A complexomic study of Escherichia coli using two-dimensional blue native/SDS polyacrylamide gel electrophoresis

Study of the complexome - all the protein complexes of the cell - is essential for a better understanding and more global vision of cell function. Using two-dimensional blue native/SDS-PAGE (2-D BN/SDS-PAGE) technology, the cytosolic and membrane protein complexes of Escherichia coli were separated. Then, the different partners of each protein complex were identified by LC-MS/MS. In this report, 306 protein complexes were separated and identified. Among these protein complexes, 50 heteromultimeric and 256 homomultimeric protein complexes were found. Among the 50 heteromultimeric protein complexes, 18 previously described protein complexes validate the technology. In this study, 109 new protein complexes were found, providing insight into the function of previously uncharacterized bacterial proteins.     

meso-四(对烷氧基苯基)卟啉合银的合成、表征和性能研究

合成了10种未见文献报道的m eso-四(对烷氧基苯基)卟啉合银配合物,研究了其合成、分离、纯化方法.用红外光谱、紫外-可见光谱、核磁共振氢谱、质谱和元素分析等对各个化合物的结构进行了表征.研究了其荧光性能,用差示扫描量热仪和偏光显微镜对其液晶性质进行了研究,发现10个配合物均具有液晶性.     

Synthesis and photoluminescence properties of BF2 complexes with 1,3-diketone ligands

BF₂ complexes with 1,3-diketone ligands were synthesized, and their optical and electrochemical properties were studied. The colors of the complexes varied depending on the structures of the 1,3-diketone ligands. The absorption and emission maxima of the complexes with 1,3-diaryl-1,3-diketone ligands were considerably red shifted as compared to those of the complexes with 1-aryl-3-trifluoromethyl-1,3-diketone ligands, suggesting an extended π-conjugation of the 1,3-diaryl-1,3-diketone moieties. The molar absorption coefficients and quantum yields of the complexes with 1,3-diaryl-1,3-diketone ligands were larger than those of the complexes with 1-aryl-3-trifluoromethyl-1,3-diketone ligands. Cyclic voltammetry measurements revealed that the reduction potentials of the BF₂ complexes were higher than those of the free ligands. These complexes exhibited various emission colors in the solid states due to the intermolecular interactions.     

Mechanistic study of beta-hydrogen elimination from organoplatinum(II) enolate complexes

A detailed mechanistic investigation of the thermal reactions of a series of bisphosphine alkylplatinum(II) enolate complexes is reported. The reactions of methylplatinum enolate complexes in the presence of added phosphine form methane and either free or coordinated enone, depending on the steric properties of the enone. Kinetic studies were conducted to determine the relationship between the rates and mechanism of beta-hydrogen elimination from enolate complexes and the rates and mechanism of beta-hydrogen elimination from alkyl complexes. The rates of reactions of the enolate complexes were inversely dependent on the concentration of added phosphine, indicating that beta-hydrogen elimination from the enolate complexes occurs after reversible dissociation of a phosphine. A normal, primary kinetic isotope effect was measured, and this effect was consistent with rate-limiting beta-hydrogen elimination or C-H bond-forming reductive elimination to form methane. Reactions of substituted enolate complexes were also studied to determine the effect of the steric and electronic properties of the enolate complexes on the rates of beta-hydrogen elimination. These studies showed that reactions of the alkylplatinum enolate complexes were retarded by electron-withdrawing substituents on the enolate and that reactions of enolate complexes possessing alkyl substituents at the beta-position occurred at rates that were similar to those of complexes lacking alkyl substituents at this position. Despite the trend in electronic effects on the rates of reactions of enolate complexes and the substantial electronic differences between an enolate and an alkyl ligand, the rates of decomposition of the enolate complexes were similar to those of the analogous alkyl complexes. To the extent that the rates of reaction of the two types of complexes are different, those involving beta-hydrogen elimination from the enolate ligand were faster. A difference between the rate-determining steps for decomposition of the two classes of complexes and an effect of stereochemistry on the selectivity for beta-hydrogen elimination are possible origins of the observed phenomena.     

Mass spectral behavior of some homoleptic and mixed aryldichalcogenide bis(diphenylphosphino)ferrocenenickel(II), palladium(II), and platinum(II), and bis(diisopropylphosphino)ferrocenepalladium(II) complexes

The mass spectral behavior of a number of organometallic complexes containing the Group 10 metals Ni, Pd, and Pt, together with various thiolate ligands were studied. For Pd, two main types of complexes, differing by the substituents on the phosphorus atom were studied. Types I and II were substituted with bis(diphenylphosphino)ferrocene and bis(diisopropylphosphino)ferrocene ligands, respectively. The Ni complexes, except for one, and the Pd Type I complexes had no molecular radical cations (M(+.)) in their EI spectra. On the other hand, all the Pt complexes showed intense M(+.) ions in their EI spectra indicating that these complexes were more stable as radical cations than those of Ni and Pd. The FAB and MALDI spectra of all the complexes displayed intense quasi-molecular ions (MH(+)) and the fragmentations in both modes were similar. The MALDI spectra of several complexes displayed only M(+.) ions while one gave evidence of both MH(+) and M(+.) ions. Several Pd Type II complexes yielded intense M(+.) in their EI spectra.     

Preparation and luminescence properties of lanthanide (Eu3+, Sm3+) complexes and their hectorite-based composites

The complexes of europium and samarium with phthalates ligands were synthesized and characterized. The luminescence behaviors of the lanthanide complexes as well as their hectorite-based composites were investigated by fluorescence spectra. The results indicated that the lanthanide complexes showed slightly lower intensities in hectorite matrix than that of corresponding pure complexes. The lanthanide ion relative fluorescence intensity (LRFI) was enhanced when the lanthanide complexes were doped into hectorite.     

4-Vinylbenzyl-substituted silver(I) N-heterocyclic carbene complexes and ruthenium(II) N-heterocyclic carbene complexes: synthesis and transfer hydrogenation of ketones

4-Vinylbenzyl-substituted Ag(I) N-heterocyclic carbene (NHC) complexes and Ru(II) NHC complexes have been synthesized. The Ag(I) complexes were synthesized from the imidazolium salts and Ag₂O in dichloromethane at room temperature. The Ru(II) complexes were prepared from Ag(I) NHC complexes by transmetallation. The six 4-Vinylbenzyl-substituted Ag(I) NHC complexes and six 4-Vinylbenzyl-substituted Ru(II) NHC complexes have been characterized by spectroscopic techniques and elemental analyses. The Ru(II) NHC complexes show catalytic activity for the transfer hydrogenation of ketones.     

环钯化合物合成及其在催化中的应用

环钯化合物由于丰富的结构、高度的稳定性和卓越的催化性能,已成为钯化学研究的热点之一。迄今已开发出了C-H键活化、氧化加成、转金属化、亲核加成和配体交换等多种方法,可制备出从三元环到十一元环的CY型环钯化合物和多种YCY型环钯化合物。环钯化合物目前已应用于偶联、烯烃氢化和不对称催化等反应中。本文简单介绍了环钯化合物的种类,重点介绍了环钯化合物的合成方法和催化应用情况,最后提出了环钯化合物在今后合成研究和催化应用中的发展建议。     

Transformation of 2-alkoxyimidate-1,10-phenanthroline metal (Mn, Co and Ni) chlorides from bis(2-cyano-1,10-phenanthroline) metal chlorides: Syntheses, characterizations and their catalytic behavior toward ethylene oligomerization

The 2-alkoxyimidate-1,10-phenanthroline complexes of manganese, cobalt and nickel have been synthesized by the reaction of 2-cyano-1,10-phenanthroline with metal dichloride in the corresponding alcohol. The metal complexes bearing two 2-cyano-1,10-phenanthrolines were isolated in non-protonic solvent as the coordination around metal core with two ligands and two chlorides. The alkoxyimidation of nitrile linked on ligand was speeded in forming the 2-alkoxyimidate-1,10-phenanthrolinyl metal complexes. All the complexes have been characterized by FT-IR spectra and elemental analysis, and some of their structures have also been confirmed by single-crystal X-ray diffraction analysis. All the metal complexes were evaluated in the catalytic oligomerization of ethylene with some alkylaluminums as co-catalyst; in which manganese complexes were less active, cobalt complexes showed low to moderate activities, and nickel complexes gave moderate to good activities.     

聚合物载体-稀土金属络合物的研究 Ⅵ.聚合物载体-钕络合物对丁二烯聚合的催化活性

 红外光谱研究表明,苯乙烯-丙烯酸共聚物载体-钕络合物具有双配位的羧酸根结构,Nd-O键富有共价性。考察了载体钕络合物催化丁二烯聚合的一般规律,载体钕络合物的组成与聚合活性的关系。在溶剂THF或二氧六环的存在下制得的苯乙烯-丙烯酸共聚物最适宜于合成高活性的载体钕络合物。功能团-COOH含量大约12％,金属钕含量与功能团含量摩尔比在0.20左右的载体钕络合物催化活性最佳。     

Theoretical study on the DNA interaction properties of copper(II) complexes

Theoretical studies on DNA-cleavage and DNA-binding properties of a series of Cu(II) complexes [Cu(bimda)(diimine)] 1–5 have been carried out by density functional theory (DFT). The optimized structures of Cu(II) complexes were docked into parallel, antiparallel and mixed G-quadruplexes, with which the binding energies of complexes 1–5 were obtained. The cytotoxicities of these complexes can be predicted preliminarily by the binding energies. To explore the energy changes of Cu(II) complexes in duplex DNA, the optimized structures of these complexes were docked into the duplex DNA, and the obtained docking models were further optimized using QM/MM method. The DNA-cleavage abilities of complexes 1–5 can be predicted accurately and explained reasonably by the computed intra-molecular reorganization energies of these complexes. This work reported here has implications for the understanding of the interaction Cu(II) complexes with the DNA, which might be helpful for the future directing the design of novel anticancer Cu(II) complexes.     

Charge-transfer complexes from decamethylferrocene and 1,4-quinone derivatives: neutral-ionic phase diagrams for metallocene complexes

Charge-transfer (CT) complexes of ferrocenes with 1,4-quinone derivatives were investigated. Deca- and octamethylferrocene complexes with 1,4-naphthoquinone derivatives were prepared and structurally characterized; these were neutral 1:2 DA complexes with mixed-stack structures. The formation of complexes with 1,4-benzoquinones was examined by applying solvent-drop grinding. CT energies and phase transitions in these neutral and other ionic complexes were investigated. Their electronic states are discussed on the basis of the phase diagrams derived for mixed-stack ferrocene-based CT complexes, taking into account their dependence on the DA ratio, dimensionality, and intermolecular interactions.     

Polymeric complexes of chitosan with proteins and hydroxyl-containing polymers

The structures of polymeric complexes of chitosan with methyl cellulose, lactoserum protein, gelatin, and polyvinyl alcohol were simulated on a computer. The mechanism of metal captures in cavities of these complexes was analyzed. The conformational and geometric characteristics of polymeric complexes of chitosan were obtained. The properties and structure of complexes in solutions and in the bulk were examined.     

Infrared and Mössbauer studies of some diamine complexes with trimethyltin halides and dimethyltin dihalides

To obtain more structural information on complexes formed between alkyltin halides and bidentate ligands, the solid-state IR and Mössbauer spectra of the 1,2-ethanediamine and 1,4-butanediamine complexes of trimethyltin halides and dimethyltin dihalides were examined. The structures of the trimethyltin halide complexes were found to be trigonal bipyramidal with coplnar methyl groups. The dimethyltin dihalide complexes were octahedral with the methyl groups in the cis-positions and the halides trans to each other. However, there were no differences in the structures of the chloro and bromo complexes of either type.     

异核稀土双亚砜配合物的合成、表征和荧光性质

合成得到一系列异核土双乙烷配合物和异核稀土双乙烷与１,１０－啡咯啉的配合物,通过元素分析,电感耦合等离子体法,电导,红外和紫外光谱对配合进行了表征,并研究了这些配合物的固体和溶液的荧光光谱。     

New metal aminocarbene-substituted cyclopentadienyliron half sandwich complexes

Some new half sandwich cyclopentadienyl aminocarbene complexes were prepared by treatment of the corresponding alkoxycarbene complexes with primary and secondary amines, including enantiopure chiral aminoalcohols and amines with acetyl, phosphine, alkene, and alkyne functionalities, all of which proved to be compatible with the substrates. In two cases the complexes were crystallographically characterized indicating that the metal–carbon double bond is – in contrast to some alkoxycarbene analogues – not in conjugation with the cyclopentadienyl π-system in the solid state. Some of the complexes were characterized by cyclic voltammetry showing similar behavior as the corresponding alkoxycarbene complexes. The complexes are the first examples of half sandwich complexes with a cyclopentadienyl-aminocarbene ligand system.     

Copper(II) complexation with 1-methyl-2-mercaptoimidazole in 7 M HCl

The complexation of copper(II) with 1-methyl-2-mercaptoimidazole in 7 M HCl was potentiometrically studied. The compositions of complexes were determined, and their stepwise formation constants were calculated. The complexes were shown to become less stable with increasing temperature. The thermodynamic functions of complexation were estimated. The copper complexes were shown to surpass the rhenium complexes in stability.     

Spectroscopic,structure and DFT studies of palladium(II) complexes with pyridine-type ligands

Five palladium(II) complexes with pyridine derivative ligands have been synthesized. The molecular structures of the complexes were determined by X-ray crystallography, and their spectroscopic properties were studied. Based on the crystal structures, computational investigations were carried out in order to determine the electronic structures of the complexes. The electronic spectra were calculated with the use of time-dependent DFT methods, and the electronic spectra of the transitions were correlated with the molecular orbitals of the complexes. The emission properties of the complexes have been examined.     

Paramagnetic NMR shift,spectroscopic and molecular modeling studies of lanthanide(III)-morin complexes

Studies on nine-coordinate lanthanide complexes of morin are described. The complexes were characterized by elemental analysis, molar conductance, UV–Vis spectra, IR spectra, thermal analysis and NMR spectra. Molecular modeling studies were also carried out. The complexes are non-electrolytes in DMSO. TGA showed anhydrous nature of the complexes. The electronic spectra of the complexes were recorded in methanol. ¹H NMR spectra of lanthanum, praseodymium, neodymium, samarium and dysprosium complexes have been studied in DMSO-d₆. The complexes do not dissociate in DMSO and retain their coordination. ¹H NMR spectra of paramagnetic and diamagnetic complexes exhibit downfield as well as upfield shifts of morin resonances that shows change in geometry during coordination.     

含二茂铁双Schiff碱配体及其Ni(Ⅱ)配合物电子光谱和二阶非线性光学性质的密度泛函理论研究

采用密度泛函理论(DFT)B3LYP方法,对含二茂铁双Schiff碱配体及其Ni(Ⅱ)配合物的几何构型进行优化.在得到稳定构型的基础上,采用含时密度泛函理论(TD-DFT)的B3LYP方法计算了配合物的电子光谱,并结合有限场(FF)方法研究了配体和配合物的极化率和二阶非线性光学(NLO)性质.结果表明,配体中引入Ni(...