Synthesis of block copolymer with polystyrene and nylon units

Bis-ε-aminocaproylaminocaproylhexamethylenediamine ( I ) was synthesized as an analog of 6-nylon pentamer diamine, and its incorporation into block copolymers was studied with the use of α,ω-dihydroxyl, α,ω-bisdimethylchlorosilyl, and α,ω-diepoxy polystyrene. In the course of the experiments, the stability and the reactivity of 4,4′-diphenylmethane diisocyanate and tetramethylene diisocyanate in aprotic dipolar solvents were examined by infrared spectroscopy. The only usable solvent, N-methylpyrrolidone, was found still inadequate for the synthesis involving I, diisocyanate, and α,ω-dihydroxyl polystyrene. A block copolymer having M _n = 18,000 was obtained by the reaction of I and α,ω-diepoxy polystyrene. All T_g values of the block copolymers were above 90°C, higher than for polystyrenes with corresponding molecular weight.     

Structure of an anti-plasmin inhibitor, eckol, isolated from the brown alga Ecklonia kurome Okamura and inhibitory activities of its derivatives on plasma plasmin inhibitors

Eckol (1), a novel phlorotannin with a dibenzo-1,4-dioxin skeleton, has been isolated from the brown alga Ecklonia kurome Okamura as a potent and specific anti-plasmin inhibitor. Its structure has been elucidated based on the spectral data, in particular, by means of negative nuclear Overhauser effect (NOE), and finally established as 1-(3,5-dihydroxyphenoxy)-2,4,7,9-tetrahydroxydibenzo-1,4-dio xin by X-ray analysis. Some partially methoxylated derivatives of eckol were prepared by methylation with diazomethane and also by selective dimethylation of eckol permethylate (1b) to establish the structural requirements for inhibitory activities on alpha 2-macroglobulin and alpha 2-plasmin inhibitor, the main plasmin inhibitors in plasma.     

Reaction of tetraazathiapentalene and thiadiazolopyrimidine derivatives with heterocumulenes: Cycloaddition and elimination reactions via hypervalent sulfur intermediates

Tetraazathiapentalene derivative 1 reacts with heterocumulenes such as diphenylketene (2) and 2‐pyridylisothiocyanate (5) to give heterocycles 3, 6 and 7 with elimination of methylisothiocyanate. The reactions of thiadiazolopyrimidine derivatives 8a‐b with ethoxycarbonyl isothiocyanate (9) and carbon disulfide (11) gives heterocycles 10 and 12 via thermal decomposition of 1:1 cycloadducts C and D which have a hypervalent sulfur. The mechanistic and reactivity features of these reactions are described.     

A new synthetic method: Direct replacement of the nitro group by hydrogen or deuterium

The nitro group in tertiary or secondary aliphatic nitro compounds is replaced by hydrogen or deuterium on treatment with tributyltin hydride or tributyltin deuteride, respectively.     

Multiplex amplified product-length polymorphism analysis of 36 mitochondrial single-nucleotide polymorphisms for haplogrouping of East Asian populations

We present a reliable, rapid, and economical multiplex amplified product-length polymorphism (APLP) method for analyzing the haplogroup-diagnostic mitochondrial single-nucleotide polymorphisms (mtSNPs) in East Asian populations. By examining only 36 haplogroup-specific mtSNPs in the coding region by using four 9-multiplex polymerase chain reaction (PCR) and subsequent electrophoresis, we could safely assign 1815 individuals from 8 populations of Japanese, Korean, Chinese, and Germans to 45 relevant haplogroups. This multiplex APLP analysis of coding-region mtSNPs for haplogrouping is especially useful not only for molecular phylogenetic studies but also for large-scale association studies due to its rapid and economical nature. This is the first panel of mtSNPs in the coding region to be used for haplogrouping of East Asian populations.     

Protein profiling of rat cerebella during development

Protein profiles of developing rat cerebella were analyzed by means of two-dimensional gel electrophoresis (2-DE) and mass spectrometry (MS). The analysis of adult rat cerebellum gave rise to a protein map comprising approximately 3000 spots detectable by silver staining following high resolution 2-DE with a pH range of 3-10 and a mass range of 8-100 kDa. To obtain landmarks for comparison of developmental profiles of cerebellar proteins, 100 spots were subjected to peptide mass fingerprinting using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS), and 67 spots were assigned on the map. Analysis of profiles of the developing cerebella revealed significant changes in the expression of proteins during development. In most cases the expression levels of proteins increased as the cerebellum matured, while the expression of 42 spots appeared specific or remarkably abundant in the immature cerebellum. Peptide mass fingerprinting of these spots allowed us to identify 29 proteins, which include, in addition to proteins of unknown function, many proteins known to have roles in the development of the central nervous system. These results suggest that the proteomic approach is valuable for mass identification of proteins involved in cerebellar morphogenesis.     

Synthesis and two-electron redox behavior of diazuleno[2,1-a:1,2-c]naphthalenes

The Diels-Alder reaction of di-2-azulenylacetylene with tetraphenylcyclopentadienone afforded 7,8,9,10-tetraphenyldiazuleno[2,1-a:1,2-c]naphthalene in one pot via autoxidation of the presumed 1,2-di-2-azulenylbenzene derivative. In contrast, a similar reaction of bis(1-methoxycarbonyl-2-azulenyl)acetylene with tetraphenylcyclopentadienone gave the 1,2-di-2-azulenylbenzene derivative. The following cyclodehydrogenation reaction of the benzene derivative with iron(III) chloride afforded diazuleno[2,1-a:1,2-c]naphthalene 6,11-bismethoxycarbonyl derivative. The redox behavior of these novel diazuleno[2,1-a:1,2-c]naphthalenes was examined by cyclic voltammetry (CV). These compounds exhibited two-step oxidation waves at +0.22 to +0.71 V upon CV, which revealed the formation of a radical cation and dication stabilized by the fused two azulene rings under the electrochemical oxidation conditions. Since the 1,2-di-2-azulenylbenzene derivative was oxidized at higher oxidation potentials (+0.83 and +1.86 V), the fusion of the two azulene rings to naphthalene increased electron-donating properties because of the formation of a closed-shell dicationic structure. Formation of the radical cation was characterized by UV-vis spectroscopy under the electrochemical oxidation conditions, although no evidence was obtained for the presumed dication under the conditions of the UV-vis spectroscopy measurement.     

Physicochemical Properties of Deuterated Compounds. 8th Communication. The kinetic isotope effect for the reaction of hydrogen atoms with methylcyclohexane and perdeuteromethylcyclohexane in the gas phase

Using H-atoms produced in the radiolysis of water vapour, we determined the kinetic isotope effect for the reaction where RH and R′D are methylcyclohexane and perdeuterated methylcyclohexane, respectively. The result obtained from the isotope competitive method can be expressed with the Arrhenius-type equation k_H/k_D = (0.51 ± 0.04) exp[(8.58 ± 0.25) kJ mol^?1/RT] over the temperature range from 363 to 483 K. The occurrence of H abstraction from primary, secondary, and tertiary C? H bonds in methylcyclohexane is taken into consideration in the interpretation of the Arrhenius-type expression obtained. Theoretical interpretation of the kinetic isotope effect has been achieved on the basis of the transition-state theory and a semiempirical London-Eyring-Polanyi-Sato potential-energy surface. The tunnel effect is found to play a role in the H-abstraction. Several methods for estimating the tunnel correction factors have been discussed.     

A facile method for the synthesis of thiocarbamates: palladium-catalyzed reaction of disulfide, amine, and carbon monoxide

[reaction: see text] A new method for the synthesis of thiocarbamates has been developed. When dialkyl or diaryl disulfides were allowed to react with secondary amines and carbon monoxide in the presence of a catalytic amount of a palladium complex, the thiocarbamates were obtained in moderate to good yields. In contrast to that of secondary amines, in the reaction of a primary amine, no formation of thiocarbamate was confirmed, but urea was formed in good yield.     

Recent progress of high-power negative ion beam development for fusion plasma heating

A negative-ion-based neutral beam injector (N-NBI) has been constructed for JT-60U. The N-NBI is designed to inject 500 keV, 10 MW neutral beams using two ion sources, each producing a 500 keV, 22 A D⁻ ion beam. In the preliminary experiment using one ion source, a D⁻ ion beam of 13.5 A has been successfully accelerated with an energy of 400 keV (5.4 MW) for 0.12 s at an operating pressure of 0.22 Pa. This is the highest D⁻ beam current and power in the world. Co-extracted electron current was effectively suppressed to the ratio of Ie/I_D⁻ < 1. The highest energy beam of 460 keV, 2.4 A, 0.44 s has also been obtained. To realize 1 MeV class NBI system for ITER (International Thermonuclear Experimental Reactor), demonstration of ampere class negative ion beam acceleration up to 1 MeV is an important mile stone. To achieve the mile stone, a prototype accelerator and a 1 MV, 1 A test facility called MeV Test Facility (MTF) were constructed. Up to now, an H⁻ ion beam was accelerated up to the energy of 805 keV with an acceleration drain current of 150 mA for 1 s in a five stage electrostatic multi-aperture accelerator.