Group symmetry in tensor categories and duality for orbifolds

A duality for orbifolds is presented as an application of group extensions in tensor categories.     

Antioxidant effects of hydroxybenzalacetones on peroxynitrite-induced lipid peroxidation in red blood cell membrane ghost and SOS response in Salmonella typhimurium TA4107/pSK1002

Antioxidant activity of a series of hydroxybenzalacetones was determined against peroxynitrite-induced lipid peroxidation in red blood cell membrane and SOS response through DNA damage in bacterial cells. Hydroxybenzalacetone derivatives with hydroxy, methoxy, ethoxy or methyl substitution were analyzed and found to be more effective than the water-soluble vitamin E analogue Trolox. The inhibitory effect against lipid peroxidation correlated well to that against the SOS response, which is dependent on decomposition of peroxynitrite by hydroxybenzalacetones outside of the cell membrane. The antioxidant activity was shown to correlate well with the electric parameter sigma+. Electron-donating substituents with more negative sigma+ values increased the potencies. The result suggests that hydroxybenzalacetones with more electron-donating substituents will protect tissue more effectively against oxidative stress.     

RAPID AND SENSITIVE OPTICAL ROTATION MEASUREMENT: KINETICS OF CONFORMATIONAL CHANGE OF RHODOPSIN INTERMEDIATE

A rapid and sensitive optical rotation (OR) measurement system using laser light has been developed to meet the demands of flash-photolysis experiments. The optimal OR resolution of the apparatus is 0.3mdeg with 10 μs time constant with single shot. The OR resolution could be easily improved less than 0.1 mdeg with accumulation of data by a kinetic processor. Applications are briefly described for the study of transient conformational change of photochemical intermediates of octopus rhodopsin following a blue light flash.     

High-performance liquid chromatography of coenzyme Q-related compounds and its application to biological materials

A convenient and precise method for the separation and determination of coenzyme Q (CoQ)-related compounds (CoQ homologues, plastoquinone-9, ubichromenol-9, etc.) was developed using high-performance liquid chromatography (HPLC). All compounds tested were separated using a reverse-phase column with a suitable mobile phase and detected at a wavelength of 275 nm. CoQ extracts in plasma and erythrocytes were purified by thin-layer chromatography prior to HPLC analysis, but such purification was not necessary when determining CoQ in urine and tissues. Hydroquinone forms of CoQ existing in animal tissues were oxidized to the corresponding quinone forms with potassium hexacyanoferrate(III). This HPLC method was applied satisfactorily to the determination of the contents of CoQ homologues in human and animal samples. CoQ10 was the only homologue detected in human samples, and CoQ8, CoQ9 and CoQ10 were native homologues of CoQ in rat tissues. Ubichromenol-9 and plastoquinone-9 were not detected in these samples.     

Synthesis and reactivities of 10-S-3 trithiadiazapentalene derivatives

1,3-Bis(p-substituted-phenylthiocarbamoyl)-2-imidazolidinethiones 3a-f reacted with bromine to give trithiadiazapentalene derivatives 5a-f , bearing the exocyclic C-N double bonds, in moderate yields. The molecular structure of 5b was elucidated by the X-ray crystallographic analysis. The treatment of 5b-f with hydrochloric acid gave the ring-opening products, 1,3-bis(p-substituted-phenylthiocarbamoyl)-2-imidazo-lidinones 9b-f , accompanied by the production of elemental sulfur. Reduction of 5b , 5d , and 5e with sodium borohydride gave the ring-opening compounds, 1,3-bis(p-substituted-phenylthiocarbamoyl)-2-imidazolidines 13b , 13d , and 13e respectively.     

Anionic polymerization and copolymerization of S-methyl thiomethacrylate

S-Methyl thiomethacrylate (methyl thiolmethacrylate, MTMA) was polymerized with a variety of anionic initiators such as n-BuLi, octylpotassium, PhMgBr, and Et₂AlNPh₂ in toluene and THF. Stereoregularity of the polymer (PMTMA) was determined from the ¹H-NMR spectrum of poly(methyl methacrylate), which had been derived from PMTMA, because the α-methyl resonance in the ¹H-NMR spectrum of PMTMA was not satisfactorily solved owing to the overlap of pentad signals. The ¹³C-NMR spectrum of PMTMA also showed the splitting due to pentad sequences. Stereoregularity of PMTMA was always low compared with that of poly(methyl methacrylate), which was prepared under the same reaction conditions. MTMA was much more reactive than methyl methacrylate and methacrylonitrile in the copolymerization with n-BuLi in toluene and in THF at ?78°C. The lower stereoregulation of the polymerization of MTMA and the higher reactivity of MTMA were mainly ascribed to the higher resonance effect of MTMA.     

Synthesis of monodispersed organic-inorganic hybrid spheres

This paper describes the attempt to prepare a new group of monodispersed silica-polymer hybrid particles, which consists of silica and amide polymer: poly(vinylpyrrolidone) (PVP) and poly(2-ethyloxazoline) (POXZ). Preparation method is based on the growth of hybrid seeds by the addition of TEOS-polymer solution.Monodispersed PVP-silica hybrid particles of 1.24 µm in diameter were prepared by growing the hybrid seeds of 0.54 µm by the addition of TEOS-PVP solution with ammonia catalyst. In the case of POXZ-silica particles, addition of TEOS-POXZ solution to the solution containing 0.54 µm seeds resulted in monodispersed POXZ-silica hybrid particles and four times repetition of the addition for particle growth gave the hybrid particles of the diameter of 1.6 µm.Improvement of mechanical properties of hybrid particles was observed when the particles were heated at 100 200°C.     

Optimization of a multi-residue screening method for the determination of 85 pesticides in selected food matrices by stir bar sorptive extraction and thermal desorption GC-MS

A multi-residue method to determine 85 pesticides, including organochlorine pesticides, carbamates, organophosphorus pesticides, and pyrethroids, in vegetables, fruit, and green tea, has been developed. The method is based on stir bar sorptive extraction (SBSE) coupled to thermal desorption (TD) and retention time locked (RTL) GC-MS operating in the scan mode. Samples are extracted with methanol and diluted with water prior to SBSE. Dilution of the methanol extract before SBSE was optimized to obtain high sensitivity and to minimize adsorption onto the glass wall of the extraction vessel as well as to minimize sample matrix effects (particularly for the pesticides with high log K(o,w) values). The optimized method consists of a dual SBSE extraction performed simultaneously on respectively a twofold and a fivefold diluted methanol extract. After extraction, the two stir bars are placed in a single glass thermal desorption liner and are simultaneously desorbed. The method showed good linearity (r2 > 0.9900) and high sensitivity (limit of detection: < 5 microg kg(-1)) for most of the target pesticides. The method was applied to the determination of pesticides at low microg kg(-1) in tomato, cucumber, green soybeans, spinach, grapes, and green tea.     

Synthesis of (±)‐Kempa‐6,8‐dien‐3‐ol (=(2aRS,3SR,4aSR,7RS,7aSR,10bSR,10cSR)‐2,2a,3,4,4a,5,6,7,7a,8,10b,10c‐Dodecahydro‐2a,7,10,10c‐tetramethylnaphth[2,18‐cde]azulen‐3‐ol)

The synthesis of kempa‐6,8‐dien‐3β‐ol ( 4a ), as a synthetic leading model of the natural product 4b , was carried out starting from intermediate 12 , the synthetic route of which has been developed previously (Scheme 1). The conversion of 12 to the model compound 4a involved the elaboration of three structure modifications by three processes, Tasks A, B, and C (see Scheme 2). Task A was achieved by epoxy‐ring opening of 41 with Me₃SiCl (Scheme 9), and Task B being performed by oxidation at the 13‐position, followed by hydrogenation, and then epimerization (Schemes 4 and 5). The removal of the 2‐OH group from 12 (Task C) was achieved via 30b according to Scheme 6, whereby 30b was formed exclusively from 30a / 31a 1 : 1 (Scheme 7). In addition, some useful reactions from the synthetic viewpoint were developed during the course of the present experiments.