α-羰基烯酮式环二硫代缩醛化学(V)——β,β-1,3-亚丙二硫基-α,β-不饱和芳酮类化合物的合成

β,β-二烷硫基-α,β-不饱和酮类化合物作为一类具多反应中心的活泼中间体在有机合成中的应用,近20年来已引人注目并进行了深入广泛的研究~[1,2].以往的研究大多是针对β,β-二甲硫基-α,β-不饱和酮类化合物1进行的,而对结构相近的β,β-1,3-亚丙二硫基-α,β-不饱和酮类化合物2的研究较少.对于1类的合成,所用碱的选择至关重要~[1].实验证明叔丁醇钠和叔丁醇钾~[3～5]在1类的合成中效果较好.前文~[6]曾以六甲基二硅氨基锂(LHMDS)为碱高

Characteristics and optical spectra of V : YAG crystal grown in reducing atmosphere

A V:YAG single crystal was grown by the temperature gradient technique (TGT) with graphite-heating elements. The as-grown crystal has different colorations of light green and yellow brown in different parts. Distribution of vanadium in three samples with different colorations was determined by inductively coupled plasma-mass spectrometry. From the absorption spectrum of the yellow-brown part with peaks at 370, 820 and 1320nm, we can deduce that the reducing atmosphere of carbon diffused from the heating elements can increase the concentration of tetrahedral V3+ ions and induce F color centers. All three samples exhibited light-green color after annealing in vacuum or H-2 atmospheres. In the vacuum annealing process, the V3+ ions in tetrahedral positions were enhanced through two methods: one method is the exchanging of octahedral V3+ and tetrahedral Al3+ ions in neighboring sites under thermal excitation, the other is that F color centers were thoroughly eliminated and the escaped free electrons could be captured by V ions with higher valance states to further improve the concentration of tetrahedral V3+ ions. Besides the two mechanisms, the H-2 annealing process greatly improved the V-tetra(3+) ions through the reduction effect of H-2. (c) 2006 Elsevier B.V. All rights reserved.

掺Yb双包层光纤激光器v形槽侧面粘和泵浦方法

一种掺Yb双包层光纤激光器v形槽侧面粘和泵浦方法，其特征在于，包括如下步骤:步骤1:在双包层光纤的内包层和外包层上用精密光学微加工技术沿双包层光纤的轴向加工一段v形槽，该v形槽的底部高于双包层光纤的纤芯的表面;步骤2:将多模尾纤的一端用化学腐蚀方法去掉涂敷层，得到裸尾纤;步骤3:将多模尾纤一端的裸尾纤放入双包层光纤的v形槽内，该裸尾纤与纤芯相隔一距离;步骤4:使用光学折射率匹配胶填充于v形槽内，使裸尾纤与纤芯平行固定于v形槽内。

Effects of reaction conditions on the selective oxidation of propane to acrylic acid on Mo-V-Te-Nb oxides

An effective Mo-1 V(0.3)Te(0.23)Nb(0.12)Ox catalysts for the selective oxidation of propane to acrylic acid was successfully prepared by using rotavap method. The catalyst was characterized by XRD and shown to contain (V0.07Mo0.93)(5)O-14, (Nb0.09Mo0.91)O-2.8,3MoO(2)(.)Nb(2)O(5), Mo5TeO16 and/or TeMo4O13, Te4Nb2O13 and a new TeMO (TeVMoO or TeVNbMoO; M = Mo, V and Nb) crystalline phase as the major phase. Regardless of the intrinsic catalytic characteristics of the catalyst, the external reaction conditions would have strong effects on the catalytic performance for propane oxidation. So in this paper, the effects of reaction conditions were investigated and discussed, including temperature, space velocity, V(air)/V(C3H8) ratio and V(steam)/V(C3H8) ratio. A stability test was also carried out on Mo1V0.3Te0.23Nb0.12Ox catalyst. The experimental run was performed during 100 h under the optimized reaction conditions. During the 100 h of operation, propane conversion and acrylic acid selectivity remained at about 59 and 64%, respectively. (C) 2004 Elsevier B.V. All rights reserved.

Syntheses, crystal structures, visible and near-IR luminescent properties of ternary lanthanide (Dy3+, Tm3+) complexes containing 4,4,4-trifluoro-1-phenyl-1,3-butanedione and 1,10-phenanthroline

The ligands 4,4,4-trifluoro-1-phenyl-1.3-butanedione (Hbfa) and 1,10-phenanthroline (phen) were used to prepare ternary lanthanide (Ln) complexes [Dy(bfa)(3)phen and Tm(bfa)(3)phen]. Crystal data: Dy(bfa)(3)phen C(42)H(26)FqN(2)O(6)Dy, triclinic, P (1) over bar, a= 9.9450(6) angstrom, b = 14.0944(9) angstrom, c = 14.6043(9) angstrom, alpha = 82.104(1)degrees, beta = 87.006(1)degrees, gamma = 76.490(1)degrees, V = 1971.1(2)angstrom(3), Z = 2; Tm(bfa)(3)phen C42H26F9N2O6Tm, triclinic, P (1) over bar, a = 9.898(5)angstrom, b = 13.918(5)angstrom, c = 14.753(5)angstrom, a = 83.517(5)degrees, alpha = 86.899(5)degrees, gamma = 76.818(5)degrees, V = 1965.3(14)angstrom(3), Z = 2. The coordination number of the central Ln(3+) (Ln = Dy, Tm) ion is eight, with six oxygen atoms from three Hbfa ligands and two nitrogen atoms from the phen ligand.

Polymerization of 1,3-butadiene with VO(P-204)(2) and VO(P-507)(2) activated by alkylaluminum

The oxovanadium phosphonates (VO(P-204)(2) and VO(P-507)(2)) activated by various alkylaluminums (AlR3, R = Et, i-Bu, n-Oct; HAIR(2), R = Et, i-Bu) were examined in butadiene (Bd) polymerization. Both VO(P-204)(2) and VO(P-507)(2) showed higher activity than those of classical vanadium-based catalysts (e.g. VOCl3, V(acac)(3)). Among the examined catalysts, the VO(P-204)(2)/Al(Oct)(3) system (I) revealed the highest catalytic activity, giving the poly(Bd) bearing M-n of 3.76 x 10(4) g/mol, and M-w/M-n ratio of 2.9, when the [Al]/[V] molar ratio was 4.0 at 40 degrees C. The polymerization rate for I is of the first order with respect to the concentration of monomer. High thermal stability of I was found, since a fairly good catalytic activity was achieved even at 70 degrees C (polymer yield > 33%); the M-n value and M-w/M-n, ratio were independent of polymerization temperature in the range of 40-70 degrees C. By IR and DSC, the poly(Bd)s obtained had high 1,2-unit content (> 65%) with atactic configuration. The 1,2-unit content of the polymers obtained by I was nearly unchanged, regardless of variation of reaction conditions, i.e. [Al]/[V], ageing time, and reaction temperature, indicating the high stability of stereospecificity of the active sites.

Synthesis and characterization of tris(cyclopentylcyclopentadienyl)lanthanide complexes (C5H9C5H4)(3)NdBrLi(THF)(3) and (C5H9C5H4)(3)SmTHF

(C5H9C5H4)(3)NdBrLi(THF)(4)(1)(C5H9=cyclopentyl) was obtained from the reaction of NdCl3 with C5H9C5H4Na and LiBr (Nd:Na:Li=1:2:1 molar ratio) in THE X-ray crystallography showed that the ten-coordinated neodymium atom is bonded to three cyclopentylcyclopentadienyl(eta(5)) rings and a single bromine atom bridging a lithium which is bonded to three THF molecules. Complex 1 is triclinic, P1 space group with unit dimensions of a= 12.048(2), b= 13.498(3), c= 13.831(3)Angstrom, a = 104.16(3), beta = 104.07(3), gamma =95.96(3)degrees, V=2083.3(7)Angstrom(3), Z=2, D-c=1.35Mg/m(3) and F(000)=874. (C5H9C5H4)(3)SmTHF (2) was synthesized by reaction of anhydrous SmCl3 with C5H9C5H4Na at a molar ratio of 1:3. The structure was determined by X-ray crystallography. The ten-coordinated samarium atom is bonded to three cycloperrtylcyclopentadienyl rings and one oxygen of THF molecule to form a pseudo-tetrahedron. Complex 2 is orthorhombic, Fdd2 space group with unit cell dimensions of a =28.175(5)Angstrom, b =46.24(2) Angstrom, c =9.167(4) Angstrom(3), V=11943(8)Angstrom(3), Z= 16, D-c = 1.38Mg/m(3) and F(000)=5136.

Synthesis and crystal structure of a novel compound: [H3PMo12O40][CO(NH2)(2)](3)center dot-5H(2)O

The title compound, [H3PMo12O40][CO(NH2)(2)](3). 5H(2)O, was synthesized and characterized by IR, C-13 NMR and X-ray diffraction. This is the first example of a urea-heteropoly acid species. Crystal data: monoclinic, C2/c, a = 17.790(4) Angstrom, b = 17.158(3) Angstrom, e = 25.512(5) Angstrom, beta = 100.65(3)degrees, V = 8514(3) Angstrom (3), Z = 6, R-1 = 0.0437, wR2 = 0. 1092. In the unit cell, the urea molecules occupy cavities in the polyoxometalate lattice ordered along b-axis. Water molecules occupy the space left by polyoxometalates, and urea. Polyoxometalate O atoms, the N atoms of urea and O atoms of water molecules are involved in hydrogen bonding. (C) 2001 Elsevier Science B.V. All rights reserved.

Syntheses of indenyl lanthanide derivatives and the molecular structures of [(C9H7)(2)PrCl(THF)](2) and [(C9H7)(3)La(THF)]

The reaction of anhydrous PrCl3 with Na(C9H7) in 1.2 mole ratio in THF gives [(C9H7)(2)PrCl(THF)](2)1. 1 crystallized in monoclinic system, space group P2(1)/c with a = 7.808(2), b = 17.796(6), c = 14.070(4) Angstrom, beta = 93.97(2)degrees, V= 1950.3(9) Angstrom(3), Dcalcd = 1.63 g/cm(3) and Z = 2. Each Pr ion is surrounded by two indenyl, two Cl and one THF in a roughly trigonal bipyramid arrangement with average Pr-C(ring) and Pr-Cl distances of 2.81 and 2.84 Angstrom. The reaction of LaCl3 with Na(C9H7) in 1:3 mole ratio gives (C9H7)(3)LaTHF 2, which crystallizes in the monoclinic space group P2(1)/a with unit cell constants a = 21.871(8), b = 10.585(3), c = 23.652(7) Angstrom,beta = 114.62(2)degrees, V = 4977.9 Angstrom(3) and Z = 8. (C) 1997 Elsevier Science S.A.

铕和铽与3,4-呋喃二甲酸双核配合物的合成、表征及其晶体结构

本文首次合成了铕(Ⅲ)和铽(Ⅲ)与3,4-呋喃二甲酸配合物,研究了它们的IR、DTA、TG、DTG和荧光光谱等性质,并完成了单晶的晶体分析。结果表明,配合物为〔Ln·HL_2(H_2O)_2〕_2·2H_2O(Ln=Eu(Ⅲ),Tb(Ⅲ);H_2L=3,4-呋喃二甲酸),属单斜晶系,P2/c空间群,Z=2,晶胞参数对铕和铽配合物分别为α=10.842(1),10.801(4);b=8.725(2),8.664(2);c=16.366(4),16.308(6)A;β=93.50(1),93.67(3)°;V=1545.3(5),1523.0(8)A~3。

Crystal structure of (5R,10R)-2,7-dibromo-3,8-dihydroxy-5,10-dimethoxy-5,10-dihydrochromeno[5,4,3-cde]chromene sesquihydrate, C16H12Br2O6 center dot 1.5H(2)O

C16H15Br2O7.5, orthorhombic, P2(1)2(1)2 (no. 18), a = 18.483(2) angstrom, b = 9.413(1) angstrom, c = 10.072(1) angstrom, V = 1752.3 angstrom(3), Z = 4, R-gt(F) = 0.083, wR(ref)(F-2) = 0.202, T= 293 K.

The manganese superoxide dismutase gene in bay scallop Argopecten irradians: Cloning, 3D modelling and mRNA expression

A novel manganese superoxide dismutase (MnSOD) was cloned from bay scallop Argopecten irradians by 3' and 5' rapid amplification of cDNA ends (RACE) PCR. The full-length cDNA of MnSOD was of 1207 bp with a 678 bp open reading frame encoding 226 amino acids. The deduced amino acid sequence contained a putative signal peptide of 26 amino acids. Sequence comparison showed that the MnSOD of A. irradians shared high identity with MnSOD in invertebrates and vertebrates, such as MnSOD from abalone Haliotis discus discus (ABG88843) and frog Xenopus laevis (AAQ63483). Furthermore, the 3D structure of bay scallop MnSOD was predicted by SWISS-MODEL Protein Modelling Server and compared with those of other MnSODs. The overall structure of bay scallop MnSOD was similar to those of zebrafish Danio rerio, fruit fly Drosophila melanogaster, Chinese shrimp Fenneropenaeus chinensis, human Homo sapiens, and had the highest similarity to scallop Mizuhopecten yessoensis and abalone H. discus discus. A quantitative real-time PCR (qRT-PCR) assay was developed to detect the mRNA expression of MnSOD in different tissues and the temporal expression in haemocytes following challenge with the bacterium Vibrio anguillarum. A higher-level of mRNA expression of MnSOD was detected in gill and mantle. The expression of MnSOD reached the highest level at 3 h post-injection with V. anguillarum and then slightly recovered from 6 to 48 h. The results indicated that bay scallop MnSOD was a constitutive and inducible protein and thus could play an important role in the immune responses against V anguillarum infection. (c) 2008 Elsevier Ltd. All rights reserved.