Structural developments in synthetic rubbers during uniaxial deformation by in situ synchrotron X‐ray diffraction

The molecular orientation and strain‐induced crystallization of synthetic rubbers—polyisoprene rubber, polybutadiene rubber, and butyl rubber [poly(isobutylene isoprene)]—during uniaxial deformation were studied with in situ synchrotron wide‐angle X‐ray diffraction. The high intensity of the synchrotron X‐rays and the new data analysis method made it possible to estimate the mass fractions of the strain‐induced crystals and amorphous chain segments in both the oriented and unoriented states. Contrary to the conventional concept, the majority of the molecules (50–75%) remained in an unoriented amorphous state at high strains. Each synthetic rubber showed a different behavior of strain‐induced crystallization and molecular orientation during extension and retraction. Our results confirmed the occurence of strain‐induced networks in the synthetic rubbers due to the inhomogeneity of the crosslink distribution. The strain‐induced networks containing microfibrillar crystals and oriented amorphous tie chains were responsible for the ultimate mechanical properties. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 956–964, 2004     

Fabrication and transport properties of multiwall carbon nanotube crossroads

A multiwall carbon nanotube crossroads has been fabricated by a manipulation technique using a glass microcapillary, and the low temperature transport properties investigated. The two-terminal conductance of an individual tube shows Tomonaga–Luttinger liquid behavior G∝T^α at high temperature and dI/dV ∝V ^α at low temperature. However, no evidence of such a power-law behavior is obtained in the four-terminal conductance at the junction, where the conductance shows an almost metallic behavior ‘corrected’ by weak localization. Weak localization would essentially appear in electron states at the junctions of MWNTs.     

New triterpenes from a Chinese medicine, goreishi

Besides serratagenic acid, three new ursane-type triterpenes, named goreishic acids I (1), II (2), and III (3), were isolated from a Chinese medicine, Goreishi (the feces of Trogopterus xanthipes Milne-Edwards). The structures of 1, 2 and 3 were respectively determined as 2 alpha,3 beta-dihydroxyursa-12,18-dien-28-oic acid, 2 alpha,3 beta-dihydroxy-23-norursa-12,18-dien-28-oic acid and 2 alpha,3 beta-dihydroxy-24-norursa-12,18-dien-28-oic acid on the basis of spectroscopic evidence.     

Copper(II)-catalyzed oxidation of d-alpha-tocopherol by oxygen in aqueous solution

alpha-Tocopherol (alpha-Toc) was solubilized in aqueous solutions using 13 solubilizing agents and the products of oxidation by oxygen in the presence and the absence of Cu(II) were analyzed by HPLC. In the presence of Cu(II), the oxidation was accelerated and 5-formyl-7,8-dimethyltocol and alpha-tocoquinone were the major oxidation products. Their yields greatly increased in the presence of Cu(II). The yields and the rates of formation of the products were dependent on the properties of solubilizing agents and other conditions as well as the presence of Cu(II) or other metal ions. It is suggested that slight changes in the structure of the solubilizing agents affect the course of the reaction.     

Synthesis of nitrogen-containing heterocycles 6. Formation and structures of imidazolinones and related compounds through cyclization of diaminomethylenehydrazones with dimethyl acetylenedicarboxylate

Diaminomethylenehydrazones 1 of aromatic and aliphatic carbonyl compounds react with dimethyl acetylenedicarboxylate (DMAD) at room temperature to give four types of heterocycles, (5-oxoimidazolin-4-ylidene) acetates 2, 3 and 6 , (2-imino-5-oxoimidazolidin-4-ylidene) acetate 4 and 6-oxo-1,6-dihydropyrimidine-4-carboxylates 5 according to the substitution patterns of 1 in moderate to high yields. Amino (N,N-dimethylamino)methylenehydrazones of ketones give exclusively (5-oxoimidazolin-4-yl-idene) acetates, both (Z)- and (E)-isomers 2 and 3 about the exocyclic alkenic linkage, with the (Z)-isomer 2 generally being predominant, while those of aldehydes give 5 . Diamino- and amino (N-methylamino)methylenehydrazones produce 5 and/or 6 and di (N-methylamino) methylenehydrazone gives (2-imino-5-oxoimidazolidin-4-ylidene) acetate 4 as the sole cyclized product.     

Spirophostins: conformationally restricted analogues of adenophostin A

The synthesis, biological evaluation, and molecular modeling of two conformationally restricted analogues of adenophostinA (1), denominated as spirophostin (3R)-10 and (3S)-11, as novel ligands for the D-myo-inositol 1,4,5-trisphosphate receptor (IP3R), is presented. These diastereoisomeric spiroketals are synthesized by spiroketalization of D-glucose derivatives (2S)-15 and (2R)-16, separation of the protected isomers (3R)-19 and (3S)-20, followed by phosphorylation and deprotection. The spirophostins (3R)-10 and (3S)-11 display comparable biological activity, with a 3H-IP3-displacing and Ca2+-releasing potency less than IP3 and adenophostin A.     

Constituents of holothuroidea.9. Isolation and structure of a new ganglioside molecular species from the sea cucumber Holothuria pervicax

A new ganglioside molecular species, HPG-7 (1) was obtained from the polar fraction of the chloroform/methanol extract of the sea cucumber, Holothuria pervicax. On the basis of chemical and spectroscopic evidence, the structure of 1 was determined, and the major component was 1-O-[alpha-L-fucopyranosyl-(1-->4)-(N-acetyl-alpha-D-neuraminosyl) - (2-->11)-(N-glycolyl-alpha-D-neuraminosyl)-(2-->4)-(N-acetyl -alpha-D- neuraminosyl)-(2-->6)-beta-D-glucopyranosyl]-(2S,3S,4R)-2-[(2R)-2- hydroxytetracosanoylamino]-14-methyl-hexadecane-1,3,4-triol. This is the first report on the isolation and structure elucidation of trisialo-ganglioside from sea cucumber. 1 showed neuritogenic activity toward the rat pheochromocytoma cell line, PC-12 cell.