SYNTHESIS AND MOLECULAR-STRUCTURE OF NBU2[(MEO)3C6H2C(O)N2CHC6H4O]SN FORMED IN THE REACTION OF DI-N-BUTYLTIN(IV) OXIDE WITH 3,4,5-TRIMETHOXY-BENZOYL SALICYLAHYDRAZONE

The title complex was synthesized and characterized by H-1, C-13, Sn-119 NMR and IR spectra. A single crystal X-ray diffraction study confirmed its molecular structure and revealed that 3,4,5-trimethoxy-benzoyl salicylahydrazone was a tridentate and approximately planar ligand. The complex crystallizes in the triclinic space group P1BAR with a = 9.208(3), b = 12.536(2), c = 12.187(4) angstrom, alpha = 113.12(2), beta = 90.58(2), gamma = 81.42(2), V = 1277.5(6) angstrom, Z = 2. The structure was refined to R = 0.033 and R(w) = 0.041 for 3944 observed independent reflections. The tin atom has a distorted trigonal bipyramidal coordination. The Sn-C bond lengths are 2.129(5) and 2.113(5) angstrom (av. 2.121(5) angstrom), the C-Sn-C angle is 123.3(2); the bond length between the tin atom and the chelating nitrogen is 2.173(3) angstrom. Two chain carbon atoms and the chelating nitrogen atom occupy the basal plane. The skeleton of two erect oxygen atoms and the tin atom is bent (O-Sn-O angle = 153.5(1)). In the complex, the ligand exists in the enol-form.

SYNTHESIS AND CHARACTERIZATION OF POLY-ORTHO-METHYLANILINE WITH DIFFERENT DEGREES OF OXIDATION

Poly-ortho-methylanilines (POT) in three states fully oxidized, fully reduced and oxidized in varying degrees were synthesized by the reaction of common POT (C-POT) having nearly equal amounts of benzenediamine and quinonediimine units with iodine or phenyl-hydrazine, and the resulting polymers were characterized by IR, C-13-NMR, SEM and elemental analysis. The results showed that the quinonediimine unit in C-POT could be reduced by phenylhydrazine to the benzenediamine unit, forming the polymer with low OD (oxidation degree) or in a fully reduced state and that iodine-oxidation resulted in the increase of quinonediimine unit and decrease of benzenediamine unit. The solubility and flexibility of the formed polymers depend strongly on the amount of quinonediimine unit in it. It is necessary to reduce the content of quinonediimine structure unit in order to improve the solubility of aniline-class polymers.

A HIGH-RESOLUTION SOLID-STATE NMR-STUDY OF THE MISCIBILITY, MORPHOLOGY, AND TOUGHENING MECHANISM OF POLYSTYRENE WITH POLY(2,6-DIMETHYL-1,4-PHENYLENE OXIDE) BLENDS

An extended Goldman-Shen pulse sequence was used to observe indirectly the proton spin diffusion in the blends of polystyrene (PS) with poly(2,6-dimethyl-1,4-phenylene oxides) (PPO). The results indicate that the average distance between PS and PPO is less than 5 angstrom in the intimately mixed phase, but there are heterogeneous domains on a 100-angstrom scale. The data of spin relaxation of carbons, T1(C), for homopolymers and their blends suggest that there is a strong pi-pi electron conjugation interaction between the aromatic rings of PS and those of PPO, while the aromatic rings of PPO drive the aromatic rings of PS to move cooperatively. It is the cooperative motion that markedly improves the impact strength of PS.

STRUCTURE INVESTIGATION OF TI(OBU)4-ALET3 CATALYST BEFORE AND AFTER HEAT-TREATMENT

The catalyst structure of Ti(OBu)4-AlEt3 at different Al/Ti ratios before and after heat aging has been investigated from the data of UV, GC-MS, ESR and C-13 NMR spectra. The complex compounds formed by HTiEt2 and AlEt2(OBu) exist mainly in the catalyst solution, and no -OBu ligands linking with Ti atoms can be found at an Al/Ti ratio of four before heat aging. Many kinds of catalytic species with different size are formed after heat aging the catalyst at 110-degrees-C for 2 h. Dehydrogenation, accompanied by the valence change from Ti3+ to Ti2+, is observed during the aging process of the catalyst.

NMR-STUDIES ON THE COORDINATION OF RARE-EARTHS WITH GLYCYL-DL-VALINE AND THE CONFORMATION OF THEIR COMPLEX IN AQUEOUS-SOLUTION

In this paper lanthanide-induced shifts have been measured for C-13 and H-1 nuclei of glycyl-DL-valine in the presence of three lanthanide cations (La3+, Ho3+ and Yb3+) in aqueous solution. The stability constants of the coordination compounds of rare earths (Ho, Yb) with glycyl-DL-valine have been calculated. The coordination of rare earths with the ligand has been discussed. The simulation for conformation of lanthanide coordination compounds with glycyl-DL-valine shows that the ligand is coordinated to lanthanide ion through oxygen atoms of carboxyl group and the bond length of Ln-O is 0.226 nm. In the coordination compounds glycyl-DL-valine is in extended state with minimal steric hindrance.

STRUCTURE OF CIS-DIAQUABIS(1,10-PHENANTHROLINE)ZINC SULFATE HEXAHYDRATE

[Zn(C12H8N2)2(H2O)2]SO4.6H2O, M(r) = 665.98, triclinic, P1BAR, a = 10.070 (4), b = 12.280 (3), c = 13.358 (2) angstrom, alpha = 109.12 (2), beta = 92.58 (2), gamma = 110.85 (2)-degrees, V = 1433.9 (7) angstrom 3, Z = 2, D(x) = 1.54 g cm-3, lambda(Mo K-alpha) = 0.71069 angstrom, mu = 10.1 cm-1, F(000) = 692, T = 293 K, R = 0.044 for 3985 observed reflections. The Zn atom is coordinated in a distorted octahedral geometry by four N atoms from two 1,10-phenanthroline (phen) ligands and two water molecules. The intermolecular ring-stacking interactions between the phen ligands occur in two forms: infinite chains and discrete dimers. Hydrogen bonds further stabilize the structure.

THE COMPOSITIONS AND STRUCTURES OF SOME COMPOUNDS IN THE SYSTEM CA-SR-CU-O

The system of Ca-Sr-Cu-O have been investigated. Two new compounds with compositions Sr3Cu5O8+alpha and CaSrCu3O5+alpha have been discovered. Both are orthorhombic with a = 6.489, b = 11.280, c = 12.240 angstrom for CaSrCu3O5+alpha and a = 3.950, b = 11.479, c = 13.420 angstrom for Sr3Cu5O8+alpha. The X-ray powder data for CaSrCu3O5+alpha, Sr3Cu5O8+alpha, Sr2CuO3 and SrCuO2 are presented. The oxidation state of Cu ion and oxygen contents are analyzed by iodometric titration. Sr0.5Ca0.5CuO2 that has a similar structure with SrCuO2 has been found and its X-ray data are presented also.

CHARACTERIZATION, MORPHOLOGY AND THERMAL-PROPERTIES OF ETHYLENE PROPYLENE BLOCK COPOLYMERS

Characterization, morphology and thermal properties of commercial ethylene-propylene block copolymers have been studied by C-13 nuclear magnetic resonance (n.m.r.) spectroscopy, differential scanning calorimetry (d.s.c.), dynamic mechanical analysis (d.m.a.) and scanning electron microscopy (SEM). The results obtained show that there exists some ethylene-propylene random copolymer in the block copolymers extractable by n-heptane. The possibility of forming PP-b-PE diblock copolymer is questionable on the basis of the effects of residual propene and the chain-transfer reaction in the sequential copolymerization. A difference in the thermal properties between commercial ethylene-propylene block copolymers and PP/PE blends was noticed, which cannot be used to identify PP-b-PE diblock copolymer. The multiphase structure has been confirmed by d.m.a. and SEM, with ethylene-propylene random copolymer and polyethylene forming the domains in the matrix of polypropylene.

取代基效应(SCS)与乙烯—α—烯烃共聚物的序列结构——Ⅱ.取代基效应方法

本文提出了一种解析乙烯-α-烯烃共聚物的~(13)C NMR谱的取代基效应方法,它揭示了存在于共聚物序列结构与~(13)C谱之间的对应关系,并对这种关系进行了系统的阐述。文章中首次按上述对应关系明显与否将共聚物~(13)C谱分成两类,并给出进行分类的三种判据:SCS参数,共单体均聚物的~(13)C谱,以及取代基的电性。文章最后比较了取代基效应方法与Grant-Paul方法的异同。

PrP_5O_(14)的晶体结构与铁弹畴

本文用X射线衍射方法研究了PrP_5O_(14)的晶体结构和铁弹相变。晶体空间群为P2_1/c,晶胞参数a=8.777(1)A,b=9.029(2)A,c=13.068(2)A,β=90.35°(1),z=4,最终R值为0.046。在130±5℃转变成正交晶系,空间群为P_(ncm),a=8.813(7)A,b=9.075(2)A,c=13.119(10)A。高温相变使晶体产生了铁弹性孪晶,室温下晶体属mmmF2/m类铁弹体。

Ca-Sr-Cu-O系中若干化合物的组成和结构的研究

研究了Ca-Sr-Cu-O三元金属复合氧化物体系,发现了两个新化合物Sr_3Cu_5O_(8+x)和CaSrCu_3·O_(5+x),两者都属正交晶系,前者a=3.950,b=11479,c=13.420 A.后者a=6.489,b=11.280,c=12.240A.文中给出了这两个化合物和SrCuO_2、Sr_2CuO_3的XRD谱.用碘量法测定了化合物中的氧含量.此外还发现了结构与SrCuO_2相似的固溶体Sr_(0.5)Ca_(0.5)CuO_2,也测定了它的XRD谱.

一种新型稀土苯甲酸铽配合物的合成、表征及其晶体结构

本文报道一种新型稀土苯甲酸配合物,[Tb(C_7H_5O_2)_3(C_7H_6O_2)(H_2O)]_2的合成。用元素分析、DTA、TG、DTG和IR光谱对其性质进行了表征,并测定了其晶体结构。晶体属三斜晶系,空间群为P1,Z=1。晶胞参数为:a=9.148(1),b=11.460(2),c=13.506(2)A;α=112.76(1),β=91.83(1),γ=91.99(1)°;V=1303.3(4)A~3。稀土离子形成九配位的单帽正方反棱柱型配合物,稍有崎变。

Chaetopyranin, a benzaldehyde derivative, and other related metabolites from Chaetomium globosum, an endophytic fungus derived from the marine red alga Polysiphonia urceolata

Cultivation of the endophytic fungus Chaetomium globosum, which was isolated from the inner tissue of the marine red alga Polysiphonia urceolata, resulted in the isolation of chaetopyranin (1), a new benzaldehyde secondary metabolite. Ten known compounds were also isolated, including two benzaldehyde congeners, 2-(2 ',3-epoxy-1 ',3 '-heptadienyl)-6-hydroxy- 5-(3-methyl-2-butenyl) benzaldehyde (2) and isotetrahydroauroglaucin (3), two anthraquinone derivatives, erythroglaucin (4) and parietin (5), five asperentin derivatives including asperentin ( 6, also known as cladosporin), 5 '-hydroxy-asperentin-8-methylether (7), asperentin-8-methyl ether (8), 4 '-hydroxyasperentin (9), and 5 '-hydroxyasperentin (10), and the prenylated diketopiperazine congener neoechinulin A (11). The structures of these compounds were determined on the basis of their spectroscopic data analysis (H-1, C-13, H-1-H-1 COSY, HMQC, and HMBC NMR, as well as low- and high-resolution mass experiments). To our knowledge, compound 1 represents the first example of a 2H-benzopyran derivative of marine algal-derived fungi as well as of the fungal genus Chaetomium. Each isolate was tested for its DPPH (1,1-diphenyl-2-picrylhydrazyl) radical-scavenging property. Compounds 1-4 were found to have moderate activity. Chaetopyranin (1) also exhibited moderate to weak cytotoxic activity toward several tumor cell lines.

An acidic polysaccharide with xylose branches from Porphyra yezoensis

An acidic polysaccharide (PY3) was isolated from the hot water extract of the red algae Porphyra yezoensis by successive column chromatographies over DEAE-cellulose and Sephadex G-200. PY3 with an average molecular weight of 1.8x10(5) was demonstrated to be composed of galactose (Gal), 3,6-anhydrogalactose (3,6-AnGal), 6-OSO3-galactose (6-OSO3-Gal) and xylose (Xyl) in an approximate molar ratio of 25 : 15, 10, 1. In view of Smith degradation and methylation and on the basis of spectral evidence including those of IR, GC, GC-MS, and H-1 and C-13 NMR, the most probable repeating unit of PY3 could be proposed as [(1-->3)beta -D-Gal(1 --> 4)alpha -L-3,6-AnGal](3)-[(1 --> 3)beta -D-Gal(1 --> 4)alpha -L-6-OSO3-Gal](2) with a xylose moiety at the C-6 of one of every twenty-five beta -D-Gal residues. To our knowledge, PY3 was shown to be the first porphyran possessing occasional xylose branches.

Methane-derived authigenic carbonates from the Ulleung basin sediments, East Sea of Korea

Authigenic carbonates were sampled in methane-enriched piston core sediments collected from gas venting sites on the western continental slope of the Ulleung Basin, East Sea of Korea. Multidisciplinary investigations on these carbonates, including the scanning electronic microscope (SEM) observations and mineralogical-geochemical compositions, were carried out to identify the carbon and oxygen sources and the forming mechanism of these carbonates. The authigenic carbonates from the study area correspond to semi-consolidated, compact concretions or nodules ranging from 2 to 9 cm in size. X-ray diffraction and electron microprobe analyses showed that most of the sampled carbonate concretions were composed of almost purely authigenic high-Mg calcite (10.7-14.3 mol% MgCO3). Characteristically, microbial structures such as filaments and rods, which were probably associated with the authigenic minerals, were abundantly observed within the carbonate matrix. The carbonates were strongly depleted in delta C-13 (-33.85 parts per thousand to -39.53 parts per thousand Peedee Belemnite (PDB)) and were enriched in delta O-18 (5.16-5.60 parts per thousand PDB), indicating that the primary source of carbon is mainly derived from the anaerobic oxidation of methane. Such methane probably originated from the destabilization of the underlying gas hydrates as strongly supporting from the enriched O-18 levels. Furthermore, the strongly depleted delta C-13 values (-60.7 parts per thousand to -61.6 parts per thousand PDB) of the sediment void gases demonstrate that the majority of the gas venting at the Ulleung Basin is microbial methane by CO2 reduction. This study provides another example for the formation mechanism of methane-derived authigenic carbonates associated with gas-hydrate decomposition in gas-seeping pockmark environments. (c) 2009 Elsevier Ltd. All rights reserved.