咪唑并吡啶类化合物的合成及其应用*

咪唑并吡啶类化合物具有与吲哚、氮杂吲哚等类似的特殊结构和良好的生物活性,在医药和农药工业有着广泛的应用,成为有机化学家和药物化学家的研究热点。咪唑并吡啶类化合物主要有咪唑并[4,5-b]吡啶、咪唑并[4,5-c]吡啶、咪唑并[1,2-a]吡啶和咪唑并[1,5-a]吡啶等4个类型。本文阐述了近年来咪唑并吡啶类化合物的合成研究进展和应用情况,主要介绍了咪唑并[4,5-b]吡啶和咪唑并[4,5-c]吡啶这两类化合物的合成方法和在医药及农药领域的应用。     

间对二氯苯在盐水溶液中活度系数的研究

本文用紫外可见分光度法测定了25℃下间位和对位二氯苯在NaF,NaCI,KBr,Na~2CO~3,K~2So~4,Et~4NBr水溶液中的活度系数,Logf-c~5关系符合Setschenow 盐效应经验公式,盐效应次序为,Na~2CO~3>K~2So~4>NaF>NaCi>NaBr>Et~4NBr. 通过比较发现:二氯苯的偶极矩对盐效应几乎没有影响,本文选取Debye-Mcaulay( DMT)和Conway-Desnoyers-smith(CDST)静电作用理论,定表标粒子理论(SPT)及改进前后的内压力理论IPT和XIPT),计算出理论值,与实验值进行比较, 证实的内压力理论计算值更接近实际.     

Average electron tunneling route of the electron transfer in protein media

We present a new theoretical method to determine and visualize the average tunneling route of the electron transfer (ET) in protein media. In this, we properly took into account the fluctuation of the tunneling currents and the quantum-interference effect. The route was correlated with the electronic factor in the case of ET by the elastic tunneling mechanism. We expanded by the interatomic tunneling currents 's. Incorporating the quantum-interference effect into the mean-square interatomic tunneling currents, denoted as , we could express as a sum of variant Planck's over 2pi(2). Drawing the distribution of on the protein structure, we obtain the map which visually represents which parts of bonds and spaces most significantly contribute to . We applied this method to the ET from the bacteriopheophytin anion to the primary quinone in the bacterial photosynthetic reaction center of Rhodobacter sphaeroides. We obtained 's by a combined method of molecular dynamics simulations and quantum chemical calculations. In calculating , we found that much destructive interference works among the interatomic tunneling currents even after taking the average. We drew the map by a pipe model where atoms a and b are connected by a pipe with width proportional to the magnitude of . We found that two groups of 's, which are mutually coupled with high correlation in each group, have broad pipes and form the average tunneling routes, called Trp route and Met route. Each of the two average tunneling routes is composed of a few major pathways in the Pathways model which are fused at considerable part to each other. We also analyzed the average tunneling route for the ET by the inelastic tunneling mechanism.     

Source Apportionment Research of Fine Particulate Matter in the Atmosphere by PAHs

Haze weather frequently occurs in many cities in China. Polycyclic aromatic hydrocarbons(PAHs) in fine particulate matter(PM_2.5) can adversely affect the environment and human health. In this paper, PM_2.5 samples were collected at nine sites in a city in northeastern China from September 2013 to October 2014. Sixteen USEPA(US Evironment Protection Agency) priority PAHs in PM_2.5 were analyzed to determine their spatial and temporal distribution characteristics. The source apportionment of PAHs was conducted with the Positive Matrix Factorization(PMF) model. The results indicate that the concentrations of total PAHs(T-PAHs) in PM_2.5 are within the range of 0.26 to 72.48 ng/m³. The seasonal variation of T-PAHs is winter >spring >autumn >summer, and the space distribution of PAHs is JZP >DP >BFH >LP >EESA >IPT >CP >HZMC >JYP. In all types of PAHs, three-ring and five-ring PAHs are significantly prominent(62%) in the heating period due to petrogenic sources and traffic emissions. Middle- and high-ring PAHs in the non-heating period are caused by coal combustion and vehicle exhaust, which accounts for 77% of the total emissions. The source apportionment results obtained by the diagnostic ratio of PAHs reflect that coal burning, traffic and other sources have a distinct influence on PAH emissions in this city. Six factors are defined by PMF v5.0, namely, coke oven emissions(7.7%), biomass burning(44.3%), petrogenic sources(10.7%), coal combustion(10.4%), gasoline engine emissions(16.7%), and diesel engine emissions(10.3%). The results indicate that the PAHs in PM_2.5 in the city are primarily caused by combustion processes and vehicle exhaust.     

金属纳米颗粒制备中的还原剂与修饰剂*

金属纳米颗粒由于其独特的光学、电学、化学性质以及各种潜在的应用价值,受到不少研究人员的广泛关注。实现金属纳米粒子尺寸、形貌可控,改善粒子分散性和稳定性,提高产率及纯度已成为具有挑战性的研究课题,不断发展和完善金属纳米粒子的合成方法则显得尤为重要。本文总结了目前制备金属纳米材料的几种化学方法：化学试剂还原法、电化学还原法、辐射还原法等,分类介绍了化学试剂还原法中常用的无机、有机还原剂,以及含氮、磷、羧基、巯基小分子有机化合物以及高分子聚合物等修饰剂并重点总结了其还原和修饰机理。     

Hydrogen-bonding interactions in ferrocene-peptide conjugates containing valine

The synthesis and characterization of a series of ferrocene (Fc) peptide conjugates containing the amino acid valine is reported, where the peptide substituents are part of the hydrophobic sequence of the amyloid β-peptide. The hydrogen-bonding (H-bonding) interaction in these compounds is studied by variable temperature ¹H NMR spectroscopy. The solid-state structures, determined by single crystal X-ray crystallography, of two of the conjugates (Fc[CO-Leu-Val-OMe]₂1 and Fc[CO-Gly-Val-OH]₂6) are reported. Both structures are stabilized by intramolecular H-bonds exhibiting the familiar “Herrick motif” involving the proximal amide NH and the amide CO of the adjacent amino acid. This motif is sufficiently rigid and is maintained in solution as suggested by CD studies. However, the intermolecular H-bonding patterns observed on conjugates 1 and 6 are significantly different resulting in very different supramolecular architectures. For conjugate 1, a more conventional set of head-to-tail stacking interactions which is stabilized by β-sheet-like H-bonding interactions between the individual molecules is observed. However, for conjugate 6, the presence of the C-terminal acid group and presumably the flexibility of the Gly linker enables the formation of a more open structure that contains hydrophobic channels occupied by solvent molecules.     

Acceleration of carbon-13 spin-lattice relaxation times in amino acids by electrolytes

Measurements of the enhancement, by various electrolytes, of the spin-lattice relaxation time of carbon-13 at different locations in a number of amino acids are reported. Spin-lattice relaxation times T1 of all the carbons in amino acids generally tend to decrease with increase in the concentration of electrolytes, the largest effects often being observed for the charged carboxylate groups of the amino acids. Carboxylic carbons in amino acids are the sensitive 'acceptor' of the 13C spin-lattice relaxation accelerating effects offered by electrolytes, and the 13C spin-lattice relaxation accelerating ability of electrolytes decreases in the order Mg(ClO4)2 > MgCl2 > CaCl2 > NaCl > KCl > LiClO4 > NaOH. The mechanisms of the observed phenomena are discussed in terms of intermolecular interaction, paramagnetic impurities in electrolytes and other mechanisms; large contributions of intermolecular interactions with electrolytes are present on complex formation between amino acids and metal ions and the incoming 'unsaturation' of the primary solvation shell of cations with the increase in electrolyte concentration.     

植物环蛋白研究进展*

植物环蛋白(cyclotides)是一类植物中富含二硫键、由28-37个氨基酸残基组成的大环蛋白,其分子中含有一个结构独特的环胱氨酸结(cyclic cystine knot, CCK)。由于其独特的结构和广泛的生物活性,如子宫收缩、溶血、抗肿瘤、抗微生物等活性,及其能耐常规的高温、酸解和酶解的稳定结构,可作为多肽药物设计中的模板分子进行结构修饰或活性多肽的载体,而在国际上引起广泛的关注。目前从堇菜科、茜草科和葫芦科约30种植物中发现100多个植物环蛋白,研究主要集中在澳大利亚、瑞典和美国等几个研究组,近年我们也在开展相关研究。本文主要从植物环蛋白的提取、分离、检测与结构鉴定方法,结构与性质,序列的同源性及分类,化学合成与生物合成,生物活性以及应用前景等几个方面介绍植物环蛋白的研究进展。     

Latest Developments in Proton Conductors

Solid proton conductors are receiving considerable attention, stimulated by the need of pollution control and with the objective to develop future microprotonics. The latest striking developments in the study of proton conductors are presented:

• i)Hydrogen containing perovskites, with a discussion of the nature and location of hydrogen inprotonic and electronic high-temperature superconductors;
• ii)Novel forms of hydrogen in disordered and mixed conductors, with the problems of the vibrational proton transfer assistance assumed by some authors and the independent proton dynamics evidenced by inelastic neutron scattering;
• iii)Frequency dependent conductivity and dielectric relaxation, including thermally stimulated current experiments in hydrated synthetic and biological gels (seeds);
• iv)Proton conducting membranes as candidates to replace Nafion®-like materials in H₂ (methanol) fuel cells.

     

Guest inclusion in cyclic imides containing flexible tethers

Guest inclusion properties of two cyclic imides which have carboxylic acids connected through flexible tether, namely, 4-(1,3-dioxo-1,3-dihydro-isoindol-2-ylmethyl)-cyclohexanecarboxylic acid (1) and 4-(1,3-dioxo-1H,3H-benzo[de]isoquinolin-2-ylmethyl)-cyclohexanecarboxylic acid (2) are studied. The crystals of host 1 containing one molecule of 1, the crystals of 4,4′-bipyridine (bpy) cocrystal of 1 containing one molecule of 1 and half molecule of bpy (1a), the crystals of 1,4-dioxane solvate of 1 containing two molecule of 1 and one and half molecule of 1,4-dioxane (1b) and the crystals of quinoline solvate of 1 containing one molecule of 1 and one molecule of quinoline (1c) in their crystallographic asymmetric units are investigated. Intermolecular hydrogen bonded two dimensional (2D) sheet structure of 1 and 3D channel network of 1b are comprised of cyclic R ₂ ² (8) hydrogen bond motifs; whereas cleavage of dimeric carboxylic acid R ₂ ² (8) motifs occurs in the structures of 1a and 1c in which 3D host–guest networks are comprised of discrete O–H···N and cyclic R ₂ ² (7) interactions, respectively. Various types of weak interactions between the two symmetry nonequivalent host molecule are found to be responsible for the formation of channels (14 × 11 Å) filled by guest 1,4-dioxane molecules in the crystal lattice of 1b. Two different solvates of 2 containing one molecule of 2 with a water molecule (2a) and one molecule of 2 with a quinoline molecule (2b) in their crystallographic asymmetric units, respectively, are also crystallized in different space groups. The quinoline molecules are held with host molecules by discrete O–H···N and C–H···O interactions and reside inside the voids formed by 3D repeated hexameric assemblies of host molecules in the crystal lattice of 2b.     

液相微萃取研究与应用

液相微萃取是近年来新兴的一种微型化样品前处理技术。该技术集萃取、净化、浓缩于一体,具有溶剂耗量少、成本低廉、操作便捷、精确和灵敏度高的特点。本文全面深入地综述了液相微萃取的各种工作模式及其原理和特点,阐述了相关的联用分析技术和方法的适用性,归纳和分析了影响萃取的主要影响因素及优化的方法,突出了上述几方面中具有发展潜力的新进展,包括各种动态萃取模式与装置、 与其它技术联用的新策略、离子液体作为萃取溶剂等,详细总结了近年来液相微萃取技术在环境、药物和食品等分析领域中的应用情况。     

Substituted benzotriazoles as inhibitors of copper corrosion in borate buffer solutions

The adsorption of substituted 1,2,3-benzotriazoles (R-BTAs) onto copper is measured via ellipsometry in a pure borate buffer (pH 7.4) and satisfactorily described by Temkin’s isotherm. The adsorption free energy (?ΔG _a ⁰ ) values of these azoles are determined. The (?ΔG _a ⁰ ) values are found to rise as their hydrophobicity, characterized by the logarithm of the partition coefficient of a substituted BTA in a model octanol–water system (logP), grows. The minimum concentration sufficient for the spontaneous passivation of copper (C _min) and a shift in the potential of local copper depassivation with chlorides (E _pt) after an azole is added to the solution (i.e., ΔE = E _pt ⁱⁿ ? E _pt ^backgr characterizing the ability of its adsorption to stabilize passivation) are determined in the same solution containing a corrosion additive (0.01М NaCl) for each azole under study. Both criteria of the passivating properties of azoles (logC _min and ΔE) are shown to correlate linearly with logP, testifying to the role played by surface activity of this family of organic inhibitors in protecting copper in an aqueous solution.     

Thermodynamic characteristics of protolytic equilibria in aqueous solutions of glycyl peptides

Protolytic equilibria in aqueous solutions of glycyl-DL-serine, glycyl-DL-threonine, and glycyl-DL-valine are investigated by means of potentiometry and calorimetry. Dissociation constants and heat effects of the above dipeptides are determined. Standard thermodynamic characteristics (pK°, Δ_disG°, Δ_disH°, Δ_disS°) of the investigated equilibria are calculated. The obtained results are compared to corresponding data on relative compounds.     

交联酶聚体技术研究进展*

交联酶聚体（CLEAs）是一类新型的固定化酶技术,具有制备简单、酶活回收率高、操作和保存稳定性强等优点。近年来,CLEAs技术与材料学、印迹工程、介质工程、反应工程学等相结合取得了一系列新进展,包括载体固定化CLEAs、包埋CLEAs、印迹法CLEAs、多酶CLEAs、CLEAs膜浆反应器等,在手性分子拆分与合成。抗生素生产等领域取得了一些成果。本文对CLEAs酶活影响因素及CLEAs技术的最新研究进展进行了分析与总结,并展望了需进一步深入开展的内容,有助于生物工程、酶工程、化学工程和材料科学等领域相关研究工作的开展。     

Studying the local structure of liquid in chloro- and alkyl-substituted benzene derivatives via the molecular scattering of light

The coefficients of scattering and the depolarization of scattered light are measured in liquid benzene, chlorobenzene, o-dichlorobenzene, o-chlorotoluene, toluene, and o-xylene in the temperature range of 293?368 K at a wavelength of 546 nm. Isothermic compressibility, internal pressure, and the functions of radial and orientational correlation are calculated for these liquids in the indicated temperature range, using the classical theory of molecular light scattering. We show that the local structure of these liquids is determined by orthogonal contacts between benzene rings (the T-configuration) and stacked (S-type) configurations. T-configurations predominate in benzene, chlorobenzene, and o-chlorotoluene, while toluene, o-xylene, and o-dichlorobenzene are characterized by S-configurations. It is also shown that the local structures of these liquids are reorganized in a certain temperature range.     

Molecular Structure of Triphenylamine in the Gas Phase

The molecular structure of triphenylamine was studied by gas-phase electron diffraction in combination with ab initio calculations. It is found that in the gas phase at 160°C the molecule possesses C₃ symmetry. The principal geometric parameters are as follows (r _a structure): N-C 1.421(4), C-C_mean 1.399(1), C-H 1.123(2) Å, bond angles NCC 123.6(10)° and 117.2(7)°, and CNC 119.9(2)°. Torsion angles around C-N bonds are ?39° and ?45°. Phenyl groups are rotated by 48° from the position in which the C₃ axis lies in the phenyl ring plane.     

Reactions of first-row transition metal ions with propargyl alcohol in the gas phase

The gas-phase reactions with propargyl alcohol (PPA) of all the singly charged ions of the first-row transition metals, generated by laser ablation in an external ion source, were studied by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICRMS.). The reactivities of the metal ions change irregularly across the periodic table, and the reactivity of each ion is a function of its electronic configuration and corresponding metal-oxygen (M-O) bond energies. The 10 metal ions were classified into three categories according to their reactivities: Sc(+), Ti(+) and V(+) are the most reactive ions which react with PPA to give many kinds of oxygen-rich products due to stronger M-O bonds; Fe(+), Co(+) and Ni(+) are less reactive; Cr(+), Mn(+), Cu(+) and Zn(+) are the most unreactive ions, due to the half and completely occupied valence electronic configurations. The order of reactivity is Ti(+) > V(+) > Sc(+) > Co(+) > Fe(+) approximately Ni(+) > Zn(+) > Cr(+) approximately Mn(+) approximately Cu(+).     

Ion-molecular interactions in solutions of potassium and cadmium thiocyanates in N-methylpyrrolidone at 298.15 k, according to calorimetry and densitometry data

The heat capacity and density of KNCS-N-methylpyrrolidone (MP), Cd(NCS)₂-MP, and KNCS-Cd(NCS)₂-MP solutions at 298.15 K are studied by means of calorimetry and densitometry. Standard partial molar heat capacities and volumes ( $\bar C^\circ _{p,2} $ and $\bar V^\circ _2 $ ) of the studied electrolytes in MP are calculated. Standard values of heat capacity $\bar C^\circ _{p,i} $ and volume $\bar V^\circ _i $ of NCS^? ions in MP at 298.15 K are determined. Values of the heat capacity and volume changes upon the formation of the three-component system KNCS-Cd(NCS)₂-MP from binary solutions are obtained and discussed.