FTIR spectroscopic study on the interaction between a fluoroionophore and metal ions.

A fluoroionophore sensor, N-[4-(1-pyrene)butyroyl]-L-tryptophan (PLT), has been reported. It can distinguish lead ion from other 12 metal ions via forming a pyrene dimer and it exhibits a very high sensitivity (0.15 microM) in aqueous solution (Chem. Commun., 2006, 2702). When the indole moiety in PLT was changed to benzene, in forming a new fluoroionophore of N-[4-(1-pyrene)butyroyl]-L-phenylalanine (PLP), it could not form a pyrene dimer in response to Pb(2+) in water. The present study describes the spectroscopic clarification of the intrinsic differences of the binding model between PLP and PLT in binding with Pb(2+). The model shows identical chelating bidentate coordination between COO(-) and Pb(2+) both in PLP-Pb and PLT-Pb; however, there is no indication of the interaction between the phenyl ring and the metal ion or the hydrogen bonding between amide groups in PLP-Pb. These differences in the binding model between PLP-Pb and PLT-Pb illustrate that the indole ring in PLT appears to play a crucial role in the high selectivity and sensitivity of PLT to lead(II) ion.     

Radially symmetric solutions of the p-Laplacian in perforated-like domain with nonlocal boundary condition

In this paper, we study the stability of solutions to a von Kármán system for Kirchhoff plate equations with a memory condition working at the boundary. We show that such dissipation is strong enough to produce exponential decay of the solution provided the relaxation functions also decay exponentially. When the relaxation functions decay polynomially, we show that the solution decays polynomially.     

Synthesis of some chiral liquid crystals and study of the effect of intramolecular hydrogen bonding on the phase behaviour

The synthesis of three new series of chiral Schiff's bases containing benzilideneaniline and 2-hydroxybenzilideneaniline moieties as mesogenic cores is presented. Differential scanning calorimetry, optical polarizing microscopy and X-ray diffraction measurements were used to study the phase transition temperatures and behaviour. The results reveal that most of these materials show chiral smectic mesomorphism.     

Studies on the thermodynamic properties of new ionic liquids: 1-Methyl-3-pentylimidazolium salts containing metal of group III

This paper reports that new ionic liquids (ILs) have been prepared by directly mixing the chloride of group III and 1-methyl-3-pentylimidazolium chloride (PMIC) with molar ratio 1/1 under dry argon atmosphere. The densities and surface tension of these ILs were determined at temperature range of 273.15 K to 343.15 ± 0.1 K. The properties for the ionic liquids were discussed by interstice model and Glasser’s theory.     

Calculations on the octupolar molecules with enhanced two-photon absorption cross sections based on the Zn (II) and Cu (I) as centers

The equilibrium geometries, electronic structures, as well as one- and two-photon absorption cross sections of a series of octupolar chromophores with Zn(2+) or Cu(+) as coordinate centers and 4,4'-bis(dibutylaminostyryl)-[2,2']-bis(bipyridyl) as ligands have been determined by using B3LYP/6-31G and ZINDO methods. These molecules are designed by controlled combination of two or three bipyridyl ligands with the metal centers. The results show that Zn(2+) is an effective template for the design of octupolar structures which enable it to form tetrahedral and octahedral coordinated complexes; while Cu(+) only exists in a tetrahedral coordinated complex, comparing the tetrahedral complex with Zn(2+) as the center with that of Cu(+) as the center, it is found that the complex with the Cu(+) center is a better two-photon absorption material than the former as far as the transparency/nonlinearity is concerned. Furthermore, for the same metal center of Zn(2+), both one- and two-photon absorptions of the tetrahedral complex are redshifted relative to those of the octahedral complex, is attributed to the spiroconjugation effect in the tetrahedral complex. Our theoretical findings are consistent with recent experimental observations and provide an important foundation for the design of improved transparency-nonlinearity two-photon absorption materials.     

Synthesis,Structure and Theoretical Calculation of Metal Coordination Polymers with Pyrazine-2,3-dicarboxylic Acid and 3-(2-Pyridyl)pyrazole as Co-ligands

A new 2D metal coordination polymer(MCP),[Mn(pzdc)_(0.5)(L)]_n(1,pzdc=pyrazine-2,3-dicarboxylic acid,HL=3-(2-pyridyl)pyrazole),was synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction,powder XRD,FT-IR,TG,fluorescence and elemental analysis techniques.Pale yellow crystals crystallize in orthorhombic system,space group Fdd2 with a=11.2368(6),b=38.280(2),c=10.5682(6) A,V=4545.9(4) A~3,C_(11)H_7MnN_4O_2,M_r=282.15,D_c=1.649 g/cm~3,μ(MoKα)=1.159 mm~(-1),F(000)=2272,Z=16,the final R=0.0613 and wR=0.1773 for 2856 observed reflections(I 2σ(I)).It shows a two-dimensional network structure and is further assembled into a three-dimensional supramolecular framework via hydrogen bonds and abundant π-π interactions.In addition,we analyzed natural bond orbital(NBO) of 1 in using the PBE0/LANL2DZ method established in Gaussian 03 Program.There is obvious covalent interaction between the coordinated atoms and Mn(Ⅱ) ions.     

Decomposition Reaction of Zn-MPA（3-Mercaptopropionic Acid） Complex Under Microwave Irradiation

The thermal decomposition of Zn-MPA complex was investigated under microwave irradiation. ZnO and ZnS nanocrystals could be obtained by decomposing Zn-MPA（3-mercaptopropionic acid） complex under different reaction conditions. It was found that both the pH value of the solution and the molar ratio of Zn2＋ and MPA can play an important role in the formation of ZnO and ZnS nanocrystals. MPA mainly acts as an S source or as a complexing agent. This study provides a new route for the controllable preparation of semiconductor nanocrystals.     

Cloning, Expression and Purification of Wheat Acetyl-CoA Carboxylases CT Domain in E.coil

The entire gene of carboxyltransferase(CT) domain of acetyl-CoA carboxylase(ACCase) from Chinese Spring wheat(CSW) plastid was cloned firstly,and the 2.3 kb gene was inserted into PET28a+ vector and expressed in E.coil in a soluble state.The (His)6 fusion protein was identified by SDS-PAGE and Western blot.The recombinant protein was purified by affinity chromatography,and the calculated molecular mass(Mr) was 88000.The results of the sequence analysis indicate that the cloned gene(GeneBank accession No.EU124675) was a supplement and revision of the reported ACCase CT partial cDNA from Chinese Spring wheat plastid.The recombinant protein will be significant for us to investigate the recognizing mechanism between ACCase and herbicides,and further to screen new herbicides.     

On the regioselectivity of the fremy's salt oxidation of phenols

A detailed study of the regioselectivity of the Fremy's salt oxidation of phenols, including a series of MNDO calculations of the intermediate phenoxy radicals, has been carried out. The analysis of these results has led us to establish a new rule for the para vs. ortho regioselectivity, namely: “C-4 unsubstituted phenols, as well as phenols substituted at C-4 with easy-to-displace groups, undergo oxidation (or oxidative degradation) by the action of Fremy's salt, thus eventually providing the corresponding p-quinones”. A similar rule for the ortho vs. ortho' regioselectivity could not be so precisely formulated since now steric effects play a significant major role.     

A simple and efficient method for the allylation of heteroarenes catalyzed by PdCl2

The PdCl₂-catalyzed allylation of heteroarenes is presented. Various heteroarenes including O-, N-, and S-based ones were allylated efficiently with a rich range of allylic acetates in the presence of only 2 mol % of PdCl₂, without the need of bases/acids, additives, and external supporting ligands. In addition, the reactions were carried out under mild and simple conditions just by stirring the two reactants and catalyst in CH₂Cl₂ at 60 °C. Moreover, the by-product produced was non-toxic acetic acid. Thus, the method presented in this work provides a general, clean, and operationally simple approach for the functionalization of heteroarenes. Finally, a preliminary mechanistic study suggested that the Pd(II) may be reduced in situ by the heteroarenes to Pd(0), which serves as the active metal center to catalyze the following allylations of heteroarenes via a Tsuji–Trost pathway.