离子受体对自由卟啉探针荧光识别性能的影响（英文）

通过对2个N,N-二吡啶胺基受体修饰的自由卟啉化合物(Porphyrin-2-DPA)光学识别性能的系统研究,可以得知:该卟啉化合物中心刚性共轭的四吡咯环状结构不仅作为灵敏的光学信号基团、更是作为第一离子配位受体,在非共轭的N,N-二吡啶胺基受体辅助下,对Pb2+/Cu2+离子表现出灵敏的多重信号分析识别功能。     

一种基于DPA识别基团的可视化检测锌离子的荧光增强型探针

以N,N-二（2-吡啶甲基）胺（DPA）为识别基团,设计合成了一种用于检测Zn²⁺的荧光增强型探针WN,在CH₃CH₂OH/Tris-HCl（1：9,V/V,pH=7.4）缓冲溶液中研究了它对Zn²⁺的识别特性。实验结果表明,WN对Zn²⁺有较高的选择性和灵敏度,它们之间的结合比为1：1,对Zn²⁺的检出限为1.14×10^-8mol·L^-1。WN能够快速地可视化检测Zn²⁺,在HeLa活细胞中对Zn²⁺的荧光显微成像表明WN可应用于生物体的检测。     

基于双核{Zn2(COO)4}次级构筑单元的二维发光配位聚合物的晶体结构和对Fe3+的检测

使用H2L配体（H2L=2-（1,3-dioxo-1H-benzo[de]isoquinolin-2（3H）-yl） terephthalic acid）和Zn²⁺通过水热反应,合成了一例基于双核{Zn₂（COO）₄}次级构筑单元的二维发光配位聚合物[Zn₂（L）₂（DMSO）₂（DMF）]（1）（DMSO=二甲亚砜,DMF=N,N-二甲基甲酰胺）。拓扑分析表明1结构中的双核{Zn₂（COO）₄}单元可视为4连接节点,并与作为连接子的L^2-形成（4,4）-网拓扑构型。1表现出对Fe³⁺离子的选择性发光猝灭响应,检测限为2.8 μmol·L^-1。1对Fe³⁺的检测具有良好的抗干扰性,且可通过DMF溶剂洗涤实现再生,可多次循环使用。     

TODGA/[C2mim][NTf2]萃取Th4+的研究

研究了N,N,N',N'-四辛基-3-氧戊二酰胺(TODGA)溶于疏水性离子液体咪唑类离子液体1-乙基-3-甲基咪唑双三氟甲磺酰亚胺盐([C₂mim][NTf₂])中对硝酸水溶液体系中四价钍离子(Th⁴⁺)的萃取行为.详细考察了接触时间、酸度、Th⁴⁺浓度、TODGA浓度、温度对TODGA/[C₂mim][NTf₂]体系萃取性能的影响.作为对比,我们还考察了TODGA在传统有机溶剂异辛烷中对Th⁴⁺的萃取.结果表明:TODGA/[C₂mim][NTf₂]体系对Th⁴⁺的萃取是吸热反应,且在50 ℃下,能在5 min内达到平衡.萃取体系随着酸度对Th⁴⁺的萃取性能先降后增大;Th⁴⁺浓度的增大,TODGA浓度的降低,对Th⁴⁺的萃取性能下降.TODGA在离子液体萃取体系中比在有机体系中有更好的Th⁴⁺萃取效果,特别是在低酸条件下.通过萃取机理研究,推测出在低酸下萃取反应是离子交换且TODGA与Th⁴⁺配比为2∶1,在高酸下萃取是中性配位.     

苯乙烯相连的卟啉-三芳胺共轭体的合成及表征

以三芳胺甲醛和4-二乙氧基甲基苄基亚磷酸二乙酯为原料经Wittig-Horner反应制得化合物4-[4-(N,N-二苯胺基)苯乙烯基]苯甲醛, 4-[4-(N,N-二对甲苯胺基)苯乙烯基]苯甲醛和4-[4-(N,N-二对甲氧基苯胺基)苯乙烯基]苯甲醛, 这些化合物与吡咯在丙酸中回流得到一类通过苯乙烯相连的卟啉-三芳胺共轭体, 并采用¹H NMR, ¹³C NMR, MS及UV-vis对卟啉化合物的结构进行了表征.     

二硫纶修饰的β-环糊精的自包合以及对金属离子的响应

利用圆二色光谱, 核磁, 等温滴定量热法和化学滴定方法研究单-6-马来二氰二硫代酸钠-β-环糊精在水溶液中的自包合性质。化学滴定实验结果表明十二烷基硫酸钠(SDS), Cu²⁺和Co²⁺可以改变单-6-马来二氰二硫代酸钠-β-环糊精的构象, 并且得出单-6-马来二氰二硫代酸钠-β-环糊精在水溶液中的存在形式是自包合的结论;Cu²⁺可以作为打开单-6-马来二氰二硫代酸钠-β-环糊精自包合结构的"钥匙", 使其构象改变后可以与中性红(NR)发生包合作用;加入EDTA与Cu²⁺配位后, 单-6-马来二氰二硫代酸钠-β-环糊精恢复自包合结构, 同时释放中性红客体分子。     

酚氧桥联多核铜(Ⅱ)配合物的合成、结构和磁性

利用柔性酚胺类配体N,N'-二甲基-N,N'-(2-羟基-4,5-二甲基苄基)乙二胺(H₂L)与Cu(Ⅱ)反应,合成了2个新的酚氧桥联多核Cu(Ⅱ)配合物[Cu₃^II(L)₂(CH₃OH)₂](ClO₄)₂(1),[Cu₃^II(L)₂(Cu^ICl₂)₂](2)。配合物1~2中,3个Cu²⁺之间通过2个酚氧桥连接,形成线性三核结构。两边的铜离子分别被配体L^2-上的N₂O₂螯合配位,轴向与甲醇分子的氧(配合物1)或[CuCl₂]^-的氯(配合物2)配位,形成四方锥配位构型。中间铜离子与两侧L^2-上的4个酚氧原子以平面四边形配位。Cu^II-O-Cu^II键角为100.14°~101.79°。对配合物1~2进行变温磁化率测量表明,铜离子之间通过酚氧桥存在强的反铁磁耦合,磁耦合常数J分别为-277(9)cm^-1(配合物1)和-299(3)cm^-1(配合物2)(基于自旋哈密顿算符Ĥ=-2J(Ŝ₁·Ŝ₂+Ŝ₂·Ŝ₃)。J值与酚氧桥桥联键角有一定相关性,即Cu-O-Cu桥联键角越大,反铁磁耦合越强。     

基于咪唑基配体的Mn(Ⅱ)配合物的水热合成及结构、理论计算和三阶非线性光学性质

在水热条件下用氯化锰和咪唑基配体合成了配合物Mn[（IPB）₂Cl₂]·4H₂O （IPB=4-（1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl） benzaldehyde）,并通过元素分析、红外光谱、紫外衍射、X射线单晶衍射法和Z-扫描技术对其结构和性质进行了表征。X射线单晶衍射结果表明,该化合物晶体属正交晶系,空间群Pnna。采用Z-扫描技术测量了该化合物的非线性光学特性,结果显示,以45 μJ的脉冲能量,在焦点处的透光率为93%,非线性吸收系数为-4.5×10^-11 m·W^-1,非线性折射率为1.0×10^-19 m²·W^-1。该化合物显示了自聚焦的性质。在紫外-可见光谱区,该化合物的最大吸收波长为282nm。     

选择性响应Cu2+、Ag+及阴离子的菲咯啉-水杨醛荧光探针

在乙酸酐中用2,9-二甲基-1,10-菲咯啉与水杨醛缩合反应得到2,2’-（1E,1’E）-2,2’-（1,10-菲咯啉-2,9-二基）双（乙烯-2,1-二基）双（2,1-亚苯基）二乙酸酯（探针1）;再将其进一步水解得到2,2’-（1E,1’E）-2,2’-（1,10-菲咯啉-2,9-二基）双（乙烯-2,1-二基）二苯酚（探针2）。经¹H NMR、¹³C NMR、IR、MS表征,探针化合物为大共轭结构,发光性能良好。两种探针分别表现出对Cu²⁺、Ag⁺不同的荧光猝灭作用,探针2还能识别阴离子F^-和AcO^-,具有双功能离子检测性能。光谱滴定、等温滴定量热及质谱等测定了配合物组成、作用常数及热力学参数,探针与金属离子的配合为放热反应,作用比为2：1。     

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)](ClO₄)₂反应合成了3个氰根桥联Cr^Ⅲ-Cu^Ⅱ-Cr^Ⅲ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,bpmb^2-=1,2-二(2-吡啶甲酰胺基)-4-甲基苯),[Cu(cyclam)][Cr(bpdmb)(CN)₂]₂(2)(bpdmb^2-=1,2-二(2-吡啶甲酰胺基)-4,5-二甲基苯)和[Cu(cyclam)][Cr(bpClb)(CN)₂]₂·4H₂O(3)(bpClb^2-=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Cr^Ⅲ和Cu^Ⅱ离子间传递弱的铁磁耦合作用,基于自旋哈密顿算符Ĥ=-2J_CrCuŜ_Cu(Ŝ_Cr1+Ŝ_Cr2)拟合得到它们的磁耦合常数分别是J_CrCu=1.53(2) cm^-1(1),0.45(1) cm^-1(2)和0.73(2) cm^-1(3)。     

Asymmetric Synthesis of （R）- and （S）-Moprolol

A simple and effective procedure for the enantioselective synthesis of （R）- and （S）-moprolol was described. The key step was the asymmetric synthesis of enantiopure （R）- and （S）-guaifenesin, which were synthesized from enantioenriched （R）-3-chloro-l,2-propanediol and （S）-epichlorohydrin via kinetics of hydrolysis resolution of racemic epichlorohydrin by chiral Salen-Co^Ⅲ complex. The e.e. values of both the optical compounds were above 98%, and the chemical structures of the target compounds were confirmed by ^1H NMR, ^13C NMR, IR, and MS.     

Stereochemistry of ketone olefination with methyl trimethylsilylacetate

High (Z)-stereoselectivity of olefination of methyl α-phenylthioalkyl and methyl α-phenylthioalkenyl ketones with methyl trimethylsilylacetate decreases in the case of ketones containing a higher alkyl-substituent in place of the methyl group. Dedicated to Corresponding Member of the Russian Academy of Sciences E. P. Serebryakov on the occasion of his 70th birthday. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 1020–1021, April, 2005.     

Darstellung und Charakterisierung von Halogeno(diethyldithiocarbamato) (triethyl- und triphenylphosphin)palladium(II)-Komplexen

The Complexes [Pd(PEt ₃)₂ dtc]X (1) and Pd(PR ₃)Xdtc (2, 3) (dtc=S₂CNEt ₃;X=Cl, Br, I;R=Et, Ph) have been prepared. Conductivity, susceptibility, UV and IR measurements show that the cations [Pd(PEt ₃)₂ dtc]⁺ of1 and the complexes2, 3 have square-planar structure.

     

Herstellung der klassischen Seltenerd(II)-chloride in Lösung

Using the reduction of the trichlorides by lithium metal/naphthalene in tetrahydrofurane (THF), SmCl₂ and EuCl₂ were prepared in solventfree state, very sparingly soluble inTHF. The reduction of YbCl₃, combined with extraction to eliminate the oxide chloride content, yielded the compound YbCl₂·THF, much more soluble inTHF than YbCl₃.

     

Electrophoretic deposition as a tool for separation of protein inclusion bodies from host bacteria in suspension

This paper shows, for the first time, that the electrophoretic deposition technique is able to selectively collect protein inclusion bodies (PBs) from the host bacteria suspensions. In the first step, zeta potential as a function of pH is carefully determined for both species involved. Based on the obtained dependencies, the pH of the mixture of PBs and bacteria is precisely adjusted and the electrophoretic experiment is carried out. We show that the efficiency of separation and the yield depends not only on the electrokinetic properties of given species but also on the electrode composition and surface morphology. The deposited species are easily removed by forced washing or reverse electric field. As a whole, the selectivity and the yields are higher than in most alternative state-of-the art techniques.     

Electrochemical studies of cytochrome c on gold electrodes with promotor of humic acid and 4-aminothiophenol

p-Aminothiophenol (PATP) and humic acids (HA or HAs) were applied jointly as the electron transfer accelerants of redox reactions of cytochrome c (Cyt c) on gold electrodes. The electrochemical properties of the modified electrodes were studied by field emission scanning electron microscope, ultraviolet-visible spectroscopy, electrochemical impedance spectroscopy, Raman spectroscopy and cyclic voltammetry. The immobilized Cyt c displayed a couple of stable and well-defined redox peaks with a formal potential of −0.101 V (vs. SCE) in pH 7.0 phosphate buffer solution. Cyt c adsorption is in the form of a monolayer with average surface coverage of 5.28 pmol cm⁻². The electron transfer rate constant was calculated to be 2.14 s⁻¹. It indicate that the HA film acted as a good adsorption matrix for Cyt c and an excellent accelerant for the redox of Cyt c. The Cyt c-HA modified gold electrode showed a new couple of well-marked redox peaks when 2,4-dichlorophenol was added to the test solution.     

Stability of bivalent metal complex with L-hydroxyproline

Potentiometric titration of L-hydroxyproline with NaOH solution at 30° ±0.1°C in a medium of constant ionic strenth, =0.1M (KNO₃) gave the stepwise formation constants of the complexes formed between Mn(II), Co(II) and Zn(II) ions. The values were logK ₁=3.45; logK ₁=4.58, logK ₂=4.03; logK ₁=5.08, logK ₂=4.66; for Mn(II), Co(II) and Zn(II) complexes. The order of stability constant is in accordance with theIrving-Williams series.

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Die Stabilität bivalenter metall-komplexe mit L-hydroxyprolin

Zusammenfassung Potentiometrische Titration von L-Hydroxyprolin in NaOH-Lösung bei 30±0,1°C und einer konstanten Ionenstärke von =0,1M-KNO₃ ergab stufenweise die Bildungskonstanten der entsprechenden Komplexe mit Mn(II), Co(II) und Zn(II). Die Werte sind logK ₁=3,45; logK ₁=4,58, logK ₂=4,03; logK ₁=5,08, logK ₂=4,66; für Mn(II); Co(II); Zn(II). Die Reihenfolge der Stabilität der Komplexe ist im Einklang mit derIrving-Williams-Reihung.

     

N-methyI-N-(triethoxysilylmethyl) andN-methyl-N-(silatran-1-ylmethyl) substituted glycine and alanine

Organosilicon derivatives of glycine, - and -alanine, and -methylalanine were prepared by the reaction of methyl esters of - and -halocarboxylic acids withN-methylaminomethyltriethoxysilane in the presence of triethylamine. The compounds synthesized were converted into the correspondingN-silatran-l-ylmethyl derivatives. Trimethylsilyliodoacetate reacts withN-methylaminomethyltrietoxysilane to give 2,2-diethoxy4-methyl-1-oxa-4-aza-2-silacyclohexane-6-one. Its reaction with triethanolamine leads toN-methyl-N-(silatran-l-ylmethyl)glycine.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 341–343, February, 1995.     

Phenylpropanoids from Medicinal Plants: Distribution, Classification, Structural Analysis, and Biological Activity

The literature and our own research results on phenylpropanoids from medicinal plants were reviewed and systematized. Data were presented for the distribution of phenylpropanoids. Their classification was proposed. The biological structure-activity relationships for compounds found in roseroot (Rhodiola rosea), thorny eleutherococcus (Eleutherococus senticosus), common lilac (Syringa vulgaris), purple echinacea (Echinacea purpurea), medicinal melissa (Melissa officinalis), variegated milk-thistle (Silybum marianum), and others were discussed.     

Spectrophotometric studies on the solvatochromism of the Fe(CN)2(phen)2 complex

Summary The solvatochromic behaviour ofbis-(cyano)-bis-(9,10-phenanthroline)-iron(II) has been reexamined spectrophotometrically in a series of 19 solvents including water, alcohols and dipolar. aprotic media. Satisfactory correlations between the wave numbers of the long-wavelength band and solvent acceptor numbers are obtained in all media; only values, for carboxylic acids deviate from the regression line.

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Spektrophotometrische Untersuchungen über die Solvatochromie der Komplexverbindung Fe(CN)₂(phen)₂

Zusammenfassung Das solvatochrome Verhalten vonbis-(Cyano)-bis-(9,10-phenanthrolin)-eisen(II) wurde in 19 Lösungsmitteln, darunter Wasser, Alkohole und dipolare aprotische Medien, spektrophotometrisch überprüft. In allen Medien wurden zufriedenstellende Korrelationen zwischen den Wellenzahlen der langwelligen Bande und den Akzeptorzahlen der Lösungsmittel erhalten; lediglich die Werte für Carbonsäuren weichen von der Ausgleichgeraden ab.