Synthesis, electrical properties and crystal structure of a new radical-ion salt based on pi-extended bis(TTF) and a Keggin heteropolymolybdate

By electrocrystallization of 2,6-[4,5-bis(n-butylsulfanyl)-1,3-dithiol-2-ylidene]-4,8-bis(6-iodo-n-hexyloxy)-1,3,5,7-tetrathia-s-indacene (BHBDTI) and [NBu4](4)[SiMo12O40] in the mixed solvent CHCl2CH2Cl and CH3CN, the new radical-ion salt [C42H60Cl2O2S12](2)[SiMo12O40] was prepared. It was characterized by means of IR and ESR spectroscopy and X-ray diffraction. In the crystal structure, organic radical dications and silicomolybdate anions are alternatively arranged along the a axis to form a 1-D conducting layer. The organic layer consists of two isolated groups of BHBDTI divided by the (011) plane without short interatomic contacts. However, in each group, BHBDTI molecules associate with each other in a head to tail manner running along the [011] direction and face-to-face overlapping with a relative shift by approximately one TTF subunit along the long axis of the molecule and a slight shift along the short axis of the molecule with significantly short S ... S contacts. The room-temperature d.c. conductivity determined by the two-probe method is 10(-4) S cm(-1), suggesting that the compound is a semiconductor.

Chain conformation of a high-performance polyimide in organic solution

An organo-soluble polyimide based on 1,4-bis(3,4-dicarboxyphenoxy) benzene dianhydride (HQDPA) and 2,2'dimethyl-4,4'-methylene dianiline (DMMDA), was synthesized via two-step polycondensation accompanied by chemical imidization. Five fractions were prepared by fractionation. The dilute solutions of the fractions were studied by LLS (Laser Light Scattering) and the intrinsic viscosities of the fractions were measured. The unperturbed dimension was determined by the intrinsic viscosity with the Stockmayer-Fox equation. The results indicate that the polyimide in this study has a flexible chain conformation in chloroform and N,N-dimethyl acetamide (DMAc). However, the degree of chain expansion differs in different solvents. (C) 1998 Published by Elsevier Science Ltd. All rights reserved.

EXTENDED SOLUBILITY AND SPIN-GLASS BEHAVIOR IN A AG-GD SOLID-SOLUTION PREPARED BY MECHANICAL ALLOYING

The effects of mechanical alloying on the solubility in a Ag-Gd solid solution have been investigated. The study shows that the solubility of Gd in Ag can be extended to about 5 at. % Gd by mechanical alloying from the equilibrium solubility of less than 0.95 at. % Gd. Ag85Gd15 prepared by mechanical alloying exhibits a spin-glass-type transition at similar to 5 K. A Curie-Weiss behavior at higher temperatures and x-ray patterns of the material indicate that Gd atoms are either dissolved in the Ag matrix or in the form of small clusters of diameters of a few nanometers;

RELATIONSHIP BETWEEN CONFORMATION OF TASTE COMPOUNDS AND THEIR ACTIVITIES

The conformation analysis and study on structure-taste relation-ships of 4 taste compounds have been performed, the results reveal that the sweetnees will decrease with the increase of the specific dihedral angle O-1-C-2-C-3-C-4, and the mechanism was intepreted.

EFFECTS OF METAL-IONS ON THE CONFORMATION OF POLAR HEADGROUP OF SPHINGOMYELIN BILAYER

With the wide application of rare earth in agriculture, medicament, especially the application of Gd-DTPA as nuclear magnetic resonance image reagent in clinical practice([1]), the studies on the toxicology in biological body, as well as the study on the use as informative probes instead of divalent calcium ion in biological and biochemical research have attracted intensive concern([2]). Phospholipids bilayers have served as a model of biomembrane in the last two decades. The effects of metal ions on the conformation of polar headgroup of dipalmitoylphosphatidylcholine (DPPC) bilayers have been reported([3]). Sphingomyelin is major component of several biological tissues such as brain and nerve cells and has identical polar headgroup to DPPC. The interaction of metal ions with sphingomyelin bilayer remains nonrevealed. This note presents the results of the study on this aspect.

EXTENDED ADJACENCY MATRIX INDEXES AND THEIR APPLICATIONS

In this paper, new topological indices, EA Sigma and EAmax, are introduced. They are based on the extended adjacency matrices of molecules, in which the influences of factors of heteroatoms and multiple bonds were considered. The results show that EA Sigm

NORMAL COORDINATE TREATMENT OF LEU(5)-ENKEPHALIN IN THE CRYSTAL-STATE

Vibrational studies on the neuropentapeptide Leu5-enkephalin were performed for the crystal state where different specific conformations can arise. In the present case, the peptide adopts a double fused folded conformation (beta-turn), the presence of which in the crystal state is directly related to the nature of the solvent used for its crystallization. This study completes other work relating to similar conformations of isolated molecules. It can be seen that specific interactions in the crystal state perturb to a large extent the vibrational relationships between the amide frequencies and the specific sets of dihedral angles characteristic of the particular type of turn. The tyrosyl moiety and its frequency dependence on its hydrogen bond state was especially investigated both for the Fermi resonance and the hydroxyl bending modes.

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.

FROM DIMER TO POLYMER .2. EXTENDED TO SYSTEMS POSSESSING 2-FOLD SCREW AXIS OR GLIDE PLANE

The approach for constructing the qualitative band structure of a polymer from corresponding dimer has been extended to the system possessing two-fold screw axis or. glide plane. The classification of energy levels of the dimer in the present case depends on pseudo-symmetry/antisymmetry instead of psendo-in-phase/out-of-phase property of the orbitals. Several typical conductive polymers are then discussed follow this approach. Among them are cis-polyacetylene, polyparaphenylene with a twist ang...

High level expression, purification, and characterization of the shrimp antimicrobial peptide, Ch-penaeidin, in Pichia pastoris

Penaeidins, members of a new family of antimicrobial peptides constitutively produced and stored in the haemocytes of penaeid shrimp, display antimicrobial activity against bacteria, and fungi. Here, a DNA sequence encoding the mature Ch-penaeidin peptide was cloned into the pPIC9K vector and transformed into Pichia pastoris. The transformed cells were screened for multi-copy plasmids using increasing concentrations of G418. Positive colonies carrying chromosomal integrations of the Chp gene were identified by phenotype and PCR. When transformed cells were induced with methanol, SDS-PAGE and Western blotting revealed the production of a similar to6100 Da recombinant CHP (rCHP) expression product. Large scale expression revealed that rCHP was produced at 108 mg/L under optimal conditions in the highest Chp-producing P. pastoris clone. The antimicrobial activities of rCHP were studied by liquid phase analysis, which revealed that rCHP exhibited activities against some Gram-negative and Gram-positive bacteria, but had a relatively low activity against some fungi. Purification of rCHP by cation exchange chromatography and subsequent automated amino acid sequencing revealed the presence of four additional amino acids (YVEF) at the N-terminus that belonged to the cleaved fusion signal peptide; these residues may account for the observed decrease in antifungal activity. Together, these observations indicate that rCHP is an effective antimicrobial peptide that can be successfully produced at high levels in the yeast, and therefore may be a potential antimicrobial candidate for practical use. (C) 2004 Elsevier Inc. All rights reserved.

Molecular cloning and expression analysis of Ch-penaeidin, an antimicrobial peptide from Chinese shrimp, Fenneropenaeus chinensis

A new member of antimicrobial peptide genes of the penaeidin family, Ch-penaeidin, has been cloned from the haemocytes of Chinese shrimp, Fenneropenaeus chinensis, by reverse transcription PCR (RT-PCR), 3'-rapid amplification of cDNA end (3'-RACE) and smart cDNA methods. The Ch-penaeidin cDNA was 655 bp and the open reading frame of the cDNA encoded a 71 amino acid peptide. Ch-penaeidin contained a putative NH2-terminal signal Sequence (1-19) followed by a mature peptide (20-71). The sequence identify with other penaeidins from Litopenaeus vannamei and Litopenaeus setiferus is between 48% and 71%. The signal sequence of Ch-penaeidin is almost completely identical to that of other penaeidins, while differing relatively in the N-terminal domain of the mature peptide. Ch-penaeidin was designated as a novel member of class penaeidin 3 according to phylogenetic analysis. The Mature peptide. with a predicted molecular weight of 5589.32 Da, and a pI of 9.77, has eight positively charged amino acids and no negatively charged amino acids. The expression and distribution of Ch-penaeidin in Unchallenged shrimps were studied by RT-PCR, Northern blot and in situ hybridisation. The results showed that the Ch-penaeidin transcripts were detected in haemocytes (granular haemocytes), heart, gill, intestine, and subcuticular epithelia of the shrimp. and that Ch-penaeidin was constitutively expressed mainly in haemocytes. (C) 2003 Elsevier Ltd. All rights reserved.

Preliminary study on a potential antibacterial peptide derived from histone H2A in hemocytes of scallop Chlamys farreri

Histone H2A is reported to participate in host defense response through producing novel antimicrobial peptides (AMPs) from its N-terminus in vertebrates and invertebrates, while the AMPs derived from H2A have not to our knowledge been reported in mollusca. In the present study, gene cloning, mRNA expression of H2A from scallop Chlamys farreri, and the recombinant expression of its N-terminus were conducted to investigate whether a similar mechanism exists in mollusca. The full-length DNA of H2A was identified by the techniques of homology cloning and genomic DNA walking, The full-length DNA of the scallop H2A was 696 bp long, including a 5'-terminal untranslated region (UTR) of 90 bp, a 3'-terminal UTR of 228 bp with a stem-loop structure and a canonical polyadenylation signal sequence AATAAA, and an open reading frame of 375 bp encoding a polypeptide of 125 amino acids. The mRNA expression of H2A in the hemocytes of scallop challenged by microbe was measured by semi-quantitative RT-PCR. The expression of H2A was not upregulated after stimulation, suggesting that H2A did not participate in immunity response directly. The DNA fragment of 117 bp encoding 39 amino acids corresponding to the N-terminus of scallop H2A, which was homologous to buforin I in vertebrates, was cloned into Pichia pastoris GS115. The transformants (His(+) Mut(+)) containing multi-copy gene insertion were selected with increasing concentration of antibiotic G418. The peptide of 39 amino acids was expressed by induction of 0.5% methanol. The recombinant product exerted antibacterial activity against both Gram-positive (G(+)) and Gram-negative (G(-)) bacteria. The antibacterial activity toward G(+) bacteria was 2.5 times more than that against G(-) bacteria. The results elucidated that N-terminus of H2A was a potential AMP and provided a promising candidate for a new antibiotic screening. However, whether H2A is really involved in scallop immune response mechanisms needs to be further investigated. (C) 2006 Elsevier Ltd. All rights reserved.

PenBase, the shrimp antimicrobial peptide penaeidin database: Sequence-based classification and recommended nomenclature

Antimicrobial peptides play a major role in innate immunity. The penaeidins, initially characterized from the shrimp Litopenaeus vannamei, are a family of antimicrobial peptides that appear to be expressed in all penaeid shrimps. As of recent, a large number of penaeid nucleotide sequences have been identified from a variety of penaeid shrimp species and these sequences currently reside in several databases under unique identifiers with no nomenclatural continuity. To facilitate research in this field and avoid potential confusion due to a diverse number of nomenclatural designations, we have made a systematic effort to collect, analyse, and classify all the penaeidin sequences available in every database. We have identified a common penaeidin signature and subsequently established a classification based on amino acid sequences. In order to clarify the naming process, we have introduced a 'penaeidin nomenclature' that can be applied to all extant and future penaeidins. A specialized database, PenBase, which is freely available at http://www.penbase.immunaqua.com, has been developed for the penaeidin family of antimicrobial peptides, to provide comprehensive information about their properties, diversity and nomenclature. (c) 2005 Elsevier Ltd. All rights reserved.