SYNTHESES AND CRYSTAL STRUCTURES OF THE COMPLEXES OF RARE EARTH WITH FUMARIC ACID

Six compounds of M2F3 center dot 1.2H(2)O (M=EU, Ga, Tb, Y, Er, LU: H2F=Fumaric acid) have been synthesized. The structures of Eu(III), T b(III), Y(III), Er(III) and Lu(III) compounds have been determined by singal crystal X-ray diffraction method. The complex of Eu(III) crystallizes in tri-clinic space group P (1) over bar, and the coordination number of Eu3+ is ten. The other four complexes crystallize in monclinic space P2(1)/c, and the coordination numbers of the metal ions are eight. Each of the complexes shows a three-dimensional net structures.

Relevance of molecular weight of chitosan-N-2-hydroxypropyl trimethyl ammonium chloride and their antioxidant activities

The antioxidant potency of high/low molecular weight quatemary chitosan derivatives was investigated employing various established systems in vitro, such as superoxide (O-2(center dot-)) and hydroxyl (center dot OH) radicals scavenging, reducing power and iron ion chelating. As expected, we obtained several satisfying results, as follow: firstly, low molecular weight quaternary chitosan had stronger scavenging effect on O-2(center dot-) and center dot OH than high molecular weight quaternary chitosan. Secondly, the reducing power of low molecular weight quaternary chitosan was more pronounced than that of high molecular weight quaternary chitosan. Thirdly, ferrous ion chelating potency were showed to increase first and decrease afterwards with increasing concentration for two kinds of quaternary chitosans, namely, they have not concentration-dependence. However, the scavenging rate and reducing power of high and low molecular weight quaternary chitosans increased with their increasing conc centrations, and hence were concentration-dependent. (c) 2007 Elsevier Masson SAS. All rights reserved.

The preparation and antioxidant activity of 2-[phenylhydrazine (or hydrazine)-thiosemicarbazone]-chitosan

Chitosan (CS) with two different molecular weight were modified by reacting with methyl hydrazine-dithiocarboxylate and methyl phenylhydrazine-dithiocarboxylate to give 2-(hydrazine-thiosemicarbazone)-chitosan (2-HTCHCS, 2-HTCLCS) and 2-(phenylhydrazine-thiosemicarbazone)chitosan (2-PHTCHCS, 2-PHTCLCS). The structure of the derivatives was characterized by FT-IR spectroscopy and elemental analysis. The antioxidant activities of the derivatives were investigated employing various established systems, such as hydroxyl radical (*OH)/superoxide anion (O-2(center dot-)) scavenging/reducing power and chelating activity. All of the derivatives showed strong scavenging activity on hydroxyl radical than chitosan and ascorbic acid (Vc), and IC50 of 2-HTCHCS, 2-HTCLCS, 2-PHTCHCS and 2-PHTCLCS was 0.362, 0.263, 0.531 and 0.336 mg/mL respectively. The inhibitory activities of the derivatives toward superoxide radical by the PMS-NADH system were strong. The results showed that the superoxide radical scavenging effect of 2-[phenylhydrazine (or hydrazine)-thiosemicarbazone]-chitosan were higher than that of chitosan. The derivatives had obviously reducing power and chelating activity. The data obtained from vitro models clearly establish the antioxidant potency of 2-[phenylhydrazine (or hydrazine)-thiosemicarbazone]-chitosan. (C) 2010 Elsevier B.V. All rights reserved.

Dichloridobis[N-(2-pyridylmethyl)-benzamide-kappa N-2,O]cadmium(II)

In the title compound, [CdCl2(C13H12N2O)(2)], the Cd-II ion is situated on an inversion centre, coordinated by two 0 atoms [Cd-O=2.3878 (17) angstrom] and two N atoms [Cd-N = 2.3404 (15) angstrom] from two N-(2-pyridylmethyl)benzamide ligands, and two Cl atoms [Cd-Cl = 2.5566 (6) angstrom], in a distorted octahedral geometry. In the crystal structure, intermolecular N-H center dot center dot center dot Cl hydrogen bonds [N center dot center dot center dot Cl = 3.1705 (18) angstrom] and pi-pi interactions, with a distance of 3.868 (3) angstrom between the centroids of the phenyl and pyridyl rings of neighbouring molecules, lead to the formation of two-dimensional layers parallel to the bc plane.

Bis(2,3,5-triphenyltetrazolium) tetrachloridocadmate(II)

The title compound, ( C19H15N4)(2)[ CdCl4], a salt comprising two 2,3,5-triphenyl-substituted tetrazolium cations and a tetrachloridocadmate(II) anion, was synthesized by hydrothermal methods. In the anion, the Cd-II ion is tetrahedrally coordinated by four chloride anions. In the crystal structure, four cations and two anions pack into inversion-related subunits linked by C-H center dot center dot center dot Cl and offset pi-stacking interactions.Each of these subunits is surrounded by six others. Intermolecular pi-pi stacking interactions between phenyl rings are observed along the a axis, with perpendicular distances between the ring planes of 3.6015 and 3.6934 angstrom.

InAs/GaSb superlattices for photodetection in short wavelength infrared range

The first report of a short wavelength infrared detector based on type II InAs/GaSb superlattices is presented. Very short period superlattices containing InAs (2ML)/GaSb (8ML) superlattices (SLs) were grown by molecular-beam epitaxy on GaSb substrates. The photoluminescence showed a cut-off wavelength at 2.1 mu m at 10 K and 2.6 mu m at 300 K. Room-temperature optical transmittance spectra shows obvious absorption in InAs (2ML)/GaSb (8ML) SL in the range of 450-680 meV, i.e. 1.8-2.7 mu m. The cut-off wavelength moved from 2.3 mu m to 2.6 mu m with temperature rising from 77 K to 300 K in photoresponse spectra. The blackbody response R-v exponentially decreased as a function of 1/T in two temperature sections (130-200 K and 230-300 K). The blackbody detectivity D-bb(center dot) was beyond 1 x 10(8) cmHz(1/2)/W at room temperature. (C) 2009 Elsevier B.V. All rights reserved.

Temperature dependent spectral response characteristic of III-V compound tandem cell

The GaInP/GaAs/Ge triple-junction tandem cells with a conversion efficiency of 27.1% were fabricated using metalorganic chemical vapor deposition (MOCVD) technique. Temperature dependence of the spectral response measurements of the GaInP/GaAs/Ge tandem cell was performed by a quantum efficiency system at temperatures ranging from 25A degrees C to 160A degrees C. The red-shift phenomena of the absorption limit for all subcells were observed with increasing temperature, which is dued to the energy gap narrowing with temperature. The short-circuit current densities (J (sc)) of GaInP, GaAs and Ge subcells at room temperature calculated based on the spectral response data were 12.9, 13.7 and 17 mA/cm(2), respectively. The temperature coefficient of J (sc) for the tandem cell was determined to be 8.9 mu A/(cm(2) center dot A degrees C), and the corresponding temperature coefficient of the open-circuit voltage deduced from the series-connected model was -6.27 mV/A degrees C.

2-C-支链-1,6-脱水吡喃葡萄糖的开环反应及吡喃烯糖的合成研究

在糖化学合成中，1,6-脱水吡喃糖不仅是合成具有生物活性低聚糖、糖共体、抗原、抗体以及天然产物等化合物重要原料，而且还是许多具有生物活性的天然产物的结构单元。同时，它还具有[3,2,1]的双环缩醛结构，使其在糖化学合成中具有高的立体选择性和区域选择性，同时减少了C-1 和C-6 位的保护和去保护的优点。此外，环内的缩醛开环后，又可以相应地在C-1 和C-6 位进行官能团转化以及糖苷化反应。 本文报道了一种新的1,6-脱水吡喃糖的合成方法，并设计合成了2-C-支链-1,6-脱水吡喃葡萄糖1-195、1-197、1-198 以及2-C-支链-6-硫代1,6-脱水吡喃葡萄糖1-225。到目前为止，1,6-脱水糖开环并进行糖苷化反应，存在选择性较差、产率低的缺点。我们发现，在乙腈做溶剂的条件下，NiCl5 能高立体选择性高产率地催化化合物1-195、1-197、1-198 开环并与ROH、RSH 发生糖苷化反应。在NiCl5-乙腈条件下，合成了一系列2-C-支链-α-糖苷和2-C-支链-β-硫代糖苷，并对2-C-支链1,6-脱水吡喃葡萄糖的生成机理以及开环机理进行了探讨。 烯糖在糖化学合成中是重要的起始原料，从Fischer 首次合成烯糖至今，一直不断地有新的合成方法出现。但目前文献报道的方法存在所用试剂有毒、价格贵和操作繁琐等缺点。我们对Fischer-Zach 方法进行了改进， 发现Zn-NaH2PO4-H2O 和Zn-PEG600-H2O 体系都能很好地合成烯糖。该方法具有条件温和、绿色环保、操作简单的优点。在Zn-NaH2PO4 溶液或Zn-PEG600 条件下，以溴代糖为原料，高产率地合成一系列的烯糖。 The 1,6-anhydrohexopyranoses are crucial subunits of myriad bioactive nature products, as well as important syntons of carbohydrate chemistry which have been extensively used to prepare the biologically potential oligosaccharides, glycoconjugates, antibiotics, and structurally varied nature products. Their particular [3.2.1] bicyclic skeleton makes them have high regio- and stereo-control in a variety of reactions, and such structure avoids protecting hydroxyl groups at C1 and C6.Additionally, the cleavage of the internal acetal under acidic conditions could be beneficial for further transformations of functional group and glycosylation of the corresponding pyranosyl sugar at the C6 or C1 site. Herein we developed a novel approach to prepare the 1,6-anhydrohexopyranose, and synthesized the 2-C-branched-1,6-anhydrohexopyranose 1-195, 1-197, 1-198 and 2-C-branched-6-thio-1,6-anhydrohexopyranose 1-225. Until now, glycosylation of 1,6-anhydrohexopyranoses has been limited because of the low yields and low stereoselectivity. In this paper, we found that NiCl5-MeCN system could selectively cleave the ring of 1,6-anhydrohexopyranoses with alcohols and thiols at room temperature in high yields. A series of 2-C-branched-α-glycosides and 2-C-branched-β-thioglycosides have been synthesized via NiCl5-catalyzed. Furthermore, we investigated the formation and ring-opening mechanism of 2-C-acetylmethyl-1,6-anhydrohexopyranose. Glycals are significant starting material in carbohydrate chemistry. After the Fischer-Zach method for forming glucal was reported for the first time, the numerous synthetic methods for glycals have been explored. However, there are several drawbacks in the existing methods, such as the usage of very expensive and toxic reagents, intricate operation, and the influence of acid-sensitive and base-sensitive functional group. We improved the Fischer-Zach method and developed a facile, mild and environmentally benign methodology towards the synthesis of the glycals in Zn-NaH2PO4-H2O or Zn-PEG600-H2O system. Our method involves the treatment of glycosyl bromides with Zn in NaH2PO4 aqueous solution or PEG600-H2O at room temperature, affording various glycals in excellent yields.

Scaling and the thermal conductivity of the Frenkel-Kontorova model

We have studied the dependence of the thermal conductivity kappa on the strength of the interparticle potential lambda and the strength of the external potential beta in the Frenkel-Kontorova model. We found that the functional relation can be expressed in a scaling form, kappa(proportional to) lambda 3/2/beta(2 center dot). This result is first obtained by nonequilibrium molecular dynamics. It is then confirmed by two analytical methods, the self-consistent phonon theory and the self-consistent stochastic reservoirs method. The thermal conductivity kappa is therefore a decreasing functon of beta and an increasing function of lambda.

Tridentate CCC-Pincer Bis(carbene)-Ligated Rare-Earth Metal Dibromides. Synthesis and Characterization

The first xylene-bridged bis(N-heterocyclic carbene) (bis(NHC))-ligated CCC-pincer rare-earth metal dibromides (PBNHC)LnBr(2)(THF) (PBNHC = 2,6-(2,4,6-Me3C6H2NCHCHNCCH2)(2)C6H3; 1: Ln = Sc; 2: Ln = Lu; 3: Lu = Sm) were prepared by in situ treatment of a THF suspension of 2,6-bis(1-mesitylimidazolium methyl)-1-bromobenzene dibromides ((PB-NHC-Br) center dot 2HBr) and lanthanide trichlorides (LnCl(3)) with dropwise addition of nBuLi at room temperature.

O-2 activation and hydrolysis of Salan rare-earth metal alkyl complexes

Salan ligated yttrium alkyl complex 1, (LY)-Y-1(CH2SiMe3)(THF) (Salan = L-1: [2-O-3,5-tBu(2)-C6H2CH2N(CH3) CH2](2)), was exposed to an oxygen/ nitrogen atmosphere to give a bimetallic alkoxide complex 4, [(LY)-Y-1(mu-OCH2SiMe3)](2). Whilst the lutetium counterparts 2 ((LLu)-Lu-1(CH2SiMe3)(THF)) and 3 ((LLu)-Lu-2(CH2SiMe3)(THF); L-2: [2-O-3-tBu-C6H2CH2N(CH3) CH2](2)) were hydrolysed with moist nitrogen to afford mixed hydroxy/silyloxy complexes 5 and 6 ([(LLu)-Lu-1,2(mu-OSiMe3)(mu-OH) LuL1,2]), respectively.

A ternary supramolecular compound of p-sulfonatocalix[8]arene with 1D channels

A ternary supramolecular complex of [Ni(bipy)(2)(H2O)](4)(C8AS)center dot 17.6(H2O) (bipy=4,4'-dimethyl-2,2'-bipyridine and C8AS = p-sulfonatocalix[8]arene) has been synthesized by a hydrothermal method and characterized by FT-IR spectroscopy, TG-DTA analysis and single crystal X-ray diffraction. In the structure. the water-soluble p-sulfonatocalix[8]arene molecule adopts a double partial cone conformation and is coordinated by four nickel atoms each of which is bonded by two 4,4'-dimethyl-2,2'-bipyridine molecules and one water molecule at the same time. The tetranuclear Subunits are stacked into an extended 3D structure with 1D water-filled channels via hydrogen bonds and C-H center dot center dot center dot pi interactions.

A polymorph of diaquabis(pyrazine-2-carboxylato-kappa N-2(1),O)copper(II)

The title compound, [Cu(C5H3N2O2)(2)(H2O)(2)], is a new polymorph of the previously reported compound [Klein et al. (1982). Inorg. Chem. 21, 1891-1897]. The Cu-II atom, lying on an inversion center, is coordinated by two N atoms and two O atoms from two pyrazine-2-carboxylate ligands and by two water molecules in a distorted octahedral geometry with the water molecules occupying the axial sites. Intermolecular O-H center dot center dot center dot O, O-H center dot center dot center dot N and C-H center dot center dot center dot O hydrogen bonds connect the complex molecules into a two-dimensional layer parallel to (10 (1) over bar), whereas the previously reported polymorph exhibits a three-dimensional hydrogen-bonded network.

Syntheses and Crystal Structures of Fused Thiophenes: [7]Helicene and Double Helicene, a D-2-Symmetric Dimer of 3,3 '-Bis(dithieno[2,3-b:3 ',2 '-d]thiophene)

The efficient synthesis of (TMS)(2)-[7]helicene (rac-3) and double helicene, a D-2-symmetric dimer of 3,3'-bis(dithieno-[2,3-b:3',2'-d]thiophene) (rac-4) was developed. The crystal structures of 3 and 4 show both strong intermolecular pi-pi interactions and S center dot center dot center dot S interactions. UV/vis spectra reveal that both 3 and 4 show significant pi-electron delocalization.

Poly[[(pentaethylenehexamine)manganese(II)] [hepta-mu-selenido-tritin(IV)]]: a tin-selenium net with remarkable flexibility

The title compound, {[Mn(C10H28N6)][Sn3Se7]}(n), consists of anionic (infinity){[Sn3Se7](2-)} layers interspersed by [Mn(peha)](2+) complex cations ( peha is pentaethylenehexamine). Pseudo-cubic (Sn3Se4) cluster units within each layer are held together to form a 6(3) net with a hole size of 8.74 x 13.87 angstrom. Weak N-H center dot center dot center dot Se interactions between the host inorganic frameworks and metal complexes extend the components into a three-dimensional network. The incorporation of metal complexes into the flexible anion layer dictates the distortion of the holes.