Lasting chemiluminescence of 3-indoleglyoxylyl chloride and its enhancement.

The chemiluminescence (CL) intensities of various indole derivatives substituted with a glyoxylyl group at the 3-position and a hydroxyl group at the 5-position of the indole ring were compared upon the addition of H2O2 in alkaline media. The CL intensities of 3-indoleglyoxylyl chloride, 3-indoleglyoxylic acid, 5-hydroxyindole and 5-benzyloxyindole in CH3CN were 5.9-, 48-, 5.9- and 3.3-fold stronger than that of 3-methylindole. A lasting CL of 3-indoleglyoxylyl chloride was found. Under appropriate conditions, the CL emission reached a maximum within 10 min after the addition of H2O2 in the presence of NaOH, and the intensity was retained for 25 min. One of the final products via the CL reaction of 3-indoleglyoxylyl chloride was indole-3-carboxylic acid. 3-Indoleglyoxylyl chloride emitted light by decompositions via both dioxetane and dioxetanedione. An enhancement effect of beta-cyclodextrin and bovine serum albumin on the CL of 3-indoleglyoxylyl chloride was also found.     

纸张上光油关键物质的成分分析

利用色相色谱／质谱联用技术，傅立叶红外及裂解－气相色谱／质谱联用技术，对印刷用上光油的关键成分进行了分析，共鉴定出７种挥发性组分，２种高分子聚合物。     

GalnAsP-InP double-heterostructure lasers

GaInAsP-InP double-heterostructure lasers which are the most promising optical sources for the long wavelength region have been investigated. In the crystal growth, it was found that the liquidus and solidus isotherms are affected by the orientation of InP source and substrate crystals in the liquid phase epitaxial growth of GaInAsP alloys. The unit cell of the GaInAsP epitaxial layer is tetragonally deformed due to the interface lattice misfit such that the lattice constant parallel to the wafer surface is invariant across the interfaces in the GaInAsP-InP wafers. Two kinds of stripe lasers, planar stripe and buried lasers, have been fabricated by use of GaInAsP cap layer for good p-type contact. The planar stripe lasers of 10,15 and 20 m wide stripe operated in fundamental-transverse mode with 20–30% differential external efficiencies per facet. The 15 m wide stripe laser showed good mode characteristics to operate in a fundamental-transverse mode up to the cw output power of 22 mW per facet and in a single longitudinal mode over a wide range of currents. The buried stripe laser operated in a fundamental-transverse mode with the threshold current as low as 30 mA by making the stripe width narrower than 2 (m. The laser succeeded in cw operation at 100 °C because of its low threshold current and low thermal resistance.The authors would like to thank K. Noda, N. Kuroyanagi and Y. Furukawa for their encouragement. Thanks are also due to H. Kano for permission to use his results of buried stripe lasers prior to publication, and S. Ando for his technical assistance.     

Biomimetic formation of gramicidin S by dimerization-cyclization of pentapeptide precursor on solid support

The biomimetic formation of gramicidin S, cyclo(-d-Phe-Pro-Val-Orn-Leu-)₂, by the dimerization and cyclization of pentapeptide precursor without the protection of δ-amino group of the Orn residue was examined on a solid support. The cyclization of H-d-Phe-Pro-Val-Orn-Leu-oxime on a resin with an oxime group of 0.62 mmol/g in 1,4-dioxane directly gave gramicidin S in a 50% yield. The dimerization-cyclization mode on the solid support was similar to that of the biosynthesis of gramicidin S on an enzyme.     

Diinsertion of fluorenylidene into a sulfur-sulfur bond of diaryl disulfides

Upon irradiation (>340 nm) of a benzene solution of diazofluorene with di-p-tolyl- or di-p-anisyl disulfide, the corresponding 9,9′-bis(arylmercapto)bifluorenyl was afforded in moderate to good yield accompanied by formation of 9,9′-bis(arylmercapto)fluorene. The major reaction pathway is considered to be a disulfur ylide formation followed by two times of successive Stevens rearrangement or by concerted electron redistribution via [2,3]sigmatropic rearrangement.     

Polymer‐Assisted Solution‐Phase Synthesis and Neurite‐Outgrowth‐Promoting Activity of 15‐Deoxy‐Δ12,14‐PGJ2 Derivatives

An efficient solution‐phase synthesis of rac‐15‐deoxy‐Δ^12,14‐PGJ₂ (15dPGJ₂) derivatives that contain variable α and ω chains based on a polymer‐assisted strategy and their neurite‐outgrowth‐promoting activity are described. The strategy for the synthesis of PGJ₂ derivatives involves the use of a vinyl iodide bearing cyclopentenone as a key intermediate, which undergoes Suzuki–Miyaura coupling and subsequent Lewis acid catalyzed aldol condensation for incorporation of the ω and α chains, respectively. For easy access to the PGJ₂ derivatives, a polymer‐supported catalyst and scavengers were adapted for use in these four diverse steps, in which workup and purification can be performed by simple filtration of the solid‐supported reagents. By using this methodology, we succeeded in the synthesis of 16 PGJ₂ derivatives with four alkyl boranes and four aldehydes. The neurite‐outgrowth‐promoting activity of the 16 synthetic compounds in PC12 cells revealed that the side‐chains play a major role in modulating their biological activity. The carboxylic acid on the α chain improved the biological activity, although it was not absolutely required. Furthermore, a PGJ₂ derivative with a phenyl moiety on the ω chain was found to exhibit an activity comparable to that of natural 15dPGJ₂.     

Interaction between the end groups and the main chain of conjugated polymers by time-resolved EPR and fluorescence spectroscopy

ABSTRACT

Interaction between a zinc porphyrin (ZnPor) as the end-group and poly(9,9-di-n-octylfluorene-2,7-vinylene) (PFV) as the main chain in a porphyrin end-modified fluorescent conjugated polymer, ZnPFV, was studied by time-resolved electron paramagnetic resonance (EPR) and fluorescence spectroscopy. While fluorescence from the PFV part of ZnPFV showed a spectral profile almost identical to that of a PFV oligomer without end-modification, the emission spectrum of the ZnPor part exhibited a much broader profile compared to that of the reference zinc porphyrin monomer. Based on the analysis of lifetimes and quantum yields, it was found that radiative rate constant of the ZnPor part was enhanced by nearly three times. The observed unusual enhancement in the radiative rate constant was rationalised in terms of a partial π-conjugation between the end group and the main chain, as a result of co-planarisation in fluid solution. On the other hand, the time-resolved EPR spectrum of ZnPFV at 100?K basically showed a similar spectral pattern to that of the reference zinc porphyrin, but with significant differences in zero-field spitting parameters and initial population ratios. The π-system of the excited triplet state is deduced to deviate from D_4h symmetry in the end zinc porphyrin groups. The obtained results show that interaction of the porphyrin end group with the main chain of the polymer significantly influences the excited singlet state properties of the porphyrin, while its triplet state properties were affected to a lesser extent.     

Comprehensive Metabolite Profiling in Genetic Resources of Garlic (Allium sativum L.) Collected from Different Geographical Regions

Garlic (Allium sativum) is the second most important Allium crop that has been used as a vegetable and condiment from ancient times due to its characteristic flavor and taste. Although garlic is a sterile plant that reproduces vegetatively through cloves, garlic shows high biodiversity, as well as phenotypic plasticity and environmental adaptation capacity. To determine the possible mechanism underlying this phenomenon and to provide new genetic materials for the development of a novel garlic cultivar with useful agronomic traits, the metabolic profiles in the leaf tissue of 30 garlic accessions collected from different geographical regions, with a special focus on the Asian region, were investigated using LC/MS. In addition, the total saponin and fructan contents in the roots and cloves of the investigated garlic accessions were also evaluated. Total saponin and fructan contents did not separate the garlic accessions based on their geographical origin, implying that saponin and fructan contents were clone-specific and agroclimatic changes have affected the quantitative and qualitative levels of saponins in garlic over a long history of cultivation. Principal component analysis (PCA) and dendrogram clustering of the LC/MS-based metabolite profiling showed two major clusters. Specifically, many Japanese and Central Asia accessions were grouped in cluster I and showed high accumulations of flavonol glucosides, alliin, and methiin. On the other hand, garlic accessions grouped in cluster II exhibited a high accumulation of anthocyanin glucosides and amino acids. Although most of the accessions were not separated based on country of origin, the Central Asia accessions were clustered in one group, implying that these accessions exhibited distinct metabolic profiles. The present study provides useful information that can be used for germplasm selection and the development of new garlic varieties with beneficial biotic and abiotic stress-adaptive traits.     

Dumbbell-Shaped 2,2’-Bipyridines: Controlled Metal Monochelation and Application to Ni-Catalyzed Cross-Couplings

2,2’-Bipyridine ligands (dsbpys) with dumbbell-like shapes and differently substituted triarylmethyl groups at the C5 and C5’ positions showed high ligand performance in the Ni-catalyzed cross-electrophile coupling and the Ni/photoredox-synergistically catalyzed decarboxylative coupling reactions. The superior ligand effects of dsbpys compared to the conventional bpy ligands were attributed to the monochelating nature of dsbpys.