Pulse radiolysis study of rapid electron transfer from electron adduct and reducing OH adduct of dAMP to riboflavin and flavin adenine dinucleotide (FAD)

Rapid electron transfer from electron adduct and reducing OH adduct of 2'-deoxyadenosine-5'-monophosphate acid (dAMP) to riboflavin (RF) and flavin adenine dinudeotide (FAD) was studied using the time-resolved pulse radiolysLs techniques. Both spectroscopic and kinetic analyses showed that transient absorption spectrum of electron adduct or OH adduct of dAMP formed at first, and then changed to that of radical anion of RF or FAD after several microseconds of pulse. The evidence indicated that electron transfer from electron adduct and reducing OH adduct of dAMP to RF or FAD did occur. From buildup or bleaching kinetics of radical anions of RF and FAD, the rate constants for electron transfer were determined, respectively.     

A new class of rhodium complexes containing free donor atoms and their intramolecular substitution reaction

A new class of rhodium complexes with high catalytic activity as well as excellent stability,which was used as catalyst for carbonylation of methanol to acetic acid,is reported.It contains free donor (namely un-coordinated donor) atoms which enable to improve its stability by intramolecular substitution reaction.Its synthesis,characteristic and catalytic reaction were discussed here.     

Metal compound-mediated hydrolytic cleavage of oxidized insulin B chain:Regioselectivity and influence of peptide secondary structure

The interaction of oxidized insulin B chain(B)with cis-[Pd-(en)Cl2](en=ethylenediamine),cis-[Pd-(dtco-3-OH)Cl2](dtco-3-OH=dithiacyclooctan-3-ol)and CuCl2 was studied by electrospray inass spectrometry.It is discovered that the binding of Pd(Ⅱ)complexes and the sites of cleavage are highly dependent on the secondary structure and local environment of B.The hydrolytic cleavage of denatured B by Pd(Ⅱ)complexes was monitored by HPLC.The reaction is regioselective and follows first order kinetics with half-life of 4.8 days at 40℃.Two amide bonds,i.e.at Leu6-Cys7 and at Gly8-Ser9,which are close to the two potential Pd(Ⅱ)binding sites His5 and His10,are selectively cleaved.In the case of Cu(Ⅱ)ion as promoter,only one cleavage site was observed which is located at Gly8-Ser9 bond.These results provide improved understanding on the design of artificial metallopeptidase.     

Structure and electrospray mass spectrometry studies on dithiacyclooctan-3-ol-containing palladium (II) complex of trans -[Pd(dtco-3-OH)_2](ClO_4)_2·2DMSO

The structure of trans-[Pd(dtco-3-OH)2] (ClO4)2·2DMSO, in which dtco-3-OH is dithiacyclooctan-3-ol and DMSO is dimethyl sulfoxide, was determined by X-ray crystallographic analysis. The crystal data: space group pi, a = 0.7077(2) nm, b = 1.0788(1) nm, c = 1.1111(1) nm, α=67.710(8)°, β = 73. 59(2)°, γ = 85. 39(2)°,R1 = 0 . 0368 and Rw = 0.0998. The palladium (II) is coordinated by four sulfur atoms with a regular square planar configuration. The Pd-S distances are 0.2314(1) and 0.2317(1) nm, respectively. Both dtco-3-OH ligands are in the boat-chair configuration and two hydroxyl groups are on the opposite sites of the PdS4 coordination plane and are towards Pd(II). The Pd-O distance is 0. 285 nm, indicating a weak interaction between them. A typical hydrogen bond between the hydroxyl group of dtco-3-OH ligand and DMSO was observed in the crystal structure. An aqueous solution prepared with the crystals of the complex was used for the investigation of electrospray mass spectrometry ( ESMS ). Besid     

Molecular-level investigation on electrochemical interfaces by Raman spectroscopy

The structure and dynamics of electrode/liquid interfaces play an increasingly important role in electrochemistry. Raman spectroscopy is capable of providing detailed structural information at molecular level and new insight into the interfacial structure, adsorption, reaction, electrocatalysis and corro-sion. In this account we will summarize some progresses of surface Raman spectroscopy in the study of electrochemical interfaces, mainly based on our group's work, laying emphasis on the detection sensitivity, spectral resolution, time resolution and spatial resolution as well as the hyphenated technique.     

Theoretical study on second-order nonlinear optical properties of unsymmetric bis (phenylethynyl) benzene series derivatives

On the basis of ZINDO methods, according to the sum-overstates (SOS) expression, the program for the calculation of the second-order nonlinear optical susceptibilities βijk and βμ of molecules was devised, and the structures and nonlinear optical properties of unsymmetric bis (phenylethynyl) benzene series derivatives were studied. The influence of the molecular conjugated chain lengths, the donor and the acceptor on βμ was examined.     

Synthesis and biological evaluation of andrographolide derivatives as potent anti-HIV agents

A series of Andro derivatives were described and evaluated for their anti-HIV activity in vitro.Compound 10 and 16b,of which TI were>10,had some anti-HTV-l activity in vitro.Therein,compound 10 which was the best potent compound,could serve as a new lead for further development of anti-AIDS agents.     

The antimicrobial activities of a series of bis-quaternary ammonium compounds

A series of bis-quaternary ammonium compounds(bis-QACs) N,N’-hevamethylenebis(1-alkyl-4-carbamoyl pyridinium bromide)(4BCAP-6,n)(alkyl chain length,n=8,10,12,14,16 and 18) were synthesized and characterized.Their surface tensions,critical micelle concentrations(CMC),and antimicrobial activities were evaluated.4BCAP-6,10 exhibited the strongest antimicrobial activities except for that against Proteus vulgari.The activities of 4BCAP-6.n against Escherichia coli zk126 were not significantly influenced by temperature.pH and initial bacteria concentration.These results indicate that bis-QACs exhibit high antimicrobial activity regardless of the environmental conditions.     

Study on Lithium Insertion in Lepidocrocite and ,λ-MnO2 Type TiO2： A First-Principles Prediction

TiO2 is a latent anode material for rechargeable lithium batteries. Our simulation models, basing lepidocrocite and 2-MnO2 type TiO2 were investigated by density functional theory （DFT）. The key issues are focused on the lithium insertion sites, electronic structures, and the conducting paths of Li＋ ions. Our calculated data indicate the calculated voltage of 2-MnO2 type TiO2 is higher than that of lepidocrocite type TiO2. The Li＋ ion migration energy barrier of lepidocroeite type YiO2 along the [1 0 0] direction （0.45 eV） is lower than that of along the [110] direction （0.57 eV）. The energy barriers of 2-MnO2 type TiO2 to move a Li＋ ion among the adjacent embedded sites （16c or 8a sites） is 0.68 eV.     

Hydrothermal synthesis and characterization of rare-earth ruthenate pyrochlore compounds R_2Ru_2O_7(R=Pr_(3+),Sm(3+)-Ho(3+))

A series of pyrochlore oxides, R2Ru2O7 (R=Pr3+, Sm3+–Ho3+) were synthesized under mild hydrothermal conditions. All the samples crystallize in uniform octahedron characteristically. The products were characterized by powder X-ray diffraction, scanning electron microscopy, energy-disperse X-ray spectroscopy, and dc susceptibility, and the factors that affected the crystallization were discussed. It was found that the purity of products depends strongly on the raw materials and the amount of alkalinity in the...