Electrochemical syntheses and structures of lead(II) and bismuth(III) complexes of 4-(trimethylammonio)benzenethiolate

Two main-group metal complexes of the zwitterionic ammonium thiolate complexes, [M(Tab)₃](ClO₄)_n (Tab = 4-(trimethylammonio)benzenethiolate) (1: M = Pb, n = 2; 2: M = Bi, n = 3), were prepared by electrochemical oxidation of Pb or Bi electrode in MeCN containing Tab and Et₄NClO₄. Each M atom in 1 and 2 is coordinated by three S atoms of three Tab ligands, forming a trigonal pyramidal coordination geometry. The resulting [M(Tab)₃]ⁿ⁺ cations are interconnected by secondary M⋯S interactions to form two different 1D cationic chains. The electrochemical properties of 1 and 2 were also investigated by cyclic voltammetry.     

Rapid complexing of oxoacylglycerols with amino acids peptides and aminophospholipids

We prepared model Schiff bases from 2-[9-oxo]nonanoyl glycerol (2-MAG-ALD) and various amino compounds. 2-MAG-ALD was obtained by pancreatic lipase hydrolysis of trioleoyl glycerol and reductive ozonolysis of the resulting 2-monooleoyl glycerol. The reaction products were purified by thin-layer chromatography. Schiff bases were synthesized in greater than 50% yield by reacting 2-MAG-ALD with twofold molar excess of valine, Nα-acetyl-l-lysine methyl ester and the tripeptides glycyl-glycyl-glycine, glycyl-glycyl-histidine, and glycyl-histidyl-lysine in aqueous methanol and with 1-palmitoyl-2-stearoyl glycerophosphoethanolamine (PE) in chloroform.methanol for 16 h at room temperature. Prior to analysis the bases were reduced with sodium cyanoborohydride in methanol for 30 min at 4°C. Reaction products were analyzed by high-performance liquid chromatography/electrospray ionization/mass spectrometry (HPLC/ESI/MS). Reduced Schiff bases of 2-MAG-ALD with PF and amino acids were analyzed by normal-phase HPLC/ESI/MS and those with peptides by reversed-phase HPLC/ESI/MS. Single adducts were obtained in all cases and both the α-amino group of valine and the ε-amino group of Nα-acetyl-l-lysine methyl ester were reactive. Molecular ions of reaction products were the only detected ions in the negative ionization mode, whereas in the positive ion mode sodiated molecular ions were also detected. The present study suggests that 2-MAG-ALD may form Schiff base adducts with amino compounds in other aqueous media, such as the intestinal lumen and in the hydrophobic environment of cell membranes.     

Potential-controlled chromatography for the separation of amino acids and peptides

Potential-controlled chromatography is introduced as a new technique for the separation of amino acids and peptides. The principle of potential-controlled chromatography depends on the use of electrically conductive material as the stationary phase of the chromatographic column. Thus from an electrochemical point of view the packed column can be regarded as a packed-bed electrode. The electrical potential of this stationary phase can be controlled by a potentiostat. The separation of amino acid and peptide molecules during their migration through the column depends on their own electric charge on the one hand and on the electrical potential of the stationary phase on the other. The chromatographic separation of some amino acids could be demonstrated.     

The syntheses,characterization and fluorescence spectra of novel,octakis(alkylthiophthalocyanato) nickel(II) and palladium(II) complexes

The syntheses, characterization and fluorescence studies of several {octakis(alkylthio)phthalocyanato} palladium(II) and nickel(II) complexes are presented. The absorption spectra of some of the complexes showed extra peaks which are attributable to non-planar distortion, the extent of which, was found to dependent on alkyl chain length. The fluorescence excitation spectra of the nickel(II) derivatives were not in agreement with their absorption spectra, owing to structural changes upon excitation. Fluorescence quantum yields were very low (<1%) for all complexes as a consequence of the open-shell electronic structures of nickel(II) and palladium(II).     

我国氨基酸与活性肽的提取精制技术进展

介绍了微滤膜、离子交换模拟移动床（SMB）、超滤膜、连续结晶、非极性吸附层析模拟移动床等现代分离技术。并介绍了用现代分离技术改造氨基酸与活性肽提取精制工艺的最新进展与成果。     

New polymer syntheses: 10. Syntheses of high molecular weight poly(4-hydroxybenzoate)s by bulk condensations of 4-hydroxybenzoic acids

The condensation of 4-hydroxybenzoic acid by means of various carboxylic acid anhydrides, acid chlorides and diphenylcarbonate has been investigated. All condensations were conducted in ‘one-pot procedures’. The average degrees of polymerization ($\text{DP}$) were determined by means of ¹H nuclear magnetic resonance (n.m.r.) spectroscopic end-group analyses. The bulk condensation of 4-hydroxybenzoic acid by means of acetic anhydride at temperatures between 320° and 350°C was found to be the simplest and least expensive procedure. Yields between 97 and 99% and $\text{DP}$ up to 300 were obtained in this way. Bulk condensations of purified acetoxybenzoic acid or condensations of 4-hydroxybenzoic acid with acetic anhydride in an inert solvent gave similar yields and $\text{DP}$. Also, the bulk condensations of 3,5-dimethyl-4-hydroxybenzoic acid, 3-methoxy-4-hydroxybenzoic acid, 3-chloro-4-hydroxybenzoic acid, 3,5-dichloro-4-hydroxybenzoic acid and 3,5-dibromo-4-hydroxybenzoic acid by means of acetic anhydride gave yields above 90%. However, the $\text{DP}$'s varied greatly with the nature of the substituents. ‘One-pot procedures’ using a variety of phosphorus derivatives as condensing reagents did not yield pure polyesters. The differential scanning calorimetry (d.s.c.) curves of the substituted poly(4-hydroxybenzoate)s do not show any endotherm, although X-ray diffraction measurements indicate a high degree of crystallinity. The thermogravimetric analyses demonstrate that the thermal stability depends largely on the synthetic procedure.     

水杨醛缩4-氨基安替比林与Zn(II),Ni(II),Co(II)配合物的合成和表征

以水杨醛、4-氨基安替比林和醋酸盐为原料,在酸性条件下,以乙醇为溶剂,合成了水杨醛缩4-氨基安替比林希夫碱及其配合物。考察了反应时间、温度、原料配比对该合成的影响。结果表明,反应的最佳条件为:水杨醛∶4-氨基安替比林∶醋酸盐(摩尔比)=1∶1∶1,在80℃条件下反应5 h,产率可达80%。通过红外和紫外光谱进行表征,研究了他们的性质。     

Interfacial self-assembly of amino acids and peptides: scanning tunneling microscopy investigation

Proteins play important roles in human daily life. To take advantage of the lessons learned from nature, it is essential to investigate the self-assembly of subunits of proteins, i.e., amino acids and polypeptides. Due to its high resolution and versatility of working environment, scanning tunneling microscopy (STM) has become a powerful tool for studying interfacial molecular assembly structures. This review is intended to reflect the progress in studying interfacial self-assembly of amino acids and peptides by STM. In particular, we focus on environment-induced polymorphism, chiral recognition, and coadsorption behavior with molecular templates. These studies would be highly beneficial to research endeavors exploring the mechanism and nanoscale-controlling molecular assemblies of amino acids and polypeptides on surfaces, understanding the origin of life, unravelling the essence of disease at the molecular level and deeming what is necessary for the "bottom-up" nanofabrication of molecular devices and biosensors being constructed with useful properties and desired performance.     

Convenient and efficient syntheses of 4-hydroxy-2(E)-nonenal and 4-oxo-2(E)-nonenal

Lipid peroxidation products 4-hydroxy-2(E)-nonenal (HNE) and 4-oxo-2(E)-nonenal (ONE) were conveniently synthesized using Wittig and Horner-Wardsworth-Emmons (HWE) reaction. Wittig or HWE reaction between an easily prepared phosphorane or phosphonate with glyoxal dimethyl acetal gave a protected 4-oxo-2(E)-nonenal. Hydrolysis gave 4-oxo-2(E)-nonenal, whereas reduction followed by hydrolysis gave 4-hydroxy-2(E)-nonenal.     

Metal-assisted syntheses and NMR characterization of square-planar Pd(II) and Pt(II) complexes with tridentate nitrogen-donor chelate ligands

The complexes [PtCl(NNN^H)](OTf) (1^H), [PdCl(NNN^H)](OTf) (2^H), [PdCl(NNN^Me)](OTf) (2^Me), [PdMe(NNN^H)](OTf) (3^H), [PdMe(NNN^Me)](OTf) (3^Me) and [PdMe(NNN^Ph)](OTf) (3^Ph) {NNN^H = (pyridin-2-ylmethylene)-quinolin-8-yl-amine; NNN^Me = (1-pyridin-2-yl-ethylidene)-quinolin-8-yl-amine; NNN^Ph = (phenyl-pyridin-2-yl-methylene)-quinolin-8-yl-amine} were prepared by reacting a stoichiometric methanolic mixture of 8-aminoquinoline and an ortho-substituted aldehydo- or keto-pyridine {2-pyridinecarboxaldehyde, 2-acetylpyridine or 2-benzoylpyridine} with the proper Pt(II) or Pd(II) precursor in methanol. In the case of the 2 ^Me derivative, the addition of a stoichiometric amount of a Ag(I) salt to the reaction mixture was necessary to obtain the desired product. Information about the formation of these complexes are reported. In particular, NMR experiments allowed to observe the different reactivity of 8-aminoquinoline towards aldehydo- and keto-pyridines and the formation of the emiaminal ligand pyridin-2-yl-(quinolin-8-ylamino)-methanol NNN(H₂O)^H 4. Finally, the methanesulphonato-complex [Pd(η¹-OSO₂CH₃)(NNN^Me)](OTf) (5^Me) was obtained by reacting the chloro-derivative 2^Me with a stoichiometric amount of AgSO₃CH₃ in nitromethane.     

Probing conserved amino acids in phospholipase D (Brassica oleracea var. capitata) for their importance in hydrolysis and transphosphatidylation activity

In addition to hydrolysis of glycerophospholipids, phospholipases D (PLDs) catalyze the head group exchange. The molecular basis of this transphosphatidylation potential, which strongly varies for PLDs from different sources, is unknown hitherto. Recently, the genes of two PLD isoenzymes from white cabbage have been sequenced and expressed in Escherchia coli, yielding the basis for mutational studies. In the present paper, three sequence characteristics of the isoenzyme (PLD2) that corresponds to the often used enzyme isolated from cabbage leaves have been probed for their importance in hydrolysis as well as transphosphatidylation activities: (i) the two HKD motifs, (ii) the C terminus and (iii) the eight cysteine residues. All these regions or amino acids are highly conserved in alpha-type plant PLDs. Based on multiple alignments, predictions of secondary structure and comparisons of hydrophobicity profiles, 35 enzyme variants were created and assayed. All positions tested proved to be very sensitive towards amino acid exchanges with respect to hydrolytic activity in the absence of glycerol as well as to the ratio of hydrolytic and transphosphatidylation activities in the presence of glycerol. A significant increase of total activity and transphosphatidylation activity could be obtained by the substitutions C310S and C625S.     

XPS and DSC Studies of Solution Cast Polystyrene/Poly(organophosphazene) Blends. II. Polystyrene/Poly(4-phenoxyphenoxy)phosphazene

Blends of polystyrene (PS) with poly(4-phenoxyphenoxy)phosphazene (PPA) were studied by differential scanning calorimetry (DSC) and X-ray photoelectron spectroscopy (XPS). A third component, poly(2,6-dimethyl-1,4-phenylene ether) (PPE), was added to improve the compatibility. While DSC and XPS reveal that PS and PPA are incompatible, the presence of PPE increases the compatibility between the two polymers.     

New syntheses of methoxypoly(oxyethylene) vinyl ether and its oligo analog

Summary A new method to synthesize vinyl ethers of methoxyoligooxyethylene, I, and methoxypoly(oxyethylene), II, is described. In this work, these derivatives were prepared by reacting the alkoxide of ethylene glycol vinyl ether with the tosylate (or mesylate) of oligo-/or methoxypoly(oxyethylene) in tetrahydrofuran. Received: 27 November 2001/Revised version: 13 March 2002/ Accepted: 18 March 2002     

绵羊骨髓细胞抗菌肽基因的改造及其在原核生物中的表达

目的通过对绵羊骨髓细胞抗菌肽(sheep myeloid antibacterial peptides with 29 amino acids,SMAP-29)的活性片段SMAP-29(1-18)基因的改造,使其以C-端融合蛋白的形式在大肠埃希菌(E.coli)BL21(DE3)中表达。方法根据大肠埃希菌偏爱密码子表,将SMAP-29的活性片段SMAP-29(1-18)基因序列进行改造,应用ProtParam分析SMAP-29的理化特性,Anthorprot软件预测其螺旋轮结构,设计新的基因片段,插入质粒pET-30a中,构建重组表达质粒pET-30aSMAP-29[1-18,K2,4,L13],转化感受态E.coli BL21(DE3),IPTG诱导表达,表达产物过2次Ni2+NTA His Bind resin柱进行纯化。结果 SMAP-29基因序列经改造后,稳定性、等电点及半衰期均明显提高。重组质粒经PCR、双酶切及测序鉴定,证明构建正确。表达的重组蛋白相对分子质量约61 257,以包涵体形式存在,表达量占菌体总蛋白的41%,纯度为81%。结论已成功对SMAP-29基因进行改造,实现了其在E.coli BL21(DE3)中的高表达,获得了纯度较高的目的蛋白,为进一步规模化生产SMAP-29奠定了理论及实践基础。     

Synthesis,crystal structures and biological activities of 2-acetylpyridine N(4)-cyclohexylthiosemicarbazone and its manganese(II) and nickel(II) complexes

2-Acetylpyridine N(4)-cyclohexylthiosemicarbazone (HL) and its manganese(II) and nickel(II) complexes formulated as [Mn(L)₂] (1) and [Ni(L)₂] (2) have been synthesized and characterized by elemental analysis, infrared spectra, mass spectra, and single-crystal X-ray diffraction studies. In the two complexes, the coordination polyhedron approaches an octahedron, where the two ligands coordinate to the metal via the pyridine nitrogen atom and the nitrogen and sulfur donors of the thiosemicarbazide moiety. Biological studies, carried out in vitro against selected bacteria and K562 leukaemia cell line, respectively, have shown that the free ligand and its complexes exhibited distinct differences in the biological activities.     

Thermal Studies of Zn(II), Cd(II) and Hg(II) Complexes of Some N-Alkyl-N-Phenyl-Dithiocarbamates

The thermal decomposition of Zn(II), Cd(II) and Hg(II) complexes of N-ethyl-N-phenyl and N-butyl-N-phenyl dithiocarbamates have been studied using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The products of the decomposition, at two different temperatures, were further characterized by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). The results show that while the zinc and cadmium complexes undergo decomposition to form metal sulphides, and further undergo oxidation forming metal oxides as final products, the mercury complexes gave unstable volatiles as the final product.