法中固相萃取柱的选择提供了科学依据。     

Isotope Effects in Organic Chemistry and Biochemistry

The present article shows the extent to which isotope effects are likely to be encountered in the use of isotope techniques and what problems are studied with primary and secondary isotope effects. By way of example, the results of studies on E2 reactions, particularly in the Hofmann degradation, are discussed, followed by a discussion of some “analytical isotope effects”. Finally, the problems encountered and the information that can be obtained from isotope effects studies on enzyme reactions, and the advantages and disadvantages of competitive and non-competitive techniques are described. In addition to a survey of isotope effects in dehydrogenase reactions, new isotope effects encountered in the dehydrogenation of T-labeled alcohols are reported.     

Anti-oxidative action of resveratrol: Implications for human health

Resveratrol, the red-wine polyphenol, is intensively studied polyphenols for its pleiotropic biological effects. A plethora of health beneficial effects of this stilbene has been reported including cardio-protective, neuro-protective, anti-cancer, anti-diabetic and interesting anti-aging. Though it has been proposed that these effects of resveratrol arise from its capacity to interact with multiple molecular targets involved in diverse intracellular pathways including activation of sirtuins, the antioxidant property of this compound is the most described one to attribute its diverse health beneficial effects. In the present review we have explained the biological activities of resveratrol with the latest laboratory evidences towards its antioxidant effects.     

Substituent Effect on the C–NO2 and N–NO2 Bond Dissociation Energies of Nitroaromatic Molecules

Six density function theory methods (B3LYP, B3P86, MPWB1K1, MPWPW91, PBEPBE, TPSS1KCIS3) were used to calculate bond dissociation enthalpies of nitro compounds, where the B3P86 method was found to give the most accurate predictions. Using the B3P86 method meta‐ and para‐substituted nitroaromatics were systematically studied for the first time. The remote substituent effects, Hammett relationships, and the origin of the substituent effects were discussed on the basis of the calculated results. Both meta‐ and para‐substituted nitromethyl‐benzenes showed significant substituent effects and a fair correlation against substituent constants σ_p⁺ The ground state effects were found to play the major role in determining the overall substituent effects. Meanwhile, nitroamino‐ benzenes showed irregular substituent effects and a poorer Hammett correlation, where both ground and radical state effects contributed to the overall substituent effects.     

Matrix effects demystified: Strategies for resolving challenges in analytical separations of complex samples

Matrix effects can significantly impede the accuracy, sensitivity, and reliability of separation techniques presenting a formidable challenge to the analytical process. It is crucial to address matrix effects to achieve accurate and precise measurements in complex matrices. The multifaceted nature of matrix effects which can be influenced by factors such as target analyte, sample preparation protocol, composition, and choice of instrument necessitates a pragmatic approach when analyzing complex matrices. This review aims to highlight common challenges associated with matrix effects throughout the entire analytical process with emphasis on gas chromatography-mass spectrometry, liquid chromatography-mass spectrometry, and sample preparation techniques. These techniques are susceptible to matrix effects that could lead to ion suppression/enhancement or impact the analyte signal at various stages of the analytical workflow. The assessment, quantification, and mitigation of matrix effects are necessary in developing any analytical method. Strategies can be implemented to reduce or eliminate the matrix effect by changing the type of ionization, improving extraction and clean-up methods, optimization of chromatography conditions, and corrective calibration methods. While development of an effective strategy to completely mitigate matrix effects remains elusive, an integrated approach that combines sample preparation, analytical extraction, and effective instrumental analysis remains the most promising avenue for identifying and resolving matrix effects.     

Some symmetry-induced isotope effects in the kinetics of recombination reactions

Symmetry-induced isotope effects in recombination and collision-induced dissociation reactions are discussed. Progress on understanding the anomalous isotope effects in ozone is reviewed. Then, calculations are performed for the simpler reaction xNe+yNe+H<-->xNeyNe+H, where x and y label either identical or different isotopes. The atomic masses in the model are chosen so that symmetry is the only difference between the systems. Starting from a single potential energy surface, the properties of the bound, quasibound, and continuum states of the neon dimer are calculated. Then, the vibration rotation infinite order sudden approximation is used to calculate cross sections for all possible inelastic and dissociative processes. A rate constant matrix that exactly satisfies detailed balance is constructed. It allows recombination to occur both via direct three-body collisions and via tunneling into the quasibound states of the energy transfer mechanism. The eigenvalue rate coefficients are determined. Significant isotope effects are clearly found, and their behavior depends on the pressure, temperature, and mechanism of the reaction. Both spin statistics and symmetry breaking produce isotope effects. Under most conditions the breaking of symmetry enhances the rates, but a wide spectrum of effects is observed; they range from isotope effects with a normal mass dependence to huge, mass-independent isotope effects to cancellation and even to reversal of the isotope effects. This is the first calculation of symmetry-induced isotope effects in recombination rates from first principles. The relevance of the present effects to ozone recombination is discussed.     

Electronic properties of amino acid side chains: quantum mechanics calculation of substituent effects

Background  

Electronic properties of amino acid side chains such as inductive and field effects have not been characterized in any detail. Quantum mechanics (QM) calculations and fundamental equations that account for substituent effects may provide insight into these important properties. PM3 analysis of electron distribution and polarizability was used to derive quantitative scales that describe steric factors, inductive effects, resonance effects, and field effects of amino acid side chains.     

Nuclear quantum effects at aqueous metal interfaces captured by molecular dynamics simulations

In this review, we summarize the recent development in modeling nuclear quantum effects at aqueous metal interfaces. First, we review the nuclear quantum effects on the water-metal interface at ultrahigh vacuum. Then, we illustrate the nuclear quantum effects at the potential of zero charge conditions. At last, we give some outlook for the perspective work in modeling the nuclear quantum effects at electrochemical interfaces and some practical simulation strategies.     

共混聚合物辐射效应研究的进展

本文综述了近十几年来国内外共混聚合物辐射效应研究的进展情况.内容包括辐射交联理论在共混聚合物体系中的适用性、共混体系的相容性、相态结构对辐射效应的影响及共混组份间的辐射敏化及保护效应等.