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.

THE USE OF LIGHT-MICROSCOPY FOR INVESTIGATIONS OF EPITAXIAL-GROWTH OF POLYMERS ON POLYMERIC SUBSTRATES

In order to study the oriented (epitaxial) crystallization of thermoplastic polymers on oriented polymer substrates, generally the transmission electron microscopy (TEM) is used. With this instrument, the crystallized material can easily be resolved and orientation relationships can be monitored by electron diffraction. Disadvantages are the time consuming sample preparations and difficulties in the in-situ observations of the crystallization events, because of the radiation sensitivity of the polymer crystals. It is demonstrated that these disadvantages of the TEM can be eleminated by the use of different methods of light optical contrasts under specific preparation conditions of the samples and that the optical microscopy being a supplementary method to the TEM for investigations of epitaxial crystallization.

THE EFFECT OF MOBILITY OF MOLECULES ON RADIATION-INDUCED CHAIN SCISSION AND RACEMIZATION OF ISO-POLY(METHYL METHACRYLATE)

The radiation-induced chain-scission and racemization of isotactic poly(methylmethacrylate)(iso-PMMA) in amorphous and semi-crystalline state as well as in solution have been studied with nuclear magnetic resonance and molar mass deter-mination. It is shown that the chain-scission is dominant for iso-PMMA in dilute solution while the racemization reaction is not favorable in this case. On the contrary, the racemization is favorable when iso-PMMA was irradiated in its crystalline state while chain-scission is not. Such experimental results could be well explained by the mobility of molecules and "cage effect". The hypothesis, we proposed previously that the chain-scission, racemization and recombination are in competition and the final result depends on the state of molecular motion at which iso-PMMA was irradiated, has been verified verified once again.

MOLECULAR-GEOMETRY AND CHAIN ENTANGLEMENT - PARAMETERS FOR THE TUBE MODEL

The tube diameter in the reptation model is the distance between a given chain segment and its nearest segment in adjacent chains. This dimension is thus related to the cross-sectional area of polymer chains and the nearest approach among chains, without effects of thermal fluctuation and steric repulsion. Prior calculated tube diameters are much larger, about 5 times, than the actual chain cross-sectional areas. This is ascribed to the local freedom required for mutual rearrangement among neighboring chain segments. This tube diameter concept seems to us to infer a relationship to the corresponding entanglement spacing. Indeed, we report here that the critical molecular weight, M(c), for the onset of entanglements is found to be M(c) = 28 A/([R2]0/M), where A is the chain cross-sectional area and [R2]0 the mean-square end-to-end distance of a freely jointed chain of molecular weight M. The new, computed relationship between the critical number of backbone atoms for entanglement and the chain cross-sectional area of polymers, N(c) = A0,44, is concordant with the cross-sectional area of polymer chains being the parameter controlling the critical entanglement number of backbone atoms of flexible polymers.

DOPING EFFECTS ON THE POLYMER-CHAIN STRUCTURE OF POLY(3-METHYLTHIOPHENE)

The C=C stretching Raman shifts and photoluminescence (PL) for poly(3-methylthiophene) (P3MT) are measured at various doping levels by in situ electrochemical Raman and PL spectroscopic techniques. It is found that the doping for P3MT induces the nonlinear excitations (soliton, Polaron, bipolaron), but also affects the polymer-chain structure, including the conjugated length and the interchain distance.

CONFORMATION OF PHENYL RINGS IN THE HELICAL CHAIN POLYMER POLY(TRIPHENYLMETHYL METHACRYLATE)

The conformation of phenyl rings in the side groups of the helical chain polymer poly(tripenyl-methyl methacrylate) (1) in solution was studied by spectroscopic methods. According to the Raman spectrum the phenyl rings of 1 and triphenylmethyl methacrylate in solution have the same depolarization ratio at 1002 cm-1. The electronic spectra (ultraviolet and fluorescence) of 1 are similar to those of model substances, except for the "red shift" of the spectra of about 5 nm. It was concluded that the phenyl rings can rotate around the phenyl-C bond.

MOLECULAR CHAIN STRUCTURE OF DOPED POLYANILINE

The chain structure of polyaniline doped with HCl or CF_3COOH has been investigated by FTIR, solid state ~(13)CNMR, resonance laser Raman and UV-VIS spectroscopies. The results show that during the protonic acid doping, a partial redox reaction takes place between the quinone-diimine and benzene-diamine units and it leads to a long conjugate system with a certain charge distribution.

HREM IMAGING OF POLY(ARYL-ETHER-KETONE) CRYSTAL

High resolution transmission electron microscope (HREM) was used to observe the rigid chain polymer poly(aryl-ether-ketone) (PEK), so as to study the morphology of the crystals and molecular arrangement within a crystal.Many kinds of material crystal structures have been studied with HREM in recent years. So far as polymeric materials are concerned, the application of HREM

cDNA cloning, characterization and mRNA expression of a pacifastin light chain gene from the Chinese mitten crab Eriocheir sinensis

The pacifastin family, characterized by several conserved arrays of six cysteine residues, is a newly identified serine protease inhibitor (SPI) family discovered uniquely in arthropods and plays important roles in multiple biological processes. In the present study, the full-length cDNA of a pacifastin light chain (designated ESPLC) was cloned from the Chinese mitten crab Eriocheir sinensis by expressed sequence tags (ESTs) and PCR techniques. The 1036 bp ESPLC cDNA contained an 831 bp open reading frame (ORF) encoding a putative pacifastin-related peptide of 276 amino acids, a 5'-untranslated region (UTR) of 67 bp, and a 3'-UTR of 138 bp. Six putative conserved domains sharing a characteristic cysteine array (Cys-Xaa(9-12)-Cys-Asn-Xaa-Cys-Xaa-Cys-Xaa(2-3)-Gly-Xaa(3-4)-Cys-Thr-Xaa(3)-Cys) were identified in the deduced amino acid sequence of ESPLC. The conservation of these PLDs (pacifastin light chain domains) and the relative higher similarity of ESPLC to other pacifastin-related precursors suggested that ESPLC was a member of pacifastin family. The mRNA transcripts of ESPLC were found to be higher expressed in hepatopancreas, gill and haemolymph than in gonad, muscle and heart, with the highest expression level in hepatopancreas. The ESPLC mRNA expression in haemolymph of Chinese mitten crab was up-regulated at 2 h and 12 h after challenged with Listonella anguillarum. The tissue distribution and temporal characteristics of ESPLC mRNA expression, similar to that of prophenoloxidase gene in E. sinensis, suggested that ESPLC was potentially involved in the response against invading bacteria, with the possibility that it functioned in the prophenoloxidase system in E sinensis. (C) 2008 Elsevier Ltd. All rights reserved.

Sources and preservation of organic matter in Plum Island salt marsh sediments (MA, USA): long-chain n-alkanes and stable carbon isotope compositions

Elemental (TOC, TN, C/N) and stable carbon isotopic (delta(13)C) compositions and n-alkane (nC(16-38)) concentrations were measured for Spartina alterniflora, a C-4 marsh grass, Typha latifolia, a C-3 marsh grass, and three sediment cores collected from middle and upper estuarine sites from the Plum Island salt marshes. Our results indicated that the organic matter preserved in the sediments was highly affected by the marsh plants that dominated the sampling sites. delta(13)C values of organic matter preserved in the upper fresh water site sediment were more negative (-23.0+/-0.3) as affected by the C-3 plants than the values of organic matter preserved in the sediments of middle (-18.9+/-0.8) and mud flat sites (-19.4+/-0.1) as influenced mainly by the C4 marsh plants. The distribution of n-alkanes measured in all sediments showed similar patterns as those determined in the marsh grasses S. alterniflora and T. latifolia, and nC(21) to nC(33) long-chain n-alkanes were the major compounds determined in all sediment samples. The strong odd-to-even carbon numbered n-alkane predominance was found in all three sediments and nC(29) was the most abundant homologue in all samples measured. Both delta(13)C compositions of organic matter and n-alkane distributions in these sediments indicate that the marsh plants could contribute significant amount of organic matter preserved in Plum Island salt marsh sediments. This suggests that salt marshes play an important role in the cycling of nutrients and organic carbon in the estuary and adjacent coastal waters. (C) 2003 Elsevier Ltd. All rights reserved.