Synthesis of two naturally occurring 3-methyl-2,5-dihydro-1-benzoxepin carboxylic acids

[structures: see text] Two naturally occurring 3-methyl-2,5-dihydro-1-benzoxepin carboxylic acids, 6-hydroxy-3-methyl-8-(phenylethyl)-2,5-dihydro-1-benzoxepin-9-carboxylic acid (radulanin E) (1) and 9-hydroxy-3-methyl-2,5-dihydro-1-benzoxepin-7-carboxylic acid (2), were synthesized using Stille coupling followed by Mitsunobu cyclization.     

Cationic polymerization of p-methylstyrene initiated by acetyl perchlorate: An approach to living polymerization

The cationic polymerization of p-methylstyrene initiated by acetyl perchlorate at ?78°C led to long-lived (living-like) polymers with a narrow molecular weight distribution (M?_w/M?_n = 1.1–1.4) in methylene chloride containing a common ion salt (n-Bu₄NClO₄) or in a less polar solvent (CH₂Cl₂/toluene, 1/4v/v). Under these conditions, the number-average molecular weight (M?_n) of the polymers increased in proportion to monomer conversion and was regulated by the monomer-to-initiator ratio. When fresh feeds of the monomer were repeatedly added to a completely polymerized solution, the polymerization ensued at the same rate as before and the linear increase in M?_n with monomer conversion continued. The effects of solvent polarity and the common ion salt on the polymerization showed the suppression of the ionic dissociation of the propagating species, resulting in a “nondissociated species,” to be the key factor for the formation of the long-lived polymers.     

Antioxidant activity and Neurite outgrowth-enhancing activity of scorbamic acid and a red pigment derived from ascorbic acid

Abstract

L-Ascorbic acid (AA), known as vitamin C, can form browning products by a non-enzymatic process during storage and the browning products cause deterioration of agricultural products. In the browning reaction, a red pigment, 2,2´-nitrilodi-2(2´)-deoxy-L-ascorbic acid ammonium salt (NDA), is generated from AA via L-scorbamic acid (SCA) as an intermediate. However, the biological activities of SCA and NDA have not yet been clarified. In this study, we assayed the antioxidant activities of SCA and NDA using ABTS radical cation and their neurite outgrowth-enhancing activities in PC12 cells. SCA showed stronger radical-scavenging activity than that of AA, while NDA hardly showed any activity. SCA and NDA enhanced the neurite outgrowth induced by dibutyryl cyclic AMP after their incorporation into cells in the same manner as that of AA. The results indicated that SCA has antioxidant activity and that SCA and NDA have neurite outgrowth-enhancing activity.     

Zirconium-catalyzed chemoselective methylalumination of ethers, amines, and sulfides bearing two terminal alkenyl groups

Chemoselectivity in the methylalumination reaction of unsymmetrical ethers, amines, and sulfides bearing two different terminal alkenyl groups, a 13-tetradecenyl group and an allyl, 4-pentenyl or 6-heptenyl group was examined. The methylalumination of the allyl derivatives proceeded with complete chemoselectivity to afford only the 13-tetradecenyl-monomethylated products. In the methylalumination reactions of the 4-pentenyl and the 6-heptenyl derivatives, in addition to the 13-tetradecenyl-monomethylated products, and dimethylated products were also obtained. However, as in the case of the allyl derivatives, monomethylation to the shorter 4-pentenyl or 6-heptenyl group was not observed, except in the case of 6-heptenyl 13-tetradecenyl amine. The unique selectivity was rationalized upon how readily the intramolecular ligand exchange reaction between intermediate zirconocenium-alkene and zirconocenium-heteroatom complexes could occur.     

Precise control and consecutive modulation of spin transition temperature using chemical migration in porous coordination polymers

Precise control of spin transition temperature (T(c)) is one of the most important challenges in molecular magnetism. A Hofmann-type porous coordination polymer {Fe(pz)[Pt(II)(CN)(4)]} (1; pz = pyrazine) exhibited cooperative spin transition near room temperature (T(c)(up) = 304 K and T(c)(down) = 284 K) and its iodine adduct {Fe(pz)[Pt(II/IV)(CN)(4)(I)]} (1-I), prepared by oxidative addition of iodine to the open metal sites of Pt(II), raised the T(c) by 100 K. DSC and microscopic Raman spectra of a solid mixture of 1-I and 1 revealed that iodine migrated from 1-I to 1 through the grain boundary after heating above 398 K. We have succeeded in precisely controlling the iodine content of {Fe(pz)[Pt(CN)(4)(I)(n)]} (1-In; n = 0.0-1.0), which resulted in consecutive modulation of T(c) in the range 300-400 K while maintaining the hysteresis width. Furthermore, it was demonstrated that iodine migration in the solid mixture was triggered by the spin transition of 1-I. The magnetically bistable porous framework decorating guest interactive open-metal-site in the pore surface makes it possible to modulate T(c) ad arbitrium through unique postsynthetic method using iodine migration.     

Mechanoluminescent light source for a fluorescent probe molecule

We have demonstrated an innovative ability of mechanoluminescent (ML) material as a light source for the first time. By appropriate smart size control and nondestructive mechanical stimulation, the ML particle can be considered a promising candidate of in situ light source for bio-imaging and photo-therapy even in a human body.     

Quantitative analysis of triphenylboron in environmental water samples by liquid chromatography/mass spectrometry.

Liquid chromatography/mass spectrometry (LC/MS) has been applied to the analysis of triphenylboron, which has been produced as a substitute for organotin compounds, in water. Although commercial triphenylboron compounds are produced as pyridinyl complexes, the chemical form in water is supposed to be mainly triphenylboron after liberating pyridine. The triphenylborons were extracted from water with an Empore C18 extraction disk under acidic condition, and the extracts were introduced directly into a liquid chromatograph-mass spectrometer equipped with a negative ion electrospray ionization interface. Identification of the compounds was performed with specific ions produced from the triphenylboron, and a quantitative analysis was carried out using the peak areas. The average recoveries from distilled water, seawater and river water at 0.30 ng/ml were 92.3, 100 and 85.3%, respectively. A detection limit of 0.023 ng/ml for triphenylboron was achieved.     

Elektronenspektren von 1,1-Diphenyl?thylen und Benzophenon

Ohne Zusammenfassung     

Molecular dynamics simulations of large integral membrane proteins with an implicit membrane model

The heterogeneous dielectric generalized Born (HDGB) methodology is an the extension of the GBMV model for the simulation of integral membrane proteins with an implicit membrane environment. Three large integral membrane proteins, the bacteriorhodopsin monomer and trimer and the BtuCD protein, were simulated with the HDGB model in order to evaluate how well thermodynamic and dynamic properties are reproduced. Effects of the truncation of electrostatic interactions were examined. For all proteins, the HDGB model was able to generate stable trajectories that remained close to the starting experimental structures, in excellent agreement with explicit membrane simulations. Dynamic properties evaluated through a comparison of B-factors are also in good agreement with experiment and explicit membrane simulations. However, overall flexibility was slightly underestimated with the HDGB model unless a very large electrostatic cutoff is employed. Results with the HDGB model are further compared with equivalent simulations in implicit aqueous solvent, demonstrating that the membrane environment leads to more realistic simulations.     

Chichibabin pyridinium synthesis

Chichibabin pyridine synthesis involves the reaction of three aldehydes and ammonia to form 2,3,5-trisubstituted pyridines. This study examined the synthesis of tetrasubstituted pyridinium from aldehydes and an amine hydrochloride in the presence/absence of Pr(OTf)₃. Important insights into the reaction mechanisms of Chichibabin pyridinium synthesis were proposed through the investigation of reaction intermediates along with quantitative GC–MS analysis.