手性二噁唑啉吡啶铁和镍配合物的制备与表征

Tridentate bis(oxazolinylpyridine)(1) reacted with nickel chloride or ferrous chloride in anhydrous ethanol to form bis(oxazolinylpyridine) Nickel(Ⅱ) and Iron(Ⅱ) complexes. The stable solid complexes were characterized with IR， UV， MS， XPS and elemental analysis. No stable complexes were formed with bidentate bis(oxazoline)(2) ins- tead of bis(oxazolinylpyridine).     

新型温度敏感性自组装胶束P(NiPAAm-co-DMAA)-co-P(L-Ala)的合成和性能

通过原子转移自由基聚合(ATRP)合成了一种带有活性—NH2基团的温度敏感性亲水型共聚物P(NiPAAm-co-DMAA), 并将其作为引发剂, 合成了P(NiPAAm-co-DMAA)-co-P(L-Ala), 其分子量分布(PDI)在1.3左右. 聚合物通过自组装形成纳米胶束. 透射电镜(TEM)结果表明, 胶束大小200~300 nm, 具有明显的核壳结构. 共聚物的最低临界溶解温度(LCST)为45.5 ℃. 温度低于LCST时, 聚合物溶解形成胶束; 高于LCST时, 胶束解离, 聚合物不溶. 聚合物对温度的响应是快速而可逆的.     

Thermal decomposition of silver(I) and mercury(I) anthranilates and salicyloaldoximates

The processes of thermal decomposition of silver(I) and mercury(I) anthranilates and salicyloaldoximates were studied. Thermal, chemical and X-ray analyses and infrared spectroscopy were used to determine the mechanisms of decomposition of these complexes. The factor determining the decomposition is the character of the Ag⁺ and Hg ₂ ²⁺ ions, which are easily reduced to free metals. The final reaction product of the compounds of silver is the pure metal; the compounds of mercury are volatilized completely when heated.     

AucoreCoshell纳米粒子的制备、表征及其表面增强拉曼光谱研究

在乙醇体系中和在制备好的Au纳米粒子表面, 用水合肼还原钴盐制备Co壳, 首次通过化学还原法制得核壳结构的Au-Co纳米粒子, 并通过控制钴盐的投料, 得到不同包裹层厚度的AucoreCoshell纳米粒子. 用扫描电子显微镜(SEM)和电化学循环伏安法(CV)等测试方法对其进行表征, 并用吡啶(Py)作为探针分子研究了其SERS效应.     

龙涎香的组成及降龙涎醚的合成研究进展

简要介绍了龙涎香的应用及其化学组成,重点介绍了以香紫苏醇为原料,通过不同的氧化-还原-环化途径合成降龙涎醚。     

Hydrolytic degradation of carbohydrate-based aromatic homo- and co-polyesters analogous to PET and PEI

The hydrolytic degradation of a series of homo- and co-polyesters analogous to poly(ethylene terephthalate) (PET) and poly(ethylene isophthalate) (PEI), prepared from carbohydrate-based monomers, was studied. The degradation process was carried out at temperatures of approximately 10 °C above the T_g of the polymers. All the studied polyesters were found to degrade at significant rates, and degradability showed a clear dependence on the configuration of the sugar units present in the polymer chain. No weight loss was detected upon degradation, apparently due to the non-solubility of the degraded products in the aqueous incubation medium. Hydrolysis of co-polyesters took place preferentially by cleavage of the ester groups of the sugar units.     

荧光和圆二色谱法用于低密度脂蛋白氧化的研究

氧化修饰低密度脂蛋白（oxidized low density lipoprotein,oxLDL）被认为是动脉硬化的关键致病因素。oxLDL的性能与其唯一的组成蛋白-载脂蛋白B-100（apoB-100）的二级结构即构象密切相关。荧光光谱和圆二色（circular dichroism,CD）光谱是研究蛋白质构象的有力手段,因此在oxLDL结构的研究中也有广泛的应用。本文综述了近年来荧光光谱和圆二色光谱在LDL氧化研究方面的应用, 并对今后的研究方向做了展望。     

烟酰型辅酶NAD(P)+和NAD(P)H再生的研究进展

大部分氧化还原酶的催化反应需要烟酰型辅酶NAD(P) 和NAD(P)H作为氧化剂或还原剂参与,由于氧化还原酶应用广泛而辅酶价格昂贵,使得辅酶再生逐渐成为研究热点.综述了近年来NAD(P) 和NAD(P)H酶法再生、电化学法及光化学法再生的研究进展,并介绍了各再生技术的应用和开发状况.     

Silyl stabilized azanes: Reactions of mono- and dilithium bis(trimethylsilyl)hydrazide with dichloro- and tetrachlorostannane

SnCl₄ acts primarily as an oxidant and oxidizes monolithium bis(trimethylsilyl) hydrazide 1 to mainly bis(trimethylsilyl)amine, BSA and tris(trimethylsilyl)hydrazine, TrSH and itself get reduced to SnCl₂. Similarly, reaction of SnCl₄ with dilithiumbis(trimethylsilyl) hydrazide 2, oxidizes it to lithium tris(trimethylsilyl)hydrazide, Li-TrSH. Reaction of dichlorostannane (reduction of oxidation state of tin from +4 to +2) with 1 gives a simple substitution reaction and give a pale yellow solid, 1,4-bis(trimethylsilyl)-1,2,4,5-tetraza-3,6-distannacyclohexane, 3b. Whereas, in reaction of 2 with SnCl₂ intermediate stannimine [(Me₃Si)₂N-NSn], tetramerizes and further loses tetrakis(trimethylsilyl)tetrazene, TST to give a cubane compound [(Me₃Si)N-Sn]₄, 4.     

Fluorinated phosphorus compounds: Part 6. The synthesis of bis(fluoroalkyl) phosphites and bis(fluoroalkyl) phosphorohalidates

Reaction of phosphorus trichloride with tert-butanol and fluoroalcohols gave bis(fluoroalkyl) phosphites (R_FO)₂P(O)H in 42-89% yield, where R_F=HCF₂CH₂, H(CF₂)₂CH₂, H(CF₂)₄CH₂, CF₃CH₂, C₂F₅CH₂, C₃F₇CH₂, (CF₃)₂CH, (FCH₂)₂CH, CF₃(CH₃)₂C, (CF₃)₂CH₃C, CF₃CH₂CH₂, C₄F₉CH₂CH₂ and C₆F₁₃CH₂CH₂. Treatment of these with chlorine in dichloromethane gave the bis(fluoroalkyl) phosphorochloridates (R_FO)₂P(O)Cl in 49-96% yield. The chloridate (CF₃CH₂O)₂P(O)Cl was isolated in much lower yield from the interaction of thionyl chloride with bis(trifluoroethyl) phosphite. Heating the latter in dichloromethane with potassium fluoride and a catalytic amount of trifluoroacetic acid gave the corresponding fluoridate (CF₃CH₂O)₂P(O)F in 84% yield. Treatment of bis(trifluoroethyl) phosphite with bromine or iodine gave the bromidate (CF₃CH₂O)₂P(O)Br and iodidate (CF₃CH₂O)₂P(O)I in 51 and 46% yield, respectively. The iodidate is the first dialkyl phosphoroiodidate to have been isolated and characterised properly—its discovery lags behind the first isolation of a dialkyl phosphorochloridate by over 130 years. The fluoroalkyl phosphoryl compounds are generally more stable than known unfluorinated counterparts.     

Synthesis of Derivatives of (4-Methyl-2-Quinolylthio)acetic and (4-Methyl-2-Quinolylthio)propionic Acids

An efficient synthesis has been developed for derivatives of (4-methyl-2-quinolylthio)acetic and (4-methyl-2-quinolylthio)propionic acids by the reaction of 4-methyl-2-thioxoquinoline with methyl methacrylate, the amide of methacrylic acid, acrylonitrile, ethyl bromoacetate, and ethyl acrylate. The hydrolysis of the resultant intermediates by (quinolylthio)acetic and (quinolylthio)propionic acids gave the corresponding acid products, which are also formed in the reaction of 4-methyl-2-thioxoquinoline with chloroacetic and acrylic acids. The reaction of 4-methyl-2-thioxoquinoline with allyl bromide was studied. The potassium permanganate oxidation of the resultant 2-allylthio-4-methylquinoline led to (4-methyl-2-quinolylthio)acetic acid.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 403–406, April, 2005.     

Preparation of poly(vinylpyrrolidone)-protected Prussian blue nanoparticles-modified electrode and its electrocatalytic reduction for hemoglobin

In this paper, a novel modified electrode was developed by using highly dispersed Prussian blue (PB) nanoparticles protected by poly(vinylpyrrolidone) (PVP). The size of the nanoparticles was controlled through adjusting the feed ratio of PVP/Fe²⁺. Physical characteristics of the nanocomposite were studied by transmission electron microscopy (TEM), UV-vis, IR spectroscopy, and X-ray powder diffraction (XRPD) analysis. The electrocatalytic reduction of hemoglobin (Hb) at PVP-protected PB nanoparticles (PVP/PB NPs)-modified electrode had been investigated. In addition, the size effects and biocompatibility of PVP/PB NPs for the electrochemistry of Hb were also observed. Experimental results indicated that the reduction peak currents of Hb were linear with its concentrations over the range from 1.0 × 10⁻⁷ to 1.2 × 10⁻⁵ mol/L and the calculated detection limit (S/N = 3) was 4.0 × 10⁻⁸ mol/L.     

Synthesis of novel bis- and poly(aryldiazenylthiazoles)

A novel series of bis- and poly(arydiazenyl)thiazoles were prepared in good yields by the reaction of the appropriate α-keto-hydrazonoyl chlorides with the corresponding bis- and poly(hydrazinecarbothioamide) in refluxing EtOH/DMF in the presence of few drops of TEA. Based on elemental analyses as well as spectral data, the structures of the new compounds were confirmed.     

Molecular orientation behavior of poly(vinyl chloride) as influenced by the nanoparticles and plasticizer during uniaxial film stretching in the rubbery stage

The structural evolution during uniaxial stretching of poly(vinyl chloride) films was studied using our real time spectral birefringence stretching machine. The effect of clay loading and the amount of plasticizer as well as the rate effects on the birefringence development and true mechanical response are presented with a final model summarizing the molecular phenomena during stretching. Mechano‐optical studies revealed that birefringence correlated with mechanical response (stress, strain, work) nonlinearly. This was primarily attributed to the preexisting strong network of largely amorphous chains connected via small crystallites that act as physical crosslinking points. These crystallites are not easily destroyed during the high‐speed stretching process as evidenced from the birefringence–true strain curves along with the X‐ray crystallinity measurements. At high speeds, the amorphous chains do not have enough time to relax and hence attain higher orientation levels. The crystallites, however, orient more efficiently when stretched at slow speeds. Apparently, some relaxation of the surrounding amorphous chains helps rotate the crystallites in the stretching direction. Overall birefringence is higher at high stretching speeds for a given true strain value. When the nanoparticles are incorporated, the orientation levels are increased significantly for both the crystalline and amorphous phases. Nanoplatelets increase the continuity of the network because they have strong interaction with the amorphous chains and/or crystallites. This in turn helps transfer the local stresses to the attached chains and increase the orientation levels of the chains. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 724–742, 2005     

Synthesis of 1,2-diferrocenyl-3-(diacylmethylidene)cyclopropenes and 1,1-diacyl-2,3-diferrocenyl-4-methylsulfanylbuta-1,3-dienes, their structures and electrochemical properties

2,3-Diferrocenyl-1-morpholinocyclopropenylium tetrafluoroborate reacts with 1,3-diketones in the presence of triethylamine to give 3-diacylmethylidene-1,2-diferrocenylcyclopropenes (8a-d). Under similar conditions, 2,3-diferrocenyl-1-methylsulfanylcyclopropenylium iodide affords 8a-c (∼25-30%) and 1,1-diacyl-2,3-diferrocenyl-4-methylsulfanylbuta-1,3-dienes (10a-c) (∼50-60%). The structures of the products obtained were established based on the data from ¹H (1D NOE) and ¹³C NMR spectra and X-ray diffraction analysis. Electrochemical properties of several (diacylmethylidene)diferrocenylcyclopropenes (8a-c) and 1,1-diacyl-2,3-diferrocenyl-4-methylsulfanylbuta-1,3-dienes (10a-c) are studied.     

Synthesis and structural studies of mixed-ligand complexes

Seven mixed-ligand complexes of cobalt(II), nickel(II) and copper(II) containing benzoylacetone andL-proline (HL¹), 2-pyrrolidone-5-carboxylic acid (HL²) orL-thioproline (HL³) were prepared and characterized by means of elemental analysis, IR, electronic spectra, magnetic moment measurements and molar conductance. Both HL¹ and HL² coordinate with these metal ions in a neutral zwitterionic form (-NH₂-CH-COO^–), whereas HL³ coordinates as a monobasic chelating agent (O/N). The continuous thermochromism of the nickel(II) complex of HL¹ (2) was attributed to a geometry change; it was investigated by DTA, TG, electronic spectra and X-ray powder diffraction techniques.     

The Solubility of Bis(cyclopentadienyl)samarium(II) and Implications for the Reaction of Samarium Metal with Bis(cyclopentadienyl)mercury(II)

Bis(cyclopentadienyl)samarium(II) has been shown to be insoluble in thf : ether mixtures, hence it cannot be isolated as a soluble product from the reaction of samarium with HgCp₂ in thf : ether.     

具有扩展的双链结构的Mn(III)酰腙配合物的合成和晶体结构

合成了含有水杨醛缩(4-甲氧基)苯氧乙酰腙(以下简写为 H2L)的锰配合物[Mn(L)(acac)-(EtOH)]?H2O (MnC23H29 N2O8, Mr = 516.42)。配合物晶体属三斜晶系, 空间群为 P1, 晶胞参数为:a = 7.6942(3), b = 11.2422(4), c = 14.9230(6) ?, α = 95.656(2), β = 104.848(2), γ = 95.642(2)°, V =1231.37(8) ?3, Z = 2, Dc = 1.393 g/cm3, μ = 0.585 mm–1, F(000) = 540。对于 4374 (I > 2σ(I)) 个可观察点, R = 0.0439, wR = 0.1150。在配合物中, 中心 Mn(III)离子具有扭曲的 NO5八面体配位构型。晶体通过分子内与分子间的氢键作用形成平行排列的无限双链结构。     

A structural variability of copper(I) chloride-tetrahydrothiophene adducts crystallizing in polymeric forms and exhibiting polymorphism: The role of the solvent

The function of the solvent in the self-assembling mode of [CuCl] with tetrahydrothiophene is reported. Copper(l) chloride has been used in the form of [CuCOCl] _n , which is slightly soluble in the most common solvents, and to allow an homogeneous phase reaction. The reaction of [CuCOCl] _n with THT gave [(CuCl)₂(THT)₃] _x ,1, in CH₃OH, [(CuCl)(THT)₂] _x ,2 in THF [(CuCl)(THT)] _x ,3, in CH₂Cl₂, and [(CuCl)₃(THT)₂] _x ,4, in DME. Compound1 consists of polymeric chains of centrosymmetric Cu₂Cl₂ dinuclear units bridged by THIT molecules running parallel to the [101] axis. In the structure of2 we found polymeric layers generated from the [(CuCl)(THT)] asymmetric unit by the center of symmetry and by the twofold axis. In compound3 the structure consists of layers generated through the center of symmetry by the [(Cu₂Cl₂)(THT)₂] asymmetric unit, while4 consists of layers generated through the center of symmetry by the [(Cu₃Cl₃)(THT)₂] asymmetric unit. Crystallographic details are as [ollows:2 is monoclinic, space group P2₁/c.a=9.657(3) A,b=6.441(2) A,c=11.459(3) A,\=111.96(2)°,V=661.0(4) A³. andR=0.075;3 is monoclinic, space group P2₁/n,a=19.327(7) A,b=6.703(2) A,c=10.116(3) A,ß=103.04(3)°,V=1276.7(7) A³ andR=0.043:4 is triclinic, space group Pl,a=12.513(2) A,b=6.698(1) A,c=9.651(1) A,=91.98(1)°,\=107.86(1)°,=74.59(1)°,V=741.2(2) A³, andR=0.044.