Modified polyoxometalates: Hydrothermal syntheses and crystal structures of three novel reduced and capped Keggin derivatives decorated by transition metal complexes

Three novel polyoxometalate derivatives decorated by transition metal complexes have been hydrothermally synthesized. Compound 1 consists of [(PMo6Mo2V8O44)-Mo-VI-V-V-O-IV{CO (2,2'-bipy)(2)(H2O)}(4)](3+) polyoxocations and [(PMo4Mo4V8O44)-Mo-IV-V-V-O-IV{Co(2,2'-bipy)(2)(H2O)}(2)](3-) polyoxoanions, which are both built on mixed-metal tetracapped [PMo8V8O44] subunits covalently bonded to four or two {Co(2,2'-bpy)(2)(H2O)}(2+), clusters via terminal oxo groups of the capping V atoms. Compound 2 is built on [(PMo8V6O42)-V-VI-O-IV{Cu-I(phen)}(2)](5-) clusters constructed from mixed-metal bicapped [(PMo8V6O42)-V-VI-O-IV](7-) subunits covalently bonded to two {Cu(phen)}(+) fragments in the similar way to 1. The structure of 3 is composed of [(PMo9Mo3O40)-Mo-VI-O-V](6-) units capped by two divalent Ni atoms via four bridging oxo groups.

From dissymmetrical mononuclear entities to centrosymmetrical heterotrinuclear complex with 2D supramolecular structure: synthesis, characterization, crystal structure, and magnetic properties

A new centrosymmetrical heterotrinuclear complex, {[Cu(oxbe)](2)Co(H2O)(2)}.2DMF.DMA with 2D supramolecular structure, has been obtained by the self-assembly of a dissymmetrical building block [Cu(oxbe)](-) with bivalent metal ion Co2+, where H(3)oxbe is dissymmetrical ligand N-benzoato-N'-(2-aminoethyl)oxamido, DMF = dimethylformamide, DMA = dimethylamine. Its structure was determined by single crystal X-ray analysis. The molecular structure is centrosymmetrical with the cobalt atom lying on an inversion center. Through the hydrogen bonds and d-pi stacking interactions, a 2D supramolecular structure is formed. This study exemplifies a new method for the assembly of supramolecular structure using a dissymmetrical brick. Magnetic susceptibility measurements (5-300 K) indicate that the central cobalt and terminal copper metal ions are antiferromagnetically coupled with J = -23.1 cm(-1).

Oxamido-bridged heterobinuclear copper(II)-nickel(II) complex and homotrinuclear nickel(II) complex with 2D supramolecular structure: synthesis, crystal structure, magnetic and spectroscopic properties

The oxamido-bridged heterobinuclear copper(II)-nickel(II) complex, [Cu(oxbe)Ni(phen)(2)]ClO4.3H(2)O (1) and homotrinuclear nickel(11) complex {[Ni(oxbe)](2)Ni(H2O)(2)}.2.5DMF (2) have been synthesized and characterized by means of elemental analysis, IR, EPR. and electronic spectra and magnetic susceptibility, where H(3)oxbe is dissymmetrical ligand N-benzoato-N'-(2-aminoethyl)ox-amido, phen = 1.10-phenanthroline, DMF = dimethylformamide. Complex I has an extended oxamido-bridged structure consisting of planar copper(II) and octahedral nickel(II) ions. The chi(M) and mu(eff) versus T plots of 1 is typical of an antiferromagnetically coupled Cu(II)-Ni(II,) pair with a spin-doublet ground state, and magnetic analysis leads to J = -57.1 cm(-1). The molecular structure of 2 is centrosymmetrical, with one octahedral nickel atom lying at an inversion center and two terminal Ni(II) atoms in approximately square planar environment. Through the hydrogen bonds and pi- pi stacking interactions, a 2D supramolecular structure is formed.

Tetra-mu-alpha-alanine-bis[tetraaquagadolinium(III)] hexaperchlorate

The title complex, [Gd-2 (C3H7NO2)(4)(H2O)(8)](ClO4)(6), contains centrosymmetric dimeric [Gd-2 (Ala)(4) (H2O)(8)](6+) cations (Ala is alpha-alanine) and perchlorate anions. The four alanine molecules act as bridging ligands linking two Gd3+ ions through their carboxylate O atoms. Each Gd3+ ion is also coordinated by four water molecules, which complete an eightfold coordination in a square-antiprism fashion. The perchlorate anions and the methyl groups of the alanine ligands are disordered.

Characterization of aconitine-type alkaloids in the flowers of Aconitum kusnezoffii by electrospray ionization tandem mass spectrometry

The fragmentation mechanism of aconitine-type alkaloids in the flowers of Aconitum kusnezoffii (FAK) was investigated using electrospray ionization tandem mass spectrometry (ESI-MSn) firstly. The analysis of the collision-induced dissociation (CID) spectra of three purified aconitine standards and six previously reported aconitines indicated that the fragmentation of the protonated aconitines at low-energy CID follows a similar pathway. The elimination of a C-8-substituent such as an acetic acid or a fatty acid is the dominant fragmentation mode in MS2. Successive losses of CH3COOH, CH3OH, H2O, BzOH, and CO are the main fragmentation pathways of aconitine-type alkaloids in MS3 spectra. Based on these features, a rapid method for the direct detection and characterization of alkaloids from an ethanolic extract of FAK is described. All the known aconitum alkaloids are detected and a series of lipo-aconitines has been found for the first time in this plant.

Synthesis and structural characterization of a new molecule-based complex constructed from dodecamolybdophosphoric acid and imidazole

A new compound, (CH5N2)(3)(PMo12O40CH4N23H2O)-C-.-H-. (1), was synthesized and structurally characterized by elemental analyses, IR spectra, UV spectra, NMR spectra and ESR spectra. This is, to our knowledge, the first example of an imidazole-polyoxometalate species. The compound was recrystallized from N,N-dimethylformamide (DMF), and then black block-like crystals of (C3H5N2)(4)((PMoMo11O40)-Mo-V-O-VI)(.)4C(3)H(7)NO(.) 2H(2)O (2), were obtained. It crystallizes in a triclinic space group P (1) over bar with n=12.423(3) Angstrom, b=12.666(3) Angstrom, c=13.341(3) Angstrom, alpha=70.56(3)degrees, beta=71.16(3)degrees, gamma=64.18(3)degrees, V= 1742.3(6) Angstrom(3), Z=1, R1 = 0.0585, wR2 = 0.1885. An X-ray crystallographic study showed that the crystal structure is constructed by electrostatic attractions and hydrogen bonds between a dodecamolybdophosphoric anion and an imidazole. The imidazole and DMF molecules occupy cavities in a polyoxometalate lattice ordered along a c-axis. The structure of (2) is similar to that of (1) from a comparison of both IR spectra and TGA Curves.

刺五加寡糖的电喷雾多级串联质谱研究

采用小柱层析法从刺五加中分离得到刺五加寡糖类系列化合物(刺五加二糖～刺五加六糖).实验结果表明, 在正离子模式下的ESI-MS谱中, 此类化合物呈现出特征的加合离子峰簇[M+Na]+/[M+K]+或[M+H2O+Na]+/[M+H2O+K]+, 可以确定其分子量; 在负离子模式下的ESI-MS谱中, 刺五加寡糖易形成[M-H]-/[M+nH2O-H]-(n<3).还利用电喷雾多级串联质谱(ESI-MSn)对刺五加三糖进行了系统的研究, 推断出刺五加三糖的组成与结构.

Three-phase extraction study in the Cyanex923-n-heptane/HNO3 system

The present paper reports a study of the extraction of HNO3 with Cyancx923 (C923)-n-heptane. A third phase appears at different aqueous HNO3 concentrations for various initial C923 concentrations. Data analysis indicates that almost all of HNO3 and H2O are extracted into the middle phase. More HNO3 and water at a fixed ratio are solubilized in the reverse micelles or microemulsion in the third phase, which leads to a sharp increase of their concentration. The effect of temperature on the phase behavior of the three-phase system has also been investigated.

A novel route for the preparation of CdS nanocrystal-poly(acrylic acid) composites using gamma-radiation

CdS nanocrystals were synthesized through AOT/heptane/H2O reverse micelles. New stable reverse mikelles were obtained by adding an appropriate amount of acrylic. acid monomer, CdS nanocrystal-poly(acrylic acid) composites were synthesized by gamma-radiation with a reverse mi'celle route at room temperature. The US nanocrystals with narrow size distribution were, found to be dispersed homogeneously in the poly(acrylic acid) matrix. (C) 2002 Elsevier Science B.V. All rights reserved.

Three-phase extraction study of Cyanex 923-n-heptane/H2SO4 system

Phase behavior of the extraction system, Cyanex 923-heptane/H2SO4-H2O has been studied. The third phase appeared at different aqueous H2SO4 concentration with varying initial Cyanex 923 concentration and temperature affects its appearance. Almost all of H2SO4 and H2O are extracted into the middle phase. The H2SO4 concentration in the third phase increases with the increasing aqueous acid concentration (C-H2SO4,C-b) while the water content first increases and then reaches a constant value at CH2SO4,(b) = 11.3 mol l(-1). In the region of C-H2SO4,C-b higher than 5.2 mol l(-1), the composition of the middle phase is only related to the equilibrium concentration of H2SO4 in the bottom phase. H2SO4 and H2O are transferred into the middle phase mainly by their coordination with Cyanex 923 when C-H2SO4,C-b is less than 11.3 mol l(-1). When C-H2SO4,C-b is higher than 11.3 mol l(-1), excess H2SO4 is solubilized into the polar layer of the aggregates. In the region considered, the extracted complex changes from C923.H2SO4 to C923 . H2SO4 . H2O and then to C923 . (H2SO4)(2) . H2O.

A highly reduced polyoxoanion with phosphorus-centered alternate layers of Mo/V oxides, [(PMo2Mo6V4O40)-Mo-V-V-VI-O-IV((VO)-O-IV)(2)](9-)

An unusual polyoxometalate [H2N(C2H4)(2)NH2](4)(H3O)[(PMO2Mo6V4O40)-Mo-V-V-VI-O-IV((VO)-O-IV)(2)].H2O is hydrothermally synthesized and characterized by IR, UV-VIS, elemental analyses, X-ray photoelectron spectrum, ESR, TG and Single crystal X-ray diffraction. The title compound crystallizes in the orthorhombic space group Pbca with a = 15-227(5), b = 19.491(4), c = 18.737(3) Angstrom, V = 5123(2) Angstrom(3), Z = 4, and R-1 (wR(2)) = 0.0726(0.1416). The compound contains an unusual highly reduced pseudo-Keggin type polyoxoanion and exhibits an interesting phosphorus-centered alternate arrangement of layers of molybdenum and vanadium oxides.

Synthesis of tetra-iron substituted sandwich-type pentadecatungstodiarsenate and its multilayers on glassy carbon electrode by self-assembly with electrocatalytic properties

A novel sandwich-type compound, Na-12 [Fe-4 (H2O)(2) (As2W15O56)(2)] . 38H(2)O (denoted as Fe(4)AS(4)W(30)) was synthesized. The compound was well characterized by means of IR, UV-Vis, W-138 NMR and elemental analyses. Redox electrochemistry of the compound has been studied in acid buffer solutions using cyclic voltammetry(CV). The compound containing multilayer films has been fabricated on the 4-aminobenzoic acid(4-ABA) modified glassy carbon electrode(GCE) surface by alternate deposition with a quaternized poly (4-vinylpyridine) partially completed with [Os(bpy)(2)Cl](2+/-) (denoted as QPVP-Os). CV, X-ray photoelectron spectroscopy (XPS) and UV-Vis spectroscopy were used to characterize the asprepared multilayer films. It is proved that the multilayer films are uniform and stable. The electrocatalytic activities of the multilayer films were investigated on the reduction of two substrates of important analytical interest, NO2- and H2O2.

Three-phase extraction study of Cyanex 923-n-heptane/Ce4+-H2SO4 system

Phase behavior of the extraction system, Cyanex 923-heptane/Ce4+-H2SO4 has been studied and compared with Cyanex 923-heptane/H2SO4 System. Cerium(IV) is mainly extracted into the third phase, and its concentration in the third phase first increases with the increasing aqueous acid concentration, reaches maximum and then decreases. At higher acidity, cerium(IV) is hardly extracted in the third phase. The phase behavior and change of the contents of acid and water are similar to those in the acid system. The acid concentration increases with increase of the aqueous acid in the whole extraction region while the water content first decreases with it and then increases after the third phase formation. The third phase has a characteristic lamellar structure formed by the aggregates of Cyanex 923 (.) (H2SO4)(2) (.) H2O as those in the case of acid system. The third phase loaded Ce(IV) has been used to prepare ultrafine CeO2 powder conveniently by precipitation with oxalic acid, and powders with size mostly smaller than 100 nm can be obtained.

Synthesis, properties and structural characterization of an intermolecular photosensitive complex: (HGly-Gly)(3)PMo12O40 center dot 4H(2)O

The first heteropoly acid-dipeptide complex, (HGly-Gly)(3)PMo12O40.4H(2)O, was synthesized and characterized by elemental analysis, IR, UV, H-1 NMR and single crystal X-ray diffraction. The X-ray crystallographic study showed that the crystal structure was constructed from N-H...O and O-H...O hydrogen bonds among the (HGly-Gly)(+), H2O and PMo12O403- units. This structure represents a model interaction between polyoxometalates and proteins. The complex has photosensitivity under irradiation by sunlight. The fluorescent activity of this compound is also reported.

Photochemical synthesis, properties and X-ray crystal structure of tetrabutylammonium dodecamolybdophosphate heteropoly blue

The title heteropoly blue, (Bu4N)(6)H-10 [(PMo11MoO40)-Mo-VI-O-V](4) . H2O has been photochemically synthesized and characterized with elemental analysis, solid diffusion reflectance electronic spectra, CV, ESR, XPS, IR spectra, conductivity measurement and X-ray single crystal analysis. The crystallographic data for C96H218Mo48N6O169P4 are as follows: M-r = 8889.76, triclinic, P (1) over bar, a = 1.4142 (3) nm, b = 2.6027 (5) nm, c = 2.6403(5) nm, alpha = 113.96(3)degrees, beta = 90.05(3)degrees, gamma = 105.71(3)degrees, V = 8.481 (3) nm(3), Z = 1, D-c = 1.741 g/cm(3), F (000) = 4264, mu = 1.798 mm(-1). The X-ray crystal structure analysis reveals that there Is one independent molecule in the unit cell of the title heteropoly blue which contains four mixed-valence heteropoly anions, six tetrabutylammonium cations and one water molecule. Its molecular structure possesses a centrosymmetrical arrangement in the unit cell. The phosphorus atom is In the crystallographic inversion center of the heteropoly anion and the eight oxygen atoms surrounding central phosphorus atom comprise of a distorted hexahedron. Heteropolyanion has two equal sets of PO4 tetrahedron. The PO4 tetrahedron and the MoO6 octahedron in the polyanion are greatly distorted.