Reactions of cyclic sulfur ylides with some carbonyl compounds

The reaction of a six‐membered sulfonium ylide 5 with aldehydes or ketones afforded the oxirane derivatives 6a–d as a mixture of cis and trans isomers in excellent yields. In addition, the same reactions, using five‐ or six‐membered cyclic oxosulfonium ylides 7 and 11 , gave the corresponding oxirane derivatives in good yields. Moreover, the reaction of 11 with two equimolar amounts of base and 4‐hexen‐3‐one afforded the cyclooctene oxide derivative 16 with high stereoselectivity in 59% yield via a sequential Michael–Michael‐type addition of the ylide and the resulting enolate ion followed by an intramolecular Corey–Chaykovsky reaction. © 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:216–222, 2002; Published online in Wiley Interscience (www.interscience.wiley.com). DOI 10.1002/hc.10022     

Molecular weight distribution formed during free‐radical polymerization in the presence of polyfunctional chain transfer agents

Free‐radical polymerization of styrene was carried out in the presence of chain transfer agents (CTAs) with functionality, f = 1–4. The size exclusion chromatography (SEC) with an ultraviolet absorption detector (UV) was used to measure the molecular weight distribution (MWD). A Monte Carlo simulation method proposed earlier was used to investigate the experimental results. In this simulation method, one can observe the structure of each polymer molecule directly, and very detailed information can be obtained in a straightforward manner, including the elution curve of SEC. It was found that up to the functionality f = 3, the equal reactivity model that assumes the reactivity of all functional groups in a CTA is equal agrees reasonably well with the experimental results. However, with f = 4, the reactivity of the fourth functional group seems to decrease and the substitution effects may need to be accounted for to fine control the formed branched structure. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1267–1275, 1999     

Synthesis,characterization, and enzymatic degradation of network aliphatic copolyesters

Network copolyesters were prepared from glycerol (Yg) and sebacic acid (10) with 10–90 mol % of either succinic acid (4), 1,12-dodecanedicarboxylic acid (14), 1,18-octadecanedicarboxylic acid (20), or terephthalic acid (T). Prepolymers prepared by melt-polycondensation were cast from dimethylformamide solution and postpolymerized at 230–250°C for various periods of time to form a network. The resultant films were transparent, flexible, and insoluble in organic solvents. The network copolyesters obtained were characterized by infrared absorption spectra, wide angle X-ray diffraction analysis, density measurement, thermomechanical analysis, differential scanning calorimetry, and tensile test. The enzymatic degradation was estimated by weight loss of the network copolyester films in a buffer solution with Rhizopus delemar lipase at 37°C. The weight loss due to the enzymatic degradation was decreased with increasing comonomer content, and the copolyesters with Yg4, Yg20 and YgT more than 50 mol % were not degraded by lipase enzyme at all. On the contrary, Yg-10/14 films were degraded appreciably over whole range of comonomer composition. With increasing comonomer content, the heat distortion temperature increased gradually, while the tensile strength and Young's modulus were not changed much. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2005–2011, 1999     

Minimum standards of clinical practice for physical therapists working in intensive care units in Japan

Objective: Early mobilization and rehabilitation has become common and expectations for physical therapists working in intensive care units have increased in Japan. The objective of this study was to establish consensus-based minimum clinical practice standards for physical therapists working in intensive care units in Japan. It also aimed to make an international comparison of minimum clinical practice standards in this area. Methods: In total, 54 experienced physical therapists gave informed consent and participated in this study. A modified Delphi method with questionnaires was used over three rounds. Participants rated 272 items as “essential/unknown/non-essential”. Consensus was considered to be reached on items that over 70% of physical therapists rated as “essential” to clinical practice in the intensive care unit. Results: Of the 272 items in the first round, 188 were deemed essential. In round 2, 11 of the 62 items that failed to reach consensus in round 1 were additionally deemed essential. No item was added to the “essential” consensus in round 3. In total, 199 items were therefore deemed essential as a minimum standard of clinical practice. Participants agreed that 42 items were not essential and failed to reach agreement on 31 others. Identified 199 items were different from those in the UK and Australia due to national laws, cultural and historical backgrounds. Conclusions: This is the first study to develop a consensus-based minimum clinical practice standard for physical therapists working in intensive care units in Japan.     

A Review of Red Yeast Rice,a Traditional Fermented Food in Japan and East Asia: Its Characteristic Ingredients and Application in the Maintenance and Improvement of Health in Lipid Metabolism and the Circulatory System

Red yeast rice has been used to produce alcoholic beverages and various fermented foods in China and Korea since ancient times; it has also been used to produce tofuyo (Okinawan-style fermented tofu) in Japan since the 18th century. Recently, monacolin K (lovastatin) which has cholesterol-lowering effects, was found in some strains of Monascus fungi. Since statins have been used world-wide as a cholesterol-lowering agent, processed foods containing natural statins are drawing attention as materials for primary prevention of life-style related diseases. In recent years, large-scale commercial production of red yeast rice using traditional solid-state fermentation has become possible, and various useful materials, including a variety of monascus pigments (polyketides) that spread as natural pigments, in addition to statins, are produced in the fermentation process. Red yeast rice has a lot of potential as a medicinal food. In this paper, we describe the history of red yeast rice as food, especially in Japan and East Asia, its production methods, use, and the ingredients with pharmacological activity. We then review evidence of the beneficial effects of red yeast rice in improving lipid metabolism and the circulatory system and its safety as a functional food.     

Asymmetric Synthesis of β2-Aryl Amino Acids through Pd-Catalyzed Enantiospecific and Regioselective Ring-Opening Suzuki–Miyaura Arylation of Aziridine-2-carboxylates

A Pd-catalyzed enantiospecific and regioselective ring-opening Suzuki–Miyaura arylation of aziridine-2-carboxylates was developed. The cross-coupling allows for the asymmetric preparation of enantioenriched β²-aryl amino acids, starting from commercially available enantiopure d - and l -serine esters. The mechanism and selectivity of the reaction was rationalized based on computational models.     

A new cyano-substituted fluorescamine superior to its original form as a fluorescent probe for amino acid detection

Synthesis and spectral study of two new cyano-substituted fluorescamine as the fluorescent probes for amino acid detection have been carried out comparing with the original fluorescamine. Of the three compounds, the derivative with a cyano group at the meta-position on the 4-phenyl group was found to be superior to the original one in the reactivity toward some amino acids as well as the fluorescence intensity of the adducts. The fluorescent amino acid adducts were also applied to the peroxyoxalate chemiluminescence system as the fluorophores, in which the derivative described above was found to be more effective also in chemiluminescence than the original one.     

Flowerlike supramolecular architectures assembled from C60 equipped with a pyridine substituent

Fullerene (C(60))-rich and photoconductive flowerlike supramolecular assembly was constructed from self-organization of pyridine substituted C(60) by a facile drop-casting method.     

Oxidative Coupling of Aromatic Substrates with Alkynes and Alkenes under Rhodium Catalysis

Aromatic substrates with oxygen‐ and nitrogen‐containing substituents undergo oxidative coupling with alkynes and alkenes under rhodium catalysis through regioselective C? H bond cleavage. Coordination of the substituents to the rhodium center is the key to activate the C? H bonds effectively. Various fused‐ring systems can be constructed through these reactions.