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     

Studies on the syntheses of heterocyclic compounds. CLXXIV. An approach to the synthesis of oxyacanthine and berbamine

Schotten-Baumann reaction of the amine (X) with 4-benzyloxy-3,4′-oxydiphenylacetyl chloride (XI) gave two amides, (XIIa) and (XIIb), which were cyclized to give the corresponding 3,4-dihydroisoquinolines, respectively. Methylation of the above 3,4-dihydro-isoquinolines, followed by hydrolysis, afforded the compounds having the same composition as berbamine (Ia) and oxyacanthine (Ib), whose structures are under examination.     

Photodimerization of benzene -photochromism of layered dithiacyclophane-

A novel cage compound was obtained by irradiation of a quadruple-layered dithiacyclophane and showed thermally reverse reaction.     

Towards the selective formation of specific isomers of fullerenes: T - and p-dependence in the yield of various isomers of fullerenes C60–C84

Systematic fractional change in the yield of various isomers of fullerenes was revealed to strongly depend on temperature of a buffer gas. A new kinetic consideration is proposed for understanding the observed temperature- and pressure-dependence of yield of fullerenes. The model consists of three competitive reactions in consideration of plausible behaviors of a precursor, (1) decomposition into smaller fragments, (2) isomerization leading to formation of a stable fullerene cage, and (3) growth into a larger carbon cluster. Arrhenius activation energy of formation of stable fullerenes was determined to be 0.8 eV for both C₆₀ and C₇₀, while a higher energy of 2.0?3.3 eV for seven different isomers of higher fullerenes ranging from C₇₆ to C₈₄. Correlation in the activation energy is noted for a series of higher fullerenes with different sizes, suggesting the existence of a specific precursor in their formation processes.     

Thermal Emulsion Polymerization without any Conventional Initiators and Emulsifiers

Stable poly(styrene-co-sodium styrene sulfonate) (P(St-NaSS) nanoparticles with broader size distribution were synthesized by thermal emulsion polymerization without any conventional initiators and emulsifiers. The obtained polymer nanoparticles have higher ξ potential, and the particle sizes have broad distribution. The stability of polymer particles originated from the addition of small amounts of ionic comonomer, NaSS, which can act as an emulsifier in somewhat. The monomer conversion could reach up to about 28 wt% in 48 h, and did not increase by further polymerization when higher polymerization temperature (120 ℃) was employed. This polymerization system may be give some further understand for mechanism of emulsion polymerization.     

Determination of aluminum in serum by capillary zone electrophoresis with laser-induced fluorescence detection

Summary A novel method of separating and detecting trace aluminum by capillary zone electrophoresis is described. Aluminum is reacted with lumogallion [4-chloro-3-(2,4-dihydroxyphenylazo)-2-hydroxybenzen-1-sulphonic acid] so that the complex can be selectively and sensitively detected by a laser-induced fluorescence detector after capillary electrophoretic separation. Using the proposed method, limits of detection in the sub parts per billion range are achieved. The technique is applied to the determination of aluminum in human serum.     

In situ monitoring of metal nanoparticle self-assembly on protein-functionalized glass by broadband optical waveguide spectroscopy

Broadband, time-resolved optical waveguide (OWG) spectroscopy has been used for in situ, real-time investigation into the self-assembly of metal nanoparticle monolayers. The OWG spectroscopy makes it possible to use the transverse electric (TE) and transverse magnetic (TM) modes to measure surface plasmon absorption of immobilized metal nanoparticles in two directions, parallel and normal to the waveguide surface. Therefore, this technique can provide direction-dependent information on the metal nanoparticles at the interface. In this paper, a 50-microm-thick glass plate was used as a slab waveguide and the kinetics of Au nanoparticle adsorption on a hemoglobin-functionalized glass substrate was examined in the early stage of self-assembly. The findings show that with the TE mode the surface plasmon resonance (SPR) behavior for immobilized Au nanoparticles is different from that with the TM mode.     

Daphniglaucins D-H, J, and K, new alkaloids from Daphniphyllum glaucescens

Five new fused-hexacyclic alkaloids, daphniglaucins D (1), E (2), F (3), G (4), and H (5), and two new yuzurimine-type alkaloids, daphniglaucins J (6) and K (7), have been isolated from the leaves of Daphniphyllum glaucescens, and the structures and relative stereochemistry were elucidated on the basis of spectroscopic data and chemical means.     

Daphniglaucins A and B,novel polycyclic quaternary alkaloids from Daphniphyllum glaucescens

[structure: see text] Two cytotoxic quaternary Daphniphyllum alkaloids with an unprecedented fused-polycyclic skeleton containing a 1-azoniatetracyclo[5.2.2.0.(1,6)0.(4,9)]undecane ring system, daphniglaucins A (1) and B (2), have been isolated from the leaves of Daphniphyllum glaucescens. Their structures and relative stereochemistry were elucidated on the basis of spectroscopic data.