吡啶-2-甲醛缩水杨酰腙锌(Ⅱ)和镍(Ⅱ)配合物的合成及晶体结构

利用水热法合成2种吡啶-2-甲醛缩水杨酰腙配合物[Zn(C13H10N3O2)2]·H2O(1)和[Ni(C13H11N3O2)2]2(CH3CH2OH)(SO4)2·3H2O(2),并测定了晶体结构.结果表明1属单斜晶系,空间群P21/c,其晶胞参数为:a=12.4352(14),b=17.878(2),c=13.8...     

新型含吡啶环席夫碱的合成及其晶体结构

[N,N'-(2-胺基苯基)-2,6-二甲酰亚胺]吡啶分别与苯甲酰丙酮和4-甲氧基水杨醛通过缩合反应合成了新型含吡啶环席夫碱(1a和1b),其结构经X-射线单晶衍射,1H NMR,IR和元素分析表征.1a属三斜晶系,空间群P-1,晶体参数a=11.895(4)(A),b=12.584(4)(A),c=13.191(4)...     

新型N-[2-((取代苯基)氨基)吡啶-3-基]嘧啶甲酰胺的合成、杀菌活性及分子对接

为寻找新型结构的琥珀酸脱氢酶抑制剂,以高效杀菌剂啶酰菌胺为先导化合物,设计、合成了17种N-[2-((取代苯基)氨基)吡啶-3-基]-4-甲基-2-甲硫基嘧啶-5-甲酰胺(4a～4g)和N-[2-((取代苯基)氨基)吡啶-3-基]-4-甲氧基-2-甲硫基嘧啶-5-甲酰胺(4h～4q),并通过~1H NMR、~(13)C NMR和MALDI-TOF-MS确证了化合物的结构.离体杀菌活性试验表明,在剂量为50μg/mL时, 16种化合物对菌核菌表现出较高的杀菌活性,抑制率在90%以上.一些化合物在此剂量下对灰霉菌显示出中等活性,抑制率为70%～84%.分子对接研究揭示了具有较高活性的化合物,N-[2-((3-氟-4-甲基苯基)氨基)吡啶-3-基]-2-甲硫基-4-甲氧基嘧啶-5-甲酰胺(4p)与琥珀酸脱氢酶(SDH)靶酶氨基酸形成4个氢键和一个阳离子-π相互作用.     

2,6-吡啶二亚胺基锰(Ⅲ)配合物的合成、晶体结构及催化性能

由三齿含氮配体2,6-二[1-(2,6-二甲基苯基亚胺)乙基]吡啶(L1)、2,6-二[1-(2,6-二乙基苯基亚胺)乙基]吡啶(L2)和2,6-二[1-(2,4,6-三甲基苯基亚胺)乙基]吡啶(L3)分别与MnCl2·4H2O在乙腈中反应,合成了3个新的具有较大空间位阻的2,6-吡啶二亚胺基氯化锰配合物L1Mn(Ⅱ)...     

吡啶-2, 6-二[N-(1′-咪唑基丙基)甲酰胺]及其锌(Ⅱ)、镉(Ⅱ)配合物的合成与光谱学研究

以吡啶-2,6-二甲酸为起始原料,经酯化后与N-(3-氨基丙基)咪唑反应合成了有机配体分子吡啶-2,6-二[N-(1'-咪唑基丙基)甲酰胺](L)及其锌(Ⅱ)、镉(Ⅱ)配合物。配体L的结构经1H NMR、13C NMR、IR、UV和元素分析表征,并采用单晶X-射线衍射方法确定了L的晶体结构,L属于正交晶系,Pbcn空间群,晶胞参数a=25.03(2),b=8.933(7),c=20.101(16),α=β=γ=90°,V=4495(6)3,Z=8,Dc=1.287g·cm-3,μ=0.095mm-1,F(000)=1856。通过元素分析确定锌(Ⅱ)、镉(Ⅱ)配合物的组成分别为(C19H23N7O2)2Zn2(ClO4)2·(CH3O)2·2H2O和(C19H23N7O2)2Cd2(ClO4)·(CH3O)3·2H2O,并采用对比分析的方法讨论了配位前后游离配体L和两种配合物的红外吸收光谱和紫外吸收光谱的谱学性质。     

咪唑/三唑羧酸配体配合物的合成及性能研究

本文以含咪唑/三唑基的两种有机羧酸H2L1和H2L2(H2L1=2-(4-(1H-1,2,4-三唑-1-基)苯基)-1H-苯并[d]咪唑-5-羧酸;H2L2=2-(4-(1H-咪唑-1-基)苯基)-1H-苯并[d]咪唑-5-羧酸)为配体,在溶剂热条件下合成三种新的金属配合物[Co(HL1)2(H2O)4] (1),[N...     

4-[2-(4,6-二甲氧基-2-嘧啶氧基)苄胺基]苯甲酸正丙酯的合成和晶体结构

2-甲砜基-4,6二甲氧基嘧啶和N-(4-丙氧羰基苯基)-2-羟基苄胺在四氢呋喃溶液中反应, 生成标题化合物4-[2-(4,6-二甲氧基-2-嘧啶氧基)苄胺基]苯甲酸正丙酯,并测定了其晶体结构。该化合物分子式为C23H25N3O5,晶体属单斜晶系,空间群为P2/n,晶胞参数为a = 14.8504(8),b = 9.4420(4),c = 16.3129(9) 牛 = 104.881(1)埃琕 = 2210.6(2) 3,Z = 4,Dc = 1.272 g/cm3,F(000) = 896.00,(MoK? = 0.91 cm-1,R = 0.051,wR = 0.118,获得19761衍射数据,其中独立衍射点5004个。经元素分析、IR、MS和HNMR等对化合物的结构进行了表征。在分子结构中,各有3个不同的共轭平面。嘧啶环和苯环(C(7) C(12)),及苯环(C(14) C(19))的夹角分别为99.18 , 164.15埃?个苯环之间的夹角为94.93啊;衔锍世啻焦瓜蟆?     

N-(1-甲基-4,5-二溴-2-三氯乙酰基)甘氨酸甲酯的合成与晶体结构

合成了N-(1-甲基-4,5-二溴-2-三氯乙酰基)甘氨酸甲酯(C9H10Br2N2O3, Mr=354.01),X-射线单晶衍射确定其属于正交晶系,P2(1)2(1)2(1) 空间群, a=6.4237(18)(A), b=13.445(4)(A), c=14.054(4)(A), α=β=γ= 90°, V=1213.8(6)(A)3, Z=4, Dc=1.937 Mg·m3, μ=6.672 mm-1, F(000)=688.有2257个可观察点[I>2σ(I)],最终R1=0.0275, wR2=0.0682.X-射线晶体结构的分析表明该化合物含羰基、酰胺基、酯基与溴原子,并且通过N(2)H与O(2)分子间氢键连成一维链状结构.     

含二胺基-锑配体的高自旋亚铁配合物:合成、表征及其与有机叠氮和重氮化合物的反应

通过PhSbCl_2与2 equiv.2-(N-锂-N-(2',6'-二氯苯基)胺基)苯基锂的反应合成了二(2-(N-(2',6'-二氯苯基)胺基)苯基)苯基锑[H_2(~(dcp)N_2Sb)].利用H_2(~(dcp)N_2Sb)与[Fe(N(SiMe_3)_2)_2]_2的胺消除反应合成得到二胺基-锑配位的亚铁配合物[(κ~3-N,N,Sb~(dcp)N_2Sb)Fe(THF)](1).配合物1为首例高自旋型有机锑-铁配合物.配合物1与有机叠氮化合物RN_3[R=dcp(2,6-Cl_2C_6H_3)],Dipp(2,6-~iPr_2C_6H_3))反应生成二胺基-锑亚胺配位的亚铁配合物[(κ~3-N,N,N-~(dcp)N_2SbN~R)Fe(py)](R=dcp,2;R=Dipp,3).配合物1与重氮化合物反应生成二胺基-锑叶立德配位的亚铁配合物[(κ~3-N,N,C-~(dcp)N_2Sb C~(R1,R2))Fe(PMe_3)](R~1=H,R~2=CO_2Bu~t,4;R~1=Ph,R~2=CO_2Et,5).锑配体H_2(~(dcp)N_2Sb)和配合物1～5经元素分析、~1H NMR、溶液相磁化率、单晶X射线衍射等进行了表征.     

基于二氰根铬的一系列氰根桥联CrⅢ-CuⅡ-CrⅢ三核配合物的合成、结构与磁性

基于一系列二氰根铬与[Cu(cyclam)](Cl O4)2反应合成了3个氰根桥联CrⅢ-CuⅡ-CrⅢ三核配合物[Cu(cyclam)][Cr(bpmb)(CN)2]2·4H2O(1)(cyclam=1,4,8,11-四氮杂环十四烷,bpmb2-=1,2-二(2-吡啶甲酰胺基)-4-甲基苯),[Cu(cyclam)][Cr(bpdmb)(CN)2]2(2)(bpdmb2-=1,2-二(2-吡啶甲酰胺基)-4,5-二甲基苯)和[Cu(cyclam)][Cr(bp Clb)(CN)2]2·4H2O(3)(bp Clb2-=1,2-二(2-吡啶甲酰胺基)-4-氯苯)。单晶衍射结果表明:3个化合物是结构类似的中性三核配合物,均含有氰根桥联的Cr(Ⅲ)-CN-Cu(Ⅱ)-NC-Cr(Ⅲ)连接;磁性研究表明:氰根桥在CrⅢ和CuⅡ离子间传递弱的铁磁耦合作用,基于自旋哈密顿算符H=-2JCr CuSCu(SCr1+SCr2)拟合得到它们的磁耦合常数分别是JCr Cu=1.53(2)cm-1(1),0.45(1)cm-1(2)和0.73(2)cm-1(3)。     

应用先进光谱技术研究无机离子的环境界面化学

发生在环境界面的吸附-解吸和氧化-还原等反应对于污染物在环境介质间传输、转化以及归趋起着重要的调控作用。传统的研究方法虽然可以在实验室模拟并进而描述污染物环境界面过程,但是不能揭示界面反应机制,限制了对污染物环境界面行为的认识。近二十年来,各种谱学技术(例如X射线吸收精细结构和傅里叶红外光谱等)应用于环境界面反应的研究,推动了这一领域研究的发展,特别是在分子水平研究污染物的环境界面过程。通过现代光/波谱技术原位分析,可以实时获取界面反应的定量与结构信息,从而更准确地判断反应机制,极大促进了对污染物在多介质环境界面迁移转化规律的认识。本文将在概述环境界面化学反应的基础上,针对无机离子在环境界面的反应过程,重点介绍几种关键光/波谱技术(X射线吸收精细结构光谱、傅里叶红外光谱、拉曼光谱、核磁共振谱和穆斯堡尔谱等)在环境界面化学研究中的应用,并展望其在环境界面过程研究中的应用前景。     

ICP-MS的KED模式测定磷酸加王水复溶土壤样品中的二十种金属元素

在研究锗测定时,磷酸先溶解样品,后加入王水复溶,可同时测定锂、铍、钪、钒、铬、钴、镍、铜、锌、锗、钼、镉、钡、镧、铈、钨、铊、铅、钍和铀元素。研究ICP-MS的最佳测量模式、最佳工作状态,以铑为内标校正仪器的漂移。通过选择高、中、低几个国家一级水系沉积物和土壤标准物质随同样品一起实验溶解建立标准曲线,消除消解、分取、定容中带来的不确定误差和基体干扰,选择8个土壤标准物质为实验样本。最终结果表明,该实验方法准确度(ΔlgC)小于0.1,精密度(RSD)小于8%,该方法满足测定要求,适用于地质普通样品的多金属检测。#$NL     

Bestimmung von Fe, Co, Cu, Zn, Se, Rb und Cs in NBS-Ochsenleber, Blutplasma und Erythrocyten durch INAA und AAS

Zusammenfassung Der Gehalt von Fe, Co, Cu, Zn, Se, Rb und Cs wurde in Blutplasma und in Erythrocyten von sechs Normalpersonen mittels der instrumentellen Neutronenaktivierungsanalyse und der flammenlosen Absorptionsspektrometrie (Cu) bestimmt. Zur Überprüfung der Richtigkeit wurde der NBS-Standard 1577, Ochsenleber, verwendet. Die erhaltenen Resultate für Elemente mit höheren Gehalten (Fe, Cu, Zn) liegen weitgehend im Bereich der bisher veröffentlichten Daten. Bei Elementen mit kleineren Gehalten (Co, Se, Rb, Cs) liegen unsere Werte in dem unteren Bereich oder darunter. Für diese Elemente wurden in Blutplasma und in Erythrocyten (hier bezogen auf Trockenmasse) die folgenden Mittelwerte ermittelt: Für Co 0,22 ±0,14 ng/ml, 0,59±0,23 ng/g, für Se 103±18 ng/ml, 401±29 ng/g, für Rb 167±36 ng/ml, 12,1±2,5 g/g und für Cs 0,88±0,18 ng/ml, 13,0±5,7 ng/g.

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Determination of Fe, Co, Cu, Zn, Se, Rb and Cs in NBS Bovine Liver, blood plasma and erythrocytes by INAA and AAS

Summary The content of the above elements has been determined in blood plasma and in erythrocytes of six normal persons by instrumental neutron activation analysis and flameless atomic absorption spectrometry (Cu). The over-all accuracy of these techniques was checked by using the NBS standard 1577, Bovine Liver. The results obtained for elements of higher content (Fe, Cu, Zn) are essentially in the range of other published data. However, our results for elements occurring with lower contents (Co, Se, Rb, Cs) are in agreement with the lowest values of the published data and in some cases they are even significantly below these. For these elements, the following contents have been determined in blood plasma and in erythrocytes (here related to dry weight): for Co 0.22±0.14 ng/ml and 0.59±0.23 ng/g, for Se 103±18 ng/ml and 401±29 ng/g, for Rb 167 ±36 ng/ml and 12.1±2.5 g/g and for Cs 0.88 ±0.18 ng/ml and 13.0±5.7 ng/g, respectively.

Diese Arbeit wurde durch die Deutsche Forschungsgemeinschaft gefördert.Dem Kernforschungszentrum danken wir für den Erlaß der Bestrahlungskosten.Herrn Dr. med. K. Spenger sind wir für die Mitwirkung bei der Blutentnahme und für wertvolle Diskussion dankbar.     

Direct benzylic functionalization of pyridines:Palladium-catalyzed mono-α-arylation of α-(2-pyridinyl)acetates with heteroaryl halides

Herein,we report a Pd-catalyzed mono-a-arylation reaction for pyridine benzylic functionalization.This approach serves as an efficient alternative to synthesize di-heteroaryl acetates in good yields and selectivities.Moreover,the method is applicable to heteroa ryl substrate combinations,and exhibits great functional group tolerance.A streamlined protocol also enables the rapid synthesis of diheteroaryl ketones.The synthetic value was also demonstrated by scale-up experiments.     

Phosphorescence of aromatic molecules in complexes with crystalline β-cyclodextrin at room temperature

The rate constants for the quenching by oxygen of triplet states of aromatic molecules (naphthalenes-d₈ and-h₈, phenanthrene) forming inclusion complexes with crystalline β-cyclodextrin in water at 290 K are equal to 900–1300 L mol⁻¹s⁻¹. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1450–1453, August, 1997.     

中文化学名词醇醛酮醚酯之由来

1932年民国教育部颁布的《化学命名原则》为中文化学名词确立了统一的标准,并对于“元素及化合物定名取字”提出“取字应以谐声为主,会意次之,不重象形”的定名总则。它确立的中文化学名词醇、醛、酮、醚、酯是意译名,这似乎与其音译为主的命名原则相悖。本文讨论了醇、醛、酮、醚、酯的各种历史译名,并分析了它们被《原则》采纳的原因。     

Determination of Violet Covasol as a cosmetic dye in water samples by a CPE-Scanometry method

The trace amounts of Violet Covasol as a cosmetic dye was determined by an efficient cloud point extraction-Scanometry(CPE-Scanometry) method. This method has many advantages such as novelty,facility, high speed, sensitivity, low cost and safety. The method is based on the CPE of an analyte from an aqueous solution, diluting the extracted surfactant-rich phase with ethanol, transferring to Plexiglas~cell and scanning of the cells containing the analyte solution with a scanner and measuring the RGB parameters with software written in visual basic(VB 6) media. Parameters impacting the extraction efficiency such as p H of the system, the concentration of surfactant, equilibration temperature and time were optimized. Detection limit(DL), relative standard deviation(RSD) and linear range for the proposed method are 0.026, 0.71 and 0.16–6.6 μg m L ~(-1)respectively. The method was successfully applied for the determination of Violet Covasol dye in several water samples, including a water sample containing the dye as a tracer(to investigate subsurface water movement).     

Electrocatalytic Oxidation and Simultaneous Determination of Uric Acid,Xanthine, Hypoxanthine and Dopamine Based on β-Cyclodextrin Modified Glassy Carbon Electrode

A novel covalently modified glassy carbon electrode with β-cyclodextrin was prepared via electropolymerization technique for the simultaneous determination of uric acid(UA), xanthine(XA), hypoxanthine(HX) and dopamine(DA). This new electrode presented an excellent electrocatalytic activity towards the oxidation of UA, XA, HX and DA by cyclic voltammetry(CV) method. The oxidation peaks of the four compounds were well defined and had the enhanced peak currents. The separation potentials of the oxidation peaks for DA-UA, UA-XA and XA-HX were 150, 390 and 360 mV in CV, respectively. By means of differential pulse voltammetry(DPV) method, the calibration curves in the ranges of 10-225, 5-105, 10-170 and 5-150 μmol/L were obtained for UA, XA, HX and DA, respectively. The lowest detection limits(S/N=3) were 5, 1.25, 5 and 1.5 μmol/L for UA, XA, HX and DA, respectively. The practical application of the modified electrode was demonstrated by the determination of DA in hydrochloride injection and UA, XA, HX in human urine samples.     

Synthesis and cytotoxic activity of 3-phenyl-4-substituted-β-carbolines

A new class of 3-phenyl-4-substituted-β-carbolines via iodine-mediated electrophilic cyclization as key step were synthesized and their inhibitory activity against three tumor cell lines was evaluated in vitro.It was found that some of the tested compounds showed better cytotoxicity against HeLa and MCF-7 cells than harmine.