甘氨酸衍生化β-环糊精键合硅胶液相色谱固定相的合成与评价

 β-环糊精键合硅胶经对甲苯磺酰化后,与甘氨酸反应得到甘氨酸衍生化β-环糊精键合硅胶固定相(GCDS)。考察了GCDS对位置异构体、丹磺酰化氨基酸异构体、苯丙酸类药物等的分离性能,研究了流动相中甲醇浓度、pH以及柱温对色谱保留行为的影响。     

有机杂化硫代碲酸盐化合物(H_2en)TeS_3和[Ni(en)_3]TeS_3的溶剂热合成与表征

用低温溶剂热法合成了2种分立结构的有机杂化硫代碲(Ⅳ)酸盐化合物(H2en)TeS3(1)和[Ni(en)3]TeS3(2)(en=乙二胺),通过X-射线单晶衍射,红外光谱,元素分析等手段对它们的结构进行了表征。晶体结构解析结果表明:2个化合物均属单斜晶系,空间群分别为P21和P21/c。化合物1和2具有孤立三角锥[TeS3]2-阴离子,化合物1的平衡阳离子为双质子化乙二胺[H2en]2+,阴离子基团[TeS3]2-和阳离子基团[H2en]2+之间通过N-H…S氢键连接。化合物2的阳离子基团为过渡金属Ni与乙二胺的配合物[Ni(en)3]2+。另外,对该2种晶体进行了紫外-可见漫反射光谱测试和热重分析。     

羧基膦酸改性氧化锆固定相的制备及其色谱性能

用十二胺-N乙酸-N亚甲基膦酸（DAPA）改性氧化锆制备了一种新的锆基质色谱固定相（DAPAZ），研究发现，DAPA在氧化锆表面有两种结合方式：红外光谱中1611cm^-1处的特征吸收表明羧基主要与胺基形成偶极离子，以羧酸根离子形式存在，大部分的DAPA分子通过膦酸基团与氧化锆结合；而与钼酸的显色反应则表明有少量DAPA以羧居与氧化锆结合，另外，对固定相的屏蔽效应、碱性条件（pH9．5）下的稳定性等色谱性能的研究也证实这两种吸附方式同时存在，但以膦酸基结合为主。     

INDUCED OSCILLATIONS GENERATED BY PROTECTIVE THRESHOLD POLICIES IN THE MANAGEMENT OF EXPLOITED POPULATIONS

Abstract Management and conservation of exploited populations have been a central issue in theoretical and empirical studies. In this work, it is shown that threshold policies can induce cyclic behavior in an otherwise exploited stable population as a consequence of the combination of harvest pressure and excessively protective threshold densities. Moreover, the dynamical outcomes generated by these extremely protective policies may vary according to the initial densities. These results may be of significant concern in conservation as well as in management of exploited population.     

Charge transfer through modified peptide nucleic acids

We studied the charge transfer properties of bipyridine-modified peptide nucleic acid (PNA) in the absence and presence of Zn(II). Characterization of the PNA in solution showed that Zn(II) interacts with the bipyridine ligands, but the stability of the duplexes was not affected significantly by the binding of Zn(II). The charge transfer properties of these molecules were examined by electrochemistry for self-assembled monolayers of ferrocene-terminated PNAs and by conductive probe atomic force microscopy for cysteine-terminated PNAs. Both electrochemical and single molecular studies showed that the bipyridine modification and Zn(II) binding do not affect significantly the charge transfer of the PNA duplexes.     

Luminescence-Based Optical Fiber Chemical Sensors

Abstract

A scheme for the simultaneous determination of temperature and analyte concentration for application in luminescence-based chemical sensors is proposed. This scheme is applied to an optical oxygen sensor, which is based on the quenching of the fluorescence of a ruthenium complex. Temperature measurement is performed using the excitation radiation and an absorption long-pass filter. Preliminary results are presented that show the viability of an oxygen measurement that is independent of temperature and optical power level. The possibility of self-referenced temperature measurements with semiconductor nanoparticles is also investigated. In order to optimize the sensor design, several different optical fiber probe geometries for oxygen sensing are tested and compared, including different methods of coupling radiation into the optical fiber system. Polyvinyl alcohol (PVA) and polyacrylamide membranes are tested as supports for sensor immobilization in fiber-optical pH sensing devices in aqueous solution. Some results are presented that show the feasibility of using fiber-optical pH indicators for remote monitoring.     

Getting the most from molecular simulation

Advanced molecular simulation methods are surveyed, emphasizing techniques that can be used to improve the quality of the results obtained by a simulation. Consideration is given to three aspects of simulation performance: sampling of configurations, analysis of data and evaluation of free energies. Monte Carlo methods are highlighted. Methods are discussed in the context of the important regions of phase space for different systems. It is stressed that the shape of the important region for a single system, or the relation between important regions for two different systems, can profoundly affect the performance of a simulation applied to them. Categories of relations for the regions are (i) no overlap; (ii) partial overlap; or (iii) a subset. The last case is especially important because it implies that there is an otherwise hidden asymmetry in the relation between the systems—this asymmetry impacts the performance of simulations applied to evaluate property differences between such systems. Effective application of advanced simulation methods sometimes requires awareness of these issues, indicating that the practice of simulation might be advanced by the development of ways to quantify shapes and relationships of phase-space regions.     

Modelling the metabolic action of human and rat CYP1A2 and its relationship with the carcinogenicity of heterocyclic amines

Cytochrome P450 (CYP) is a family of enzymes responsible for organism detoxification. However, some of the members of the CYP1A subfamily also catalyse the activation of heterocyclic amines (HAs), present in cooked meat, to carcinogenic compounds which have been shown to increase the risk of breast, colorectal and lung cancer. In humans, CYP1A2 is the enzyme with the most significant action in HA metabolism but in rodents CYP1A1 is also important in this biotransformation. Understanding the metabolic action of these enzymes is essential to predict the factors that enable the formation of the carcinogenic products. We have built two models of CYP1A2, one for the human enzyme and one for the rat homologue. The templates chosen include the only X-ray structure published to date for a mammal CYP, a quimeric C2A5 from rabbit, as well as CYPs belonging to Bacillus megaterium (CYPBm-3), Pseudomonas putida (CYPcam), Pseudomonas sp. (CYPterp), and Saccharopolyspora erythraea (CYPeryf). Two HAs, MeIQ (2-amino-3,4-dimethylimidazo[4,5-?]quinoline) and MeIQx (2-amino-3,8-dimethylimidazo[4,5-?]quinoxaline), known substrates of human and rat CYPIA2, were docked in the active site of the models, providing information regarding the different catalytic rates associated with the metabolisms in both enzymes. This is important for analysing the behaviour of animal models concerning the testing of anticancer drugs.     

Equivalent properties of single event burnout induced by different sources

The experimental results of single event burnout induced by heavy ions and 252Cf fission fragments in power MOSFET devices have been investigated. It is concluded that the characteristics of single event burnout induced by 252Cf fission fragments is consistent to that in heavy ions. The power MOSFET in the "turn-off" state is more susceptible to single event burnout than it is in the "turn-on" state. The thresholds of the drain-source voltage for single event burnout induced by 173 MeV bromine ions and 252Cf fission fragments are close to each other, and the burnout cross section is sensitive to variation of the drain-source voltage above the threshold of single event burnout. In addition, the current waveforms of single event burnouts induced by different sources are similar. Different power MOSFET devices may have different probabilities for the occurrence of single event burnout.