纤维堆囊菌发酵液中埃博霉素含量的HPLC法分析

采用反馈神经网络结合遗传算法(BPANN-GA)对高效液相色谱(HPLC)法同时测定纤维堆囊菌(Sorangium cellulosum)代谢物中埃博霉素A(Epo A)和埃博霉素B(Epo B)含量的条件进行优化, 采用均匀设计(U₁₂³)方案对流动相中乙腈的体积分数、色谱柱温度和流动相的pH等3个因素进行实验设计; 以色谱函数(COF)值为优化指标, 运用双层反馈神经网络建立色谱优化函数(COF)值, 考察因素间的预测模型, 采用Levenberg-Marquardt backpropagation算法对所建立的神经网络预测模型进行训练, 以逼近度(D_a)为优化参数, 选择预测模型的最适隐含层节点数. 最优预测模型预测的COF值与实验值之间的相关系数(R)达到0.98165, 采用遗传算法在实验考察范围内进行全局寻优, 得到最优化的HPLC分析条件: 流动相中乙腈体积分数为29.2%, 色谱柱温度为34 ℃, 流动相pH为4.23. 在此最优条件下对纤维堆囊菌代谢产物进行HPLC分析, 结果表明, 该方法对两种埃博霉素色谱峰均具有较好的分离度.     

两个埃博霉素生物合成中间体修饰化合物的合成

为了使用前体定向生物合成技术研究埃博霉素的生物合成过程并对其进行分子改造, 选定了两个中间体修饰化合物2-甲基噻唑-4-羧酸2-乙酰氨基乙硫基硫酯和(E)-2-甲基-3-(2-甲基噻唑-4-基)丙烯酸2-乙酰氨基乙硫基硫酯进行了化学全合成的研究. 合成方法比已有的合成方法更易操作, 经济性更好. 所有化合物经红外光谱、质谱、核磁共振谱及元素分析确证了结构.     

二价金属离子对平阳霉素与DNA作用的影响

二价金属离子对平阳霉素与ＤＮＡ作用的影响王自春，黄登宇，袁静明（山西大学分子科学研究所，太原，０３０００６）关键词二价金属离子，平阳霉素，ＤＮＡ平阳霉素（简称ＢＬＭ－Ａ５）是抗肿瘤抗生素博莱霉素的成分之一，其化学结构、理化性质和药理作用虽基本相同［１...     

基于三维分子描述符的埃坡霉素类衍生物抗癌活性预测

为预测埃坡霉素类衍生物的抗癌活性, 定义了一套表征分子形状的描述符, 即K阶形状参数, 并计算了67个表征分子的电子、拓扑和几何结构的分子描述符. 描述符经遗传算法筛选, 用于建立基于支持向量学习机(SVM)的抗癌活性分类模型; 用留一法和5重交叉验证法对SVM模型参数进行了优化. 结果表明模型具有较高的预测性且两种方法得到相近结果, 交叉验证的预测正确率达80.6%; 经筛选后的描述符有30个, 其中含有5个K阶形状参数, 这些描述符对埃坡霉素类衍生物的抗癌活性的模型建立具有比较重要的作用.     

纳米羟基磷灰石负载埃博霉素B的细胞活性研究

羟基磷灰石(HA)纳米材料因其生物相容性好,比表面积大,可以吸附大量的药物分子,因此在纳米医药领域极具应用前景。本文通过共沉淀法制备出纳米HA(HA NPs),然后利用XRD,FT IR,SEM,TEM进行表征,结果表明,所制备的HA NPs呈针形,长约70~90nm。实验表明,采用二氯甲烷作为溶剂,埃博霉素B(Epo B)负载效率最高,最大负载量达0.53g/(g HA)。应用MTT法对HA NPs及复合物的抗肿瘤活性进行分析,结果显示HA-Epo B复合物对肺癌细胞NCI-H292和LLC的IC50浓度分别为15和35 ng/m L,明显低于游离Epo B的IC5035和50 ng/m L。这可能是HA NPs更容易进入细胞内,然后将药物释放,进而抑制肿瘤细胞生长。     

纳米羟基磷灰石负载Epothilone B的细胞活性研究

羟基磷灰石(HA)纳米材料因其生物相容性好,比表面积大,可以吸附大量的药物分子,因此在纳米医药领域极具应用前景。本文通过共沉淀法制备出纳米HA(HA NPs),然后利用XRD,FT IR,SEM,TEM进行表征,结果表明,所制备的HA NPs呈针形,长约70~90nm。实验表明,采用二氯甲烷作为溶剂,埃博霉素B(Epo B)负载效率最高,最大负载量达0.53g/(g HA)。应用MTT法对HA NPs及复合物的抗肿瘤活性进行分析,结果显示HA-Epo B复合物对肺癌细胞NCI-H292和LLC的IC50浓度分别为15和35 ng/m L,明显低于游离Epo B的IC5035和50 ng/m L。这可能是HA NPs更容易进入细胞内,然后将药物释放,进而抑制肿瘤细胞生长。     

基于硝基苯并呋咱的荧光探针

硝基苯并呋咱(NBD)作为一种通常从4-氯-7-硝基-苯并呋咱衍生化的荧光团,在荧光分析中具有简便、高效、灵敏度高以及检测限低等显著优点,已广泛应用于化学、生物、医药和环境等诸多研究领域。基于NBD的荧光探针是检测和识别重要的无机/有机小分子化合物、酶和蛋白质的研究热点之一。本文综述了近年来NBD作为荧光团在重金属离子(Zn2+,Cu2+和Hg2+)、活性氧、DNA、细胞膜、小分子化合物(硫酚、糖类、金刚烷/胆酸、氟甲沙明/埃博霉素、双酚A、多胺、TNT和PPi)、酶和蛋白质等检测领域的新进展。在不久的将来,设计合成结构更加精巧的NBD探针分子仍将是荧光检测和生物成像领域的主要发展趋势之一。这些新颖的NBD探针分子的应用将为全面深入探索与理解复杂的生命过程提供强有力的研究工具。     

新型酰胺金属配合物的热力学稳定性研究

酰胺在自然界中广泛存在,生物体内很多金属酶中的酰胺都参与了金属配位,文献表明,配位的金属离子可以促进酰胺的去质子化,去质子后的酰胺氮原子是一种良好的电子授体,当前对酰胺配体的研究已有报道,为模拟抗癌药物博莱霉素,Rowland等合成了一个新型五齿酰胺配体：N,N-双(2-吡啶甲基)胺-N-乙基-2-吡啶-2-甲酰胺(L),并对其三价铁配合物的单晶结构进行了表征,实验证明此配体在配合物中的配位环境和化学性质与博莱霉素非常相似。     

反相高效液相色谱法测定链霉菌中安来霉素A量

安来霉素又名恩来霉素、恩霉素,根据末端脂肪酸种类的不同,分为安来霉素A和安来霉素B两种组分。安来霉素对革兰氏阳性菌有很强的抑制作用,可作为饲料添加剂,安来霉素具有优良的促生长和改善饲料利用率的作用,同时具有稳定性高、肠道内不易降解、无交叉耐药性、无残留等优点。     

用低能电子衍射计算Ni(001)表面化学吸附氧族元素的表面原子层间距

用一维能带理论计算了Ni(001)表面化学吸附氧族元素(O、S、Se和Te)的表面原子层间距dx(X表示O、S、Se和Te). 当表面原子层间距dO=0.87±0.005埃, dS=1.29±0.01埃, dSe=1.44±0.01埃和dTe=1.93±0.01埃时, LEED谱计算值与实验结果一致.     

Review of Analytical Methods for Atmospheric Oxidants Measurements

Abstract

Instrumental and manual methods currently available for the measurement of atmospheric oxidants are surveyed. Techniques used in the United States are emphasized and their advantages and disadvantages are discussed. Commercial systems are evaluated in terms of general operating principles rather than of specific instruments. The ability of these techniques to meet the measurement requirements defined by U.S. Federal air quality oxidant criteria are discussed. Alternative chemical techniques that may have some advantages over the neutral, buffered KI procedure are discussed. Also some attractive, alternative instrumental procedures that are ozone-specific are presented. These systems are based on chemiluminescence and ultraviolet absorption photometry. Electrochemical and colorimetric methods for total oxidant measurements are compared. Finally, some data are presented on relationships of ozone and total oxidants.     

Densities,speeds of sound,excess volumes and viscosities of binary mixtures of mtbe with tetralin and decalin at 303.15 k

Measurements of densities, speeds of sound, excess volumes and viscosities of binary mixture of methyl tert-butyl ether with tetralin and decalin are reported at 303.15?K over the entire range of composition. Excess volumes are measured using batch dilatometer technique. Sound speeds are obtained using ultrasonic interferometer. Densities are computed from excess volume data. Isentropic compressibilities are derived from density and sound speed data. Speeds of sound are evaluated on the basis of Jacobson's free length theory and Schaff's collision factor theory. The predicted values are in good agreement with the experimental results. The viscosity data are analysed on the basis of corresponding states approach. Excess volumes and deviation in isentropic compressibilities are negative and deviation in viscosities are positive over the entire composition range. The experimental results are discussed in terms of possible molecular interactions between unlike molecules.     

若干含多硫基的配合物的合成方法及结构特征

本文综述了近年来我们合成的十二种多硫基的配合物，这些配合物含有Ｓ＾２－２，Ｓ＾２－４，Ｓ＾２－５，Ｓ＾２－６，Ｓ＾２－７等多硫革配体，总结了这些配合物中的金属配位构型，比较了各种多硫基的Ｓ－Ｓ键长及有关键角，归纳了配合物外光谱，并阐述了其中几个配合物与ＮＨ２ＮＨ２的反应性能。     

Some Strategies for the Refinement of Disordered Structures with the SHELXL-97 Refinement Program

1 INTRODUCTION finement stage. The person performing the crysta- llographic manipulations works on numerical data The high degree of order in the arrangement of that are quite different from the diffraction images atoms in a crystal is a fundamental characteristic of on a computer terminal, and most often does not even the crystalline state, an ideal crystal being envisaged see the images. to be constructed of regularly-stacked unit cells, each The refinement program, SHELXL-97[1], has …     

Contactless conductivity detection for microfluidics: designs and applications

Different methods for construction of contactless conductivity detectors (CCD) for microchip electrophoresis device are described in this review. This includes three main schemes of CCD for microchips, such as (i) the detection electrodes are placed along the microchannel from outside of the microchip and they are insulated from the channel by the cover lid of microchip device; (ii) the electrodes are placed across of the microchannel in the same plane and they are insulated by thin separation channel walls and (iii) electrodes are buried in widened part of microchannel and they are insulated from solution by ultrathin layer of silicon carbide. Specific issues related to the CCD on microfluidics are discussed, such as an influence of shape and magnitude of ac voltage and placement of electrodes and their insulation. Various applications for security, pharmacological, bioassays and food analysis purposes are described.     

Inorganic electrides

Inorganic electrides are a novel kind of ionic compounds in which the anions are electrons confined in a complex array of cavities or channels and the cations are nanoscale arrays of alkali metal ions that provide charge balance. In electrides the donated electron behaves like a low-density correlated electron gas, whereby the dimensionality of the electron gas and its electronic and magnetic properties are determined by the topology of the cavities in the host matrix. Unlike traditional electrides, in which alkali cations are encapsulated within an organic cage, inorganic electrides are thermally stable. The current inorganic electrides based on alkali metal loaded zeolites can be designed as useful reduced-dimensionality materials. Inorganic electrides are powerful reducing agents, and they are able to reduce small aromatic molecules to the radical anions within the channels of the zeolite.     

Synthesis,Redox and Spectroscopic Properties of Pterin of Molybdenum Cofactors

Pterins are bicyclic heterocycles that are found widely across Nature and are involved in a variety of biological functions. Notably, pterins are found at the core of molybdenum cofactor (Moco) containing enzymes in the molybdopterin (MPT) ligand that coordinates molybdenum and facilitates cofactor activity. Pterins are diverse and can be widely functionalized to tune their properties. Herein, the general methods of synthesis, redox and spectroscopic properties of pterin are discussed to provide more insight into pterin chemistry and their importance to biological systems.     

Nitrenium Salts in Lewis Acid Catalysis

Molecular compounds featuring nitrogen atoms are typically regarded as Lewis bases and are extensively employed as donor ligands in coordination chemistry or as nucleophiles in organic chemistry. By contrast, electrophilic nitrogen‐containing compounds are much rarer. Nitrenium cations are a new family of nitrogen‐based Lewis acids, the reactivity of which remains largely unexplored. In this work, nitrenium ions are explored as catalysts in five organic transformations. These reactions are the first examples of Lewis acid catalysis employing nitrogen as the site of substrate activation. Moreover, these compounds are readily accessed from commercially available reagents and exhibit remarkable stability toward moisture, allowing for benchtop transformations without the need to pretreat solvents.     

钼、钨系过氧化物在Sharpless烯烃环氧化反应中的应用*

钼、钨系过氧化物是非常重要的Sharpless烯烃环氧化催化剂,有着非常广泛的工业发展前景。本文综述了钼、钨系过氧化物的种类,结构,合成方法及催化活性,分析了各种钼、钨系过氧化物的特点以及在催化环氧化领域的发展现状。同时,本文还讨论了钼、钨系过氧化物催化烯烃环氧化反应的机理。评述了在催化环氧化领域中两种主要理论——Mimoun机理与Sharpless机理的争论焦点及发展现状,以及计算化学对两种理论中间过渡态的研究进展,并且重点分析了Sharpless机理的过渡态结构。此外,本文还综述了影响钼、钨系过氧化物催化剂反应活性的各种因素以及质子所产生的副反应。最后,本文对应用于催化环氧化领域的钼、钨系过氧化物未来的研究方向提出了建议。