Extended multicanonical method combined with thermodynamically optimized potential: application to the liquid-crystal transition of silicon

A novel method is proposed to study first-order phase transition in real materials. It is applied to the liquid-crystal transition of silicon successfully. It consists of two parts: a direct simulation of the transition by an extended multicanonical ensemble with an order parameter defined with structure factors that characterize the transition, and optimization of a model interatomic potential in terms of the ensemble from an accurate one. These provide a principle to project a first-principles approach on a model-based approach conserving thermodynamic properties of multiple phases.     

Development of an analytical method using microchip capillary electrophoresis for the measurement of fluorescein-labeled salivary components in response to exercise stress

We have developed an analytical method using microchip capillary electrophoresis (microchip CE) for the high-speed separation of fluorescein-labeled salivary components in response to exercise stress. Optimal separation was obtained using a borate buffer at pH 9.5 containing 10 mM beta-cyclodextrin and 1.0% (w/v) methylcellulose. To minimize individual differences in human saliva, such as viscosity, conductivity, and contaminants, the concentration of methylcellulose in the analytical conditions played a key factor. The optimized separation conditions produced identical electropherograms successfully despite of the use of different microchips made from quartz glass or poly-methylmethacrylate (PMMA). In addition, a practical application of bicycle ergometer stress was performed. Some components in human saliva showed a marked decrease after exercise stress.     

A new class of rhodamine luminophores: design, syntheses and aggregation-induced emission enhancement

A new class of rhodamine luminophores, 3',3'-bis(oxospiroisobenzofuran)-3,7-bis(dialkylamino)benzopyrano-xanthene derivatives (ABPX), have been successfully developed. The emission behavior of ABPX series is directly opposite to the concentration quenching of conventional rhodamine dyes. ABPX series exhibit aggregation-induced emission enhancement (AIEE).     

A local second-order Møller-Plesset method with localized orbitals: a parallelized efficient electron correlation method

Using orthogonal localized occupied orbitals we have developed and implemented a parallelized local second-order M?ller-Plesset (MP2) method based on the idea developed by Head-Gordon and co-workers. A subset of nonorthogonal correlation functions (the orbital domain) was assigned to each of the localized occupied orbitals using a distance criterion and excitations from localized occupied orbitals that were arranged into subsets. The correlation energy was estimated using a partial diagonalization and an iterative efficient method for solving large-scale linear equations. Some illustrative calculations are provided for molecules with up to 1484 Cartesian basis sets. The orbital domain sizes were found to be independent of the molecular size, and the present local MP2 method covered about 98%-99% of the correlation energy of the conventional canonical MP2 method.     

Method Development of Enantiomer Separations by Affinity Capillary Electrophoresis,Cyclodextrin Electrokinetic Chromatography and Capillary Electrophoresis-Mass Spectrometry

 Capillary electrophoresis (CE) has become a powerful tool for enantiomer separations during the last decade. Since 1993, the author has investigated enantiomer separations by affinity capillary electrophoresis (affinity CE) with some proteins and by cyclodextrin electrokinetic chromatography (CDEKC) with some charged cyclodextrins (CDs). Many successful enantiomer separations are demonstrated from our study in this review article. In the enantiomer separations by affinity CE, the deterioration of detection     

Synthesis and antitumor activity of novel pyrimidinyl pyrazole derivatives. II. Optimization of the phenylpiperazine moiety of 1-[5-methyl-1-(2-pyrimidinyl)-4-pyrazolyl]-3-phenylpiperazinyl-1-trans-propenes

A series of novel 3-substituted-1-[5-methyl-1-(2-pyrimidinyl)-4-pyrazolyl]-1-trans-propenes in order to improve the in vitro and in vivo activity of our prototype 3-[4-(3-chlorophenyl)-1-piperazinyl]-1-[5-methyl-1-(2-pyrimidinyl)-4-pyrazolyl]-1-trans-propene (2) were synthesized and evaluated by assays of growth inhibition against several tumor cell lines in vitro and antitumor activity against some tumor models when dosed both intraperitoneally and orally in vivo. Compounds 7a and 7e, the 3,5-difluorophenyl and 3,5-dichlorophenyl analogues of 2, respectively, showed significantly more potent cytotoxicity than 2 in vitro and potent antitumor activities without causing decrease of body temperature related to side effects.     

Synthesis of 5-acetyl-2-aminopyrrole C-deoxyribonucleoside

A novel C-deoxyribonucleoside bearing 2-aminopyrrole was synthesized. The C-glycosidation between deoxyribose and pyrrole ring was carried out using palladium-catalyzed Heck coupling in the presence of excess amount of lithium chloride as an additive. The synthesized aminopyrrole nucleoside is expected to become a promising counterpart of the artificial nucleoside pair.     

γ-Cyclodextrins possessing an azido group and a triisopropylbenzenesulfonyl group as useful synthetic and authentic intermediates for unsymmetrically functionalized derivatives

Seven isomers of cyclomaltooctaose (γ-cyclodextrin) whose C6s were unsymmetrically disubstituted with both an azido group and an arenesulfonyloxy group were prepared and each of them was isolated by reversed phase chromatography. The assignment of the modified positions in each regioisomers was unambiguously performed by chemical correlation with the authentic compounds and chemical conversion to the 3,6-anhydro derivatives followed by high-resolution 2D-¹H NMR (COSY, TOCSY, and HOHAHA) analyses. The compounds are versatile synthetic and authentic intermediates to prepare sophisticated derivatives with two different functionalities at desired positions on the molecule for supramolecular chemistry.     

Impact of the state of water on the dispersion stability of a skin cream formulation elucidated by magnetic resonance techniques

This study investigated the relationship between the state of water and the dispersion stability of a skin cream formulation. Hydrophilic ointments treated with a high-pressure wet-type jet mill were used as model formulations. Spin-lattice relaxation times (T(1)) were measured by magnetic resonance techniques to estimate the state of water in samples. A shorter T(1) relaxation time was obtained from samples with higher surfactant content, whereas the processing pressure of the jet mill and 1-week storage at 40 °C did not influence the T(1) relaxation time. Observations using scanning electron microscopy (SEM) showed that coalescence occurred in samples with lower surfactant contents (1.0% by weight) following 1-week storage at 40 °C. We also investigated samples prepared using a hydrophilic surfactant with a short polyethylene glycol (PEG) chain and with PEG-4000. From the change in T(1) relaxation times after removing the oil phase from samples by centrifugation, it was clarified that most of the surfactant was located on the surface of oil droplets. Furthermore, SEM observations showed that phase separation was facilitated as the PEG chain length of the surfactant shortened. Thus, a thin water layer over oil droplets is the most important factor for stabilizing their dispersion. This study provides proof-of-principle results on the contribution of the state of water to the dispersion stability of a skin cream formulation.     

Synthesis of an Optically Active Trisubstituted α,β-Butenolide, (S)-4, 6-Dihydroxy-2, 3-dimethyl-2-hexesoic Acid 1, 4-Lactone,from 2-Deoxy-D-ribose

The title compound has been synthesized efficiently from 2-deoxy-D-ribose. The synthesis involves : 1) an aldol like carbon-carbcr. bond formation of (S)-3, 5-dibenzyioxy-2-pentanor.e (8) with a lithium enolate of methyl propanoate, and 2) O-de-benzylation of the aldol adducts (11) for a γ-lactonization followed by β-elimination of the desired butenolide skeleton.