Synthesis of bis [bis (tert-butylcyclopentadienyl) neodymium chloride] and structural trend of bis[bis(tertbutylcyclopentadienyl) lanthanide chloride]

The reaction of NdCl3 with 2 equiv. of Na-(BuC5H4)-C-t in THF(tetrahydrofuran) gives blue crystals [((BUC5H4)-C-t)(2)NdCl](2), C36H52Cl2Nd2(M-r = 844.11) Which crystallizes in the triclinic system with space group . The crystal data are a=11.978 (1), b=12.671(4), c=12.706(2)Angstrom, alpha=105.47(2), beta=99.38(1)? gamma=93.15 (2)degrees, V=1825 (3) Angstrom(3), Z = 2 , D-c = 1.53g/cm(3), F(000) = 450 , T = 298K , lambda(MoK alpha) = 0.71069 Angstrom, , mu = 14.97cm(-1). Final R = 0.0390, R-w = 0.0376 for 4329 reflections with I greater than or equal to 3 sigma(I-o). The molecule has a dimer structure with two certrosymmetrical chlorine bridges. The structural trend of these analogous complexes is discussed.

In-situ Fourier transform infrared spectroelectrochemistry as a probe of the glassy carbon electrode chemically modified by nickel (II)-cyanometallates

A new nickel (II)-cyanometallates modified on glassy carbon electrode was prepared by a new method and studied by cyclic voltammetry and in situ Fourier transform infrared (FTIR) spectroelectrochemistry. It was found that the NiHCF film existed in two forms: Ni2Fe(II)-(CN)(6) and M2NiFe(II)(CN)(6), Fe(CN)(3)(6-) codeposited in the NiHCF film existing in free cation or bridged-bond state depended on the property of the cations in electrolyte: in NaCl and LiCl solution, it is in bridges-bonded, but in HCl and KCl, it is free.

Metallocene polyethylenes with broad or bimodal molecular weight distribution

Seven new binuclear titanocenes with different linking bridges, unsubstituted or substituted on the Cp rings, were synthesized and tested for their effect on ethylene polymerization in the presence of MAO. The polyethylenes thus obtained had broad MWD or even bimodal GPC curves, as compared with that from two reference mononuclear titanocenes. This is explained by the difference in degree of steric hindrance around the active center sites imposed by the bulky substituted ligands assuming different configurations in the rotation of the catalyst molecules. Lower polymerization temperatures alleviate the effect of these configuration differences, as reflected in change in MW and (M) over bar(w)/(M) over bar(n). This effect is not caused by decomposition or disproportionation of the binuclear titanocenes as evidenced by the stability of the catalyst.

The reactivity of lanthanide alkyl compounds with phenylacetylene: Synthesis and structure of [(Bu(t)Cp)(2)LnC CPh](2) (Ln=Nd, Gd)

[(Bu(t)Cp)(2)LnCH(3)](2) (Ln = Nd, Gd) react with PhC=CH to form the dimeric alkynide-bridged complexes [(Bu(t)Cp)(2)LnC=CPh](2) [Ln = Nd (I), Gd (II)]. Both compounds crystallized from toluene in the monoclinic space group C2/c. The two complexes are homologous, composed of asymmetric metal-alkynide bridges with Nd-C, Gd-C (alkynide) bond lengths of 2.602(4), 2.641(5) (I) and 2.532(6), 2.601(7) Angstrom (II), respectively. The average Nd-C (ring) and Gd-C (ring) distances are 2.746(13) and 2.703(19)Angstrom.

STRUCTURE OF AQUABIS-(PICOLINATO)SCANDIUM HYDROXIDE DIHYDRATE

The crystal structure of the title complex was established by X-ray diffraction analysis. Each scandium ion is seven-coordinated by two oxygen atoms and two nitrogen atoms from the picolinato ions, one water oxygen atom and two hydroxide ions. The nitrogen atom and one carboxyl oxygen atom of each picolinato ion are coordinated to the same scandium ion to form a five-membered chelating ring. Each hydroxide ion is coordinated to two scandium ions to form hydroxide bridges and a dimeric molecule unit.

HOST-GUEST INTERACTIONS OF THIAMINE WITH ANIONS - CRYSTAL-STRUCTURE OF THIAMINE IODIDE SESQUIHYDRATE

The crystal structure of thiamine iodide sesquihydrate has been determined by X-ray diffraction methods as a host-guest model for coenzyme-substrate interactions. The asymmetric unit contains two chemical units. Both the thiamine molecules A and B, which are crystallographically independent, assume the usual F conformation and have a disordered hydroxyethyl side chain. An iodide anion (or a water molecule) bridges the pyrimidine and thiazolium rings of molecule A (or B) by forming a hydrogen bond with the amino group and an electrostatic contact with the thiazolium ring to stabilize the molecular conformation. In the crystal the thiamine molecules self-associate to form a pipe-like polymeric structure, in which four thiamine hosts surround an iodide guest and hold it through C(2)-H...I hydrogen bonds and thiazolium...I electrostatic interactions. Crystal data: C12H17N4OS+.I- . 1.5 H2O, monoclinic, P2(1)/c, a = 12.585(2), b = 25.303(5), c = 12.030(2) angstrom, beta = 115.15(1)degrees, V = 3468(1) angtrom3, Z = 8, D(c) = 1.606 g cm-3, R = 0.045 for 3328 observed reflections.

INTERACTIONS OF THIAMINE WITH ANIONS - STRUCTURE OF THIAMINE DITHIOCYANATE

The crystal structure analysis of {3-[(4-amino-2-methyl-5-pyrimidinyl)methyl]-5-(2-hydroxyethyl)-4-methylthiazol}ium dithiocyanate reveals that there are two types of anion bridges between the two aromatic rings of the same thiamine which adopts the usual F conformation, one of which involves a contact between H(C2) on the thiazolium ring and the hydroxy O atom from a neighbouring molecule. The crystal packing shows a novel triple helical structure formed by strongly hydrogen-bonded thiamine-SCN- molecular chains.

STRUCTURE OF AN ERBIUM COORDINATION COMPOUND WITH L-PROLINE, ([ER(PRO)2(H2O)5]CL3)(N)

catena-Poly[{pentaaqua(L-proline-O)-erbium-mu-(L-proline-O:O')} trichloride], {[Er(C5H9-NO2)2(H2O)5]Cl3}n, M(r) = 594.0, monoclinic, P2(1), a = 8.294 (1), b = 10.981 (3), c = 11.934 (3) angstrom, beta = 107.04 (2)degrees, V = 1039.2 (4) angstrom3, Z = 2, D(x) = 1.90 g cm-3, lambda(Mo Kalpha) = 0.71069 angstrom, mu = 45.2 cm-1, F(000) = 586, T = 298 K, R = 0.0244 for 1711 unique reflections [I > 3 sigma(I(o))]. The crystal consists of one-dimensional chains of infinite length in which one L-proline ligand bridges two neighboring Er ions, the other L-proline ligand being monodentate.

STRUCTURE OF THIAMINE BROMIDE SESQUIHYDRATE

3-[(4-Amino-2-methyl-5-pyrimidinyl)-methyl]-5-hydroxyethyl-4-methylthiazolium bromide sesquihydrate, C12H17N4OS+.Br-.1.5H2O, M(r) = 372.28, monoclinic, P2(1)/a, a = 11.676 (2), b = 24.819(7), c = 12.344 (3) angstrom, beta = 113.74(2)-degrees, V= 3274 (1) angstrom3 , Z = 8, D(x) = 1.51 g cm-3 (Mo Kalpha) = 0.71069 angstrom, mu = 26.2 cm-1, F(000) = 1528, T 293 K, R = 0.062 for 2720 observed reflections. Both the independent thiamine molecules A and B in the asymmetric unit adopt the common F conformation. A bromide anion is held by four neighbouring thiamine molecules through C(2)-H...Br hydrogen bonds and Br ... thiazolium-ring electrostatic interactions. Another bromide anion (or a water molecule) bridges the pyrimidine and thiazolium moieties of molecule A (or B) through a hydrogen bond with the amino group and an electrostatic interaction with the thiazolium ring.

PREPARATION AND MOLECULAR-STRUCTURE OF METHYLBIS(TERT-BUTYLCYCLOPENTADIENYL)NEODYMIUM AND METHYLBIS(TERT-BUTYLCYCLOPENTADIENYL)GADOLINIUM

Bis(t-butylcyclopentadienyl)lanthanide chloride (Ln = Nd or Gd) reacts with one equivalent of methyllithium in ether/tetrahydrofuran to give the complex [(C5H4tBu)2LnCH3]2 (Ln = Nd or Gd). The structure of [(C5H4tBu)2NdCH3]2 has been determined by X-ray analysis. The crystals are monoclinic of space group Cm with a = 9.538(2), b = 23.298(4), c = 9.505(3) angstrom, beta = 119.53(2)-degrees, V = 1828.0(7) angstrom 3, D(calc.) = 1.458 g/cm3 and Z = 2 for the dimer. The two (C5H4tBu)2Nd units in the dimer are connected by asymmetrical methyl bridges with independent Nd-C bond lengths of 2.70(2) and 2.53(2) angstrom and Nd-C-Nd angles of 94.7(9) and 87.3(6)-degrees.

Cflec-4, a multidomain C-type lectin involved in immune defense of Zhikong scallop Chlamys farreri

C-type lectins are a superfamily of carbohydrate-recognition proteins which play crucial roles in the innate immunity. In this study, a novel multidomain C-type lectin gene from scallop Chlamys farreri (designated as Cflec-4) was cloned by RACE approach based on EST analysis. The full-length cDNA of Cflec-4 was of 2086 bp. The open reading frame was of 1830 bp and encoded a polypeptide of 609 amino acids, including a signal sequence and four dissimilar carbohydrate-recognition domains (CRDs). The deduced amino acid sequence of CflecA shared high similarities to other C-type lectin family members. The phylogenetic analysis revealed the divergence between the three N-terminal CRDs and the C-terminal one, suggesting that the four CRDs in Cflec-4 originated by repeated duplication of different primordial CRD. The potential tertiary structure of each CRD in Cflec-4 was typical double-loop structure with Ca2+-binding site 2 in the long loop region and two conserved disulfide bridges at the bases of the loops. The tissue distribution of Cflec-4 mRNA was examined by fluorescent quantitative real-time PCR. In the healthy scallops, the Cflec-4 transcripts could be only detected in gonad and hepatopancreas, whereas in the Listonella anguillarum challenged scallops, it could be also detected in hemocytes. These results collectively suggested that CflecA was involved in the immune defense of scallop against pathogen infection and provided new insight into the evolution of C-type lectin superfamily. (C) 2009 Elsevier Ltd. All rights reserved.

Cloning and characterization of a novel C-type lectin gene from shrimp Litopenaeus vannamei

In invertebrates, C-type lectins play crucial roles in innate immunity responses by mediating the recognition of host cells to pathogens and clearing microinvaders, which interact with carbohydrates and function as pattern recognition receptors (PRRs). A novel C-type lectin gene (LvLec) cDNA was cloned from hemocytes of Litopenaeus vannamei by expressed sequence tag (EST) and rapid amplification of cDNA ends (RACE) PCR. The full-length cDNA of LvLec was of 618 bp, consisting of a 5'-terminal untranslated region (UTR) of 60 bp and a 3'-UTR of 87 bp with a poly (A) tail. The deduced amino acid sequence of LvLec possessed all conserved features critical for the fundamental structure, such as the four cysteine residues (Cys(53), Cys(128), Cys(144), Cys(152)) involved in the formation of disulfides bridges and the potential Ca2+/carbohydrate-binding sites. The high similarity and the close phylogenetic relationship of LvLec shared with C-type lectins from vertebrates and invertebrates. The structural features of LvLec indicated that it was an invertebrate counterpart of the C-type lectin family. The cDNA fragment encoding the mature peptide of LvLec was recombined and expressed in Escherichia coli BL21(DE3)-pLysS. The recombinant protein (rLvLec) could agglutinate bacteria E. coli JM109 depending on Ca2+, and the agglutination could be inhibited by mannose and EDTA. These results indicated that LvLec was a new member of C-type lectin family and involved in the immune defence response to Gram negative bacteria in Litopenaeus vannamei. (C) 2008 Elsevier Ltd. All rights reserved.

Molecular cloning, characterization and expression of a novel serine proteinase inhibitor gene in bay scallops (Argopecten irradians, Lamarck 1819)

Serine protease inhibitors, critical regulators of endogenous proteases, are found in all multicellular organisms and play crucial roles in host physiological and immunological effector mechanisms. The first mollusk serine proteinase inhibitor (designated AISPI) cDNA was obtained from the bay scallop Argopecten irradians by randomly sequencing a whole tissue cDNA library and rapid amplification of cDNA ends (RACE). The full-length cDNA of the scallop serine protease inhibitor was 1020 bp, consisting of a 5'-terminal untranslated region (UTR) of 39 bp, a 3'-terminal UTR of 147 bp with a canonical polyadenylation signal sequence AATAAA and a poly(A) tail, and an open reading frame of 834 bp. The AISPI cDNA encoded a polypeptide of 278 amino acids with a putative signal peptide of 22 amino acids and a mature protein of 256 amino acids. The deduced amino-acid sequence of AISPI contained six tandem and homologous domains similar to that of Kazal-type serine protease inhibitors, including the conserved sequence C-X(7)-C-X(6)-Y-X(3)-C-X(2,3)-C and six cysteine residues responsible for the formation of disulfide bridges, indicating that the AISPI protein from bay scallop should be a member of the Kazal-type serine protease inhibitor family. The temporal expression of AISPI was measured by semi-quantitative RT-PCR after injury or bacterial challenge. After the adductor muscle was wounded or injected with Vibrio anguillarum, the expression of AISPI mRNA in hemolymph was up-regulated and reached the maximum level at 8 and 16 h, respectively, and then progressively dropped back to the original level. The results indicated that AISPI could play an important role in injury healing and immune response in mollusks as it could be induced by injury and bacterial challenge. (c) 2005 Elsevier Ltd. All rights reserved.

长江口水文、泥沙过程与圆桩冲刷的数值模拟

本文主要利用ECOMSED模式对长江口及邻近海域的水文、泥沙过程进行三维数值模拟，并结合实测资料分析其水动力、泥沙输运、底床冲淤等特征；然后利用欧拉二相流模型模拟小尺度条件下长江口底床上圆桩周围的水流和泥沙冲刷、输运规律。 通过资料分析和ECOMSED数值模拟结果比较，我们得出：长江口口门内为非正规半日潮流区，潮流运动形式多为往复流，落潮流占优。落潮流速大于涨潮流速，流速垂向分布从表层到底层递减。悬沙浓度与流速关系密切，一般来说，流速越大，悬沙浓度越高；一个潮周期过程中会出现两次、三次或四次泥沙再悬浮，分别是涨急、落急、涨转落、落转涨时刻；盐水楔结构对粘性与非粘性悬沙浓度的分布起决定性作用，转流时泥沙再悬浮主要是由于这时会出现盐水楔，并形成垂向环流，使床面大量未被固结的泥沙再悬浮，形成峰值。悬浮泥沙垂向分布可分为垂线型，斜线型，抛物线型和L型。流场和底床冲淤变化与水深关系密切：深水区，流速较大，底床冲淤变化也较大。其中，受径流影响区表现为淤积，受潮流影响区表现为冲刷；浅水区基本表现为淤积。 从模式运行结果和实测资料比较可以看出，该模型可以较好的模拟长江口水流、悬浮泥沙分布与变化；能够再现在径流入海口处，盐水楔结构及其诱生的垂向环流从形成到发展，又到消失的完整过程；也能够展示底床的冲淤变化。对于我们模拟长江口背景流场，了解该区域内水动力变化、悬浮泥沙输运、底床冲淤等有重要意义。 在欧拉二相流模型对长江口底床上圆桩周围的水流和局部冲刷数值模拟过程中，我们不仅考虑水流和泥沙之间的作用，还引入泥沙颗粒之间的相互影响。模拟结果较合理的展示了圆桩周围的流场类型和底床冲刷变化：在圆桩前方，流速减小并形成垂向涡旋，从而产生局部冲刷；在圆桩两侧，水流加速，挟带上游泥沙向下输送，并在内侧堆积；而在圆桩后面，存在流速分离区。在该分离区内流速很小，并且当流速较大时，会产生回流，形成两个对称的漩涡。流速越大，圆桩前由垂向涡旋引起的局部冲刷就越明显；而当底床泥沙粒径变小时，泥沙临界起动流速变小，底床也更容易被冲刷。悬浮泥沙浓度分布受流场的影响，并且当粒径小而流速大时，能悬浮到更高的深度。

Catena-Poly[[[tetra-mu(2)-aqua-heptaaqua-(mu(2)-benzene-1,3,5-tricarboxylato)-mu(3)-hydroxido-trinickel(II)sodium]-mu(4)-benzene-1,3,5-tricarboxylato]sesqui-hydrate]

The title coordination polymer, {[Ni3Na(OH)(C9H3O6)(2)( H2O)(11)] center dot 1.5H(2)O}(n), is built up from three independent Ni-II ions and one Na-I cation bridged by benzene-2,4,6-tricarboxylate ( BTC) ligands and water molecules. Three Ni-II ions are bridged by three bidentate carboxylate groups of three BTC ligands, two aqua ligands and one OH- unit, to form a trinuclear metal cluster. The Na-I cation is bonded to the Ni-II cluster by two bridging water molecules. One of the three BTC ligands bridges neighbouring clusters into one-dimensional chains, which are further connected through a complex hydrogen-bonding scheme, forming a three-dimensional suprastructure. The title complex is isomorphous with the previously reported Co-II complex.