光卟啉(YHPD)光敏作用的分子机制——YHPD对蛋白质微观光敏损伤的激光喇曼光谱研究

本文用已确定空间结构的溶菌酶为对象,采用可同时探测其主、侧链各基团变化的激光喇曼光谱技术,研究了YHPD对蛋白质空间结构的微观光敏损伤,获得以下新结果:(1)除5种已经发表的氨基酸(Trp,Tyr,Met,1/2 Cys和 His)外,还有苯丙氨酸和胱氨酸亦受到了光敏损伤;(2)定出氨基酸各基团对光敏作用敏感的次序;(3)被“埋藏”在蛋白质三维结构内部的色氨酸和酪氨酸也受到较强的损伤;(4)蛋白质的主链构象亦发生了明显的变化,有序结构(α-螺旋、β-折叠、β-回折)减少,无规卷曲增加.     

芳香氨基酸光敏化瞬态产物的光谱学及动力学表征

运用KrF激光闪光光解瞬态吸收光谱 ,以丙酮为光敏剂 ,研究了水溶液中芳香氨基酸的光化学反应 .通过动力学分析和猝灭实验 ,鉴别了光化学反应过程中的瞬态产物 ,获取了激发三重态的瞬态吸收光谱及动力学参数 .在丙酮存在下 ,色氨酸(Trp)和酪氨酸 (Tyr)的水溶液光解 ,分别观察到Trp激发三重态、N中心色氨酸自由基 (Trp/N·)和酪氨酸的酚氧自由基 (Tyr/O·) ,阐述了二者是丙酮三重态与Trp ,Tyr分别通过三重态 三重态 (T T)激发能转移和电子转移生成 ;苯丙氨酸 (Phe)不能与丙酮三重态进行激发能转移和电子转移 .进一步 ,在色氨酰酪氨酸 (Trp Tyr)敏化光解过程中 ,观察到分子内的电子转移 ,即Trp/N· Tyr→Trp Tyr/O·自由基的生成过程 .     

反相胶束膜模拟体系中氨基酸的光敏化氧化

研究了AOT/H_2O/甲苯反相胶束体系中,光敏剂H[TBC(O~iPr)_4P(OH)]的光化学性质及其对氨基酸的光敏化氧化.结果表明,反相胶束可促使光敏剂解聚,并提高其敏化产生和~1O_2~-的效率,溶于反相胶束水团中的色氨酸和酪氨酸可被H[TBC(O~iPr)_4P(OH)]光敏化氧化,反应以Ⅱ型机制(~1O_2)为主.氨基酸光氧化动力学研究表明,反相胶束所形成的微多相体系可改变光敏化反应的途径和动力学控制因素.     

UV-Vis-草酸铁络合物-H_2O_2体系产生羟自由基的Fe(phen)_3~(2+)光度法测定

UV-Vis-草酸铁络合物 -H2O2 法是一种新的高级氧化工艺 ,该工艺产生的羟自由基·OH具有极强的氧化能力 ,可与水中大多数有机物迅速反应而使其降解 ;用Fe(phen)32+ 光度法研究了该体系中羟自由基·OH产生的规律 ,·OH可将Fe(phen)32+(Fe2 +-菲咯啉络合物)氧化成Fe(phen)33+(Fe3 +-菲咯啉络合物),通过测定Fe(phen)32+ 在508nm处吸光度的变化可间接求出·OH的生成量 ;结果表明 ,在 pH=4.0,n(Fe2+)∶n(H2O2)∶n(C2O42-)=1∶5∶10(化学计量数 )时 ,·OH的生成量最大;该分析方法具有简单、快速的优点     

过渡金属离子掺杂Zn3(OH)2V2O7·2H2O的合成及其光催化性质

利用水热法合成了3d过渡金属离子掺杂Zn3(OH)2V2O7·2H2O的微米花结构,其分子式可表达为Zn3-3xM3x(OH)2V2O7·2H2O(其中M=Cu,Co,Ni,Mn;0.001≤x≤0.20)。应用XRD、SEM、TEM、UV-Vis DRS、EDX和BET等分析测试技术对产物进行了表征。结构和形貌分析结果显示过渡金属离子掺杂后产物仍保持Zn3(OH)2V2O7·2H2O的六方晶体结构,微米花由主晶面为(0001)的纳米片组装而成。紫外-可见漫反射光谱显示过渡金属离子掺杂后带边吸收红移,其中以Cu的掺杂产物Zn3-3xCu3x(OH)2V2O7·2H2O最为明显,带边吸收扩展到可见光区。首次对Zn3(OH)2V2O7·2H2O及其不同金属离子掺杂产物Zn3-3xM3x(OH)2V2O7·2H2O进行了可见光催化降解有机污染物的研究,结果显示与其它产物相比掺0.1at%Cu的Zn2.997Cu0.003(OH)2V2O7·2H2O对亚甲基蓝(MB)的可见光催化降解效果最好。对掺杂离子种类、掺杂离子浓度对产物可见光催化性质的影响也进行了考察。     

酪氨酸、脯氨酸和组氨酸的示波极谱连续测定

提出了用示波极谱法连续测定酪氨酸 ( Tyr)、脯氨酸 ( Pro)、组氨酸( His) 3种氨基酸的新方法。在 p H9.2硼酸缓冲溶液中 ,上述 3种氨基酸与镍发生配位反应 ,用示波极谱仪进行单扫描时 ,出现 3组灵敏度和分辨率均很高的二阶导数波谱 ,峰电位分别为 :Tyr - 1 .0 4 V,Pro - 1 .2 0 V,His - 1 .34V。酪氨酸、脯氨酸、组氨酸的峰电流与浓度分别在 2 .0× 1 0 -5～ 3.0× 1 0 -4 mol/L,3.2× 1 0 -6～ 2 .2× 1 0 -4 mol/L,4.0× 1 0 -5～ 2 .5× 1 0 -4 mol/L的范围内呈线性关系。该法已用于复方氨基酸注射液中酪氨酸、脯氨酸、组氨酸含量的测定。     

以316L不锈钢为基体的嵌入式预阳极化超薄碳糊电极同时测定多巴胺和酪氨酸

本文以316L不锈钢为基体,以简便快速的方法构建了嵌入式预阳极化超薄碳糊电极(316L-PAIUCPE).探究了多巴胺(DA)和酪氨酸(Tyr)在该电极上的电化学响应行为.详细讨论了酸度对DA和Tyr氧化峰电位和峰电流大小的影响.并且DA和Tyr的氧化峰电流与其浓度分别在8.0×10-7～8.0×104mol·L-1和...     

黄香楝树皮提取物的多酚含量及抗氧化研究

本文采用甲醇、乙醇、乙酸乙酯和水4种溶剂提取黄香楝树皮中的活性成分,Folin-Ciocalteu法测定提取物中的总酚含量,甲醇、乙醇提取物中酚类活性成分含量较高,总酚含量分别为58.59、50.47mg·g-1。采用DPPH自由基清除法、邻二氮菲-Fe2+氧化法、过氧化氢清除法、还原力法、磷钼络合物法等5种抗氧化性测定方法研究提取物的抗氧化活性,乙醇提取物浓度为1.0mg·mL-1时,对DPPH、·OH、H2O2的清除率均大于90%,对DPPH、·OH、H2O2的IC50值分别为234.2、555.2、60.1μg·mL-1。     

C_6H_2(OH)_3CH_3氧化成羟基苯甲酸反应路径的DFT研究

运用密度泛函(DFT)理论,采用Materials Studio 8.0,用GGA/BP方法研究了C_6H_2(OH)_3CH_3氧化成羟基苯甲酸的反应路径。结果表明,甲基上的氢原子被氧化成羟基以及羟基被氧化为醛基及醛基被氧化成羧基均为放热过程。分子C_6H_2(OH)_3CH_3中甲基氧化成羧基的主路径为三个氢原子氧化反应路径,其路径为C_6H_2(OH)_3CH_3+3O→C6H2(OH)3C(OH)3→C6H2(OH)3COOH+H2O,该路径受限于羟基直接被氧化成羧基过程,需克服130 k J/mol的反应势垒,反应速率常数对数ln(k)为-22.96 s-1;醛基、羟基优先被氧化成羧基的顺序为:-CHO-C(OH)3-HC(OH)2-H2C(OH);提高反应温度、氧气浓度均有利于羟基苯甲酸的生成,适当的催化剂有利于促进整个反应的进行。     

XMgO·YMg(OH)_2吸附剂除氟机理及其净化水的水质研究

研究了XMg O·YMg(OH)2对水中氟离子的吸附性能,考察了吸附时间、吸附剂用量、含氟水p H值、温度、含氟水初始浓度等因素对吸附的影响。实验结果表明,在较宽的p H(3.4~8.4)值和水温(22~51℃)范围内,XMg O·YMg(OH)2对水中氟离子具有极强的吸附能力,室温下0.4g XMg O·YMg(OH)2可将100m L浓度为30mg F-1·L-1含氟水处理为符合含氟标准的饮用水。氟离子在XMg O·YMg(OH)2上的吸附速率较大,30min内基本达到吸附平衡,吸附平衡符合Langmuir方程,在50min内达到饱和吸附,室温下饱和吸附量为13.46mg·g-1。净化水呈微碱性,含有5.68~15.07mg·L-1Mg2+,有益于人体健康。吸附饱和后的XMg O·YMg(OH)2经焙烧再生,除氟率可达81%。     

Thin-layer chromatographic separation of serotonin from epinephrine and norepinephrine

A thin-layer chromatographic procedure is reported for the separation of serotonin from epinephrine and norepinephrine. The method involves the use of ethylenediaminetetraacetic acid-impregnated silica gel G plates and n-butanol-ethanol-acetic acid-water (8:2:1:3) as developer. Serotonin is well separated from both epinephrine and norepinephrine. Epinephrine and norepinephrine overlapped slightly but were both detectable. The procedure is thus applicable to the separation of all three biogenic amines in spite of the absence of an absolutely clear separation of epinephrine from norepinephrine.     

Gels from a semifluorinated n-alkane in fluorinated solvents as a probe for intermolecular interactions

Diblock semifluorinated n-alkanes can form aggregates and gels in fluorinated solvents. We have investigated the thermal behavior of binary mixtures comprising F(CF₂)₈(CH₂)₁₆H and fluorinated solvents. The solvents were perfluorohexane, perfluoroheptane, perfluorooctane, perfluorooctyl bromide, perfluorodecalin, and perfluorotributylamine. The phase diagrams were used to calculate the activity coefficients of the two components and the main excess thermodynamic functions. The solubility and self-assembly behavior of F₈H₁₆ in the fluorinated solvents are related to the different solute–solvent dispersion interactions that depend on the polarizabilities and ionization potentials of the interacting species, and on the structural properties of the solvent.     

HCOO在Cu(110)、Ag(110)和Au(110)表面的吸附

采用密度泛函理论(DFT)以及广义梯度近似方法(GGA)计算了甲酸根(HCOO)在Cu(110)、Ag(110)和Au(110)表面的吸附. 计算结果表明, 短桥位是最稳定的吸附位置, 计算的几何参数与以前的实验和计算结果吻合. 吸附热顺序为Cu(110)(-116 kJ·mol-1)>Ag(110)(-57 kJ·mol-1)>Au(110)(-27 kJ·mol-1), 与实验上甲酸根的分解温度相一致. 电子态密度分析表明, 吸附热顺序可以用吸附分子与金属d-带之间的Pauli 排斥来关联, 即排斥作用越大, 吸附越弱. 另外还从计算的吸附热数据以及实验上HCOO的分解温度估算了反应CO2+1/2H2→HCOO的活化能, 其大小顺序为Au(110)>Ag(110)>Cu(110).     

Transition metal complexes of the tripodal ligand 4-(2′-pyridylmethyl)-4-azaheptane-1,7-diamine. Crystal structures of [CuLCl]ClO4 and [NiL(MeCN)2](ClO4)2

The tripodal ligand 4-(2′-pyridylmthyl)-4-azaheptane-1,7-diamine has been prepared by reaction of 2-aminemethyl pyridine with acrylonitrile, followed by the reduction of the nitrile groups. Copper(II), nickel(II), zinc(II), cobalt(III) and chromium(III) complexes of the ligand have been prepared and characterized and the crystal structures of the complexes [CuLCl]ClO₄ and [NiL(MeCN)₂](ClO₄)₂ determined. The copper complex is five coordinate with approximate square pyramidal stereochemistry with the apical position occupied by a primary amine donor. The nickel complex is octahedral with the pyridine nitrogen donor lying trans to an acetonitrile ligand.     

Magnetism of metal-nitroxide compounds involving bis-chelating imidazole and benzimidazole substituted nitronyl nitroxide free radicals

Coordination compounds based on imidazole and benzimidazole substituted nitronyl nitroxide radicals with transition metal ions and trivalent lanthanide ions are described from the perspective of their magnetic properties.For the transition metal compounds the crystal structures show various metal-nitroxide dimensionalities including mononuclear (0D), one-dimensional (1D) and two-dimensional (2D) complexes. The mononuclear complexes were isolated with most metal ions of the first transition series. One copper(II) complex shows a copper(II)-radical ferromagnetic coupling (J = +75 cm⁻¹) while for the other mononuclear compounds, mainly with manganese(II), the metal-radical interactions are antiferromagnetic. The one-dimensional and two-dimensional complexes are manganese(II) compounds which show canting effects leading to weak ferromagnetism.For the trivalent lanthanide ions [La(III), Gd(III) and Eu(III)], three series of mononuclear complexes were obtained in which the metal center is bound to four, two or one nitroxide radicals depending on the counter ions and ancillary ligands. Unexpectedly, in most gadolinium(III) complexes, the Gd(III)-radical interactions were found to be antiferromagnetic in contradiction with other foundings and previous theoretical models. In support to the magnetic studies, the optical properties of the lantanide complexes have also been investigated and are briefly described.     

Simple,Selective, and Sensitive Spectrophotometric Method for Determination of Trace Amounts of Nickel（Ⅱ）, Copper （Ⅱ）, Cobalt （Ⅱ）, and Iron （Ⅲ） with a Novel Reagent 2-Pyridine Carboxaldehyde Isonicotinyl Hydrazone

A selective and sensitive reagent of 2-pyridine carboxaldehyde isonicotinyl hydrazone（2-PYAINH） was synthesized and studied for the spectrophotometric determination of nickel, copper, cobalt, and iron in detail. At a pH value of 7.0, 9,0, 9.0, and 8.0, respectively, which greatly increased the selectivity; nickel, copper, cobalt, and iron reacted with 2-PYAINH to form a 1：2 yellow-orange, 1：2 yellow-green, 1：2 yellow and 1：1 yellow complexes, with absorption peaks at 363, 352, 346, and 359 nm, respectively. Under the optimal conditions, Beer＇s law was obeyed over the ranges of 0.01-1.4, 0.01-1.5, 0.01-2.7, and 0.01-5.4 mg/L respectively. The apparent molar absorptivity and Sandell＇s sensitivities were 8.4×10^4, 5.2×10^4, 7.1×10^4, and 3.9×10^4 L·mol^-l·cm^-1, respectively, and 0.00069, 0.0012, 0.00078, and 0.0014 μg·cm2, respectively. The detection limits were found to be 0.001, 0.002, 0.003, and 0.01 mg/L, respectively. The detailed study of various interfering ions to make the method more sensitive was carried out and selective and several real samples were analyzed with satisfactory results.     

柴油加氢精制催化剂制备技术

柴油加氢精制催化剂制备技术的发展大致经历了3个阶段,由此形成了三代柴油加氢催化剂:单层分散的负载型金属硫化物催化剂,多层分散的负载型金属硫化物催化剂和非负载型金属硫化物催化剂。本文对金属硫化钼基柴油加氢精制催化剂的应用背景、制备思想及催化剂研究开发现状进行了系统的总结,对柴油加氢催化剂的发展方向进行了展望。     

New Complexes of Ditopic Ligands with “d” and/or “s” Metal Ions

Abstract

The asymmetric compartmental macrocycles containing one N₂O₂ or N₃O₂ Schiff base and one O₂O₃ or O₂O₄ crown-ether like chamber, have been obtained by condensation reaction of the formyl precursors 3,3′-(3-oxapentane-1, 5-diyldioxy) bis (2-hydroxybenzaldehyde) or 3,3′-(3,6-dioxaoctane-1,8-diyldioxy)-bis(2-hydroxybenzaldehyde) with ethyl ethylenediamine (H₂L_A, H₂L_C), 1,5-diamino-3-azamethylpentane(H₂L_B, H₂L_D), also in the presence of metal ions as templating agents. These ditopic ligands, with dissimilar coordination sites, have been designed and used for the selective complexation of “d” and/or “s” metal ions, respectively into the Schiff base and the crown ether chamber. The selectivity of these processes strongly depends on the size and on the donor atom sets of the sites. The possibility to obtain mononuclear M(L)·nH₂O (M = Ni²⁺, Cu²⁺, Co²⁺), Mn(L)(CH₃COO)·nH₂O or Na(L) and hetero-dinuclear MNa(L)(CH₃COO) (M = Ni²⁺, Cu²⁺, Co²⁺) and MnNa(L)(CH₃COO)₂·nH₂O complexes has been successfully tested. The ligands and complexes have been characterized by ir, nmr, mass spectrometry and magnetic susceptibility measurements.

Two of the ligands used for the preparation of the solid samples, i.e., to H₂L_A and H₂L_B, have been employed to study complexation reactions of Co(II) and Na(I) in solution. In order to obtain information on the ligand preorganization effect toward the complex stabilities, a simpler open chain parent compound of H₂L_B (H₂L_E) has been also prepared and studied. FT-IR spectra show that H₂L_A is unable to complex Na⁺ in DMSO while the complexation reactions of Na⁺ by H₂L_B and of Co²⁺ by H₂L_A take place with slow kinetics. Therefore, thermodynamic data have been obtained only for the systems Co²⁺/H₂L_B and Co²⁺/H₂L_E. The thermodynamic parameters obtained for the complexation reactions show that the pre-organization of the donor atoms in H₂L_B does not add a significant contribution to the stabilities of the complexes. Both H₂L_B and H₂L_E form in DMSO 1:1, 1:2 and 1:3 = M:L complexes with very similar stabilities and almost equal enthalpies of formation. Physico-chemical studies suggest besides that the slow reaction of Na⁺ with H₂L_B is probably due to the formation of a 1:1 complex where the metal cation, initially occupying the O₃ cage of the ligand, slowly binds also the oxygens of the phenolic moieties. Spectral and calorimetric data on solutions containing H₂L_B and different Co²⁺: Na⁺ ratios evidence that in DMSO no stable heterodinuclear complexes form when the neutral ligand is considered.     

Synthesis of Some Novel Class of Bis(isoxazoline) and Bis(aziridine) Derivatives

Synthesis of some new bis(isoxazoline) derivatives has been described from terepthaldehyde derived bis(nitrones) using microwave irradiation via 1,3‐dipolar cycloaddition reaction. Bis(isoxazoline) derivatives in turn successfully converted into new bis(aziridine) derivatives via Baldwin rearrangement. Simple reaction methodology, non involvement of catalysts, and good to excellent yields are the important features noticed in this synthesis.     

PMDA-BPDA-HAB聚苯并噁唑的合成及耐热性

用廉价的均苯四甲酸二酐(PMDA)代替部分或全部3,3,′4,4′-联苯四羧酸二酐(BPDA),与3,3′-二羟基联苯胺(HAB)进行缩聚,然后脱水酰亚胺化,制备了5种聚酰亚胺(PI)。TGA分析显示,这些PI的DTG曲线为2个峰,可分为生成聚苯并唑(PBO)再发生PBO分解的2个阶段。PI膜在500℃通N2气1 h,所得聚合物膜的DTG曲线仅为1个峰,表明这些PI可充分转变成PBO。用FTIR表征了PI和PBO膜的结构。PBO的耐热性(用失重5%时的温度Td表示)比PI高100~170℃。PMDA-HAB PBO的耐热性高于BPDA-HABPBO。HAB-BPDA-PMDA PBO的耐热性优于二元PBO。当PMDA在二酐单体中所占的摩尔分数为75%时,PBO的Td高达643℃。