Development of miniaturized multi-channel high-performance liquid chromatography for high-throughput analysis

We have developed miniaturized multi-channel high-performance liquid chromatography (HPLC) system. With this system, we can simultaneously separate multiple samples, using a single high-pressure gradient pump, a chip-based sample injection unit, a monolithic silica capillary column array, and a multi-channel UV detection unit based on fiber optics. The injection unit has a simplified structure composed of brass housing and a quartz microchip having microchannels and access ports, which enable a direct injection of sample to multi-channel by commercial multichannel micropipette. Moreover, that possesses a function of microvalve, and on-chip definition of sample injection plugs achieved with a cross channel injection method, providing each column of monolithic silica capillary array. The substances in channels were simultaneously detected with UV having multiple cells. Standard samples were analyzed for characterizing newly developed system, and sharp peaks were obtained with reproducibility data of < 0.9% (R.S.D.). Analysis of tryptic digestion of casein was also employed. These results show that the novel multi-channel HPLC system has the benefits for the high-throughput analysis in the post-genomic analysis/combinatorial chemistry.     

Dehydrogenation of ethylbenzene with CO2 over Cr-MCM-41 catalyst

M-MCM-41 catalysts (M: V, Cr, Fe, and Ga) prepared by direct hydrothermal synthesis (DHT) have been tested for dehydrogenation of ethylbenzene with CO₂. The synthesized materials were characterized by X-ray diffraction (XRD), N₂ adsorption (77 K), and diffuse reflectance UV–vis spectroscopic measurements. Cr-MCM-41 showed the highest activity among M-MCM-41 catalysts tested, resulting in the production of styrene with the conversion of 65% and the selectivity above 90%. The rate of styrene formation increased with increasing Cr loading up to 1.7 wt.%. It is suggested that Cr(VI)O₄ in tetrahedral coordination is formed as an active monochromate species and reduced to Cr(III)O₆ in octahedral coordination as a less active polychromate species during the reaction. Deactivated catalyst was regenerated by a treatment with gaseous oxygen or CO₂, during which redistribution as well as reoxidation of polymeric Cr(III)O₆ octahedra to monomeric Cr(VI)O₄ tetrahedra was observed. The rate of CO formation increased together with that of styrene formation, while the rate of H₂ formation decreased, with increasing partial pressure of CO₂. It was confirmed that reverse water-gas shift reaction took place over Cr-MCM-41 by a separate experiment. The rate of CO formation during the dehydrogenation of ethylbenzene with CO₂ over Cr-MCM-41 was well accounted for by assuming parallel occurrence of two reactions, i.e., direct oxidative dehydrogenation of ethylbenzene with CO₂ and simple dehydrogenation of ethylbenzene thermodynamically assisted by reverse water-gas shift reaction.     

Structural Studies of Transition Metal Compounds

A historical overview will be given on the structural studies on transition metal compounds and their interaction with other fields of coordination chemistry. About three decades have passed away since the structure and absolute configuration of tris(ethylenediamine)cobalt(III) complex ion were determined. At present accumulation of the structural data for isomers has enabled us to understand structural principles of chelate complexes in considerable detail. The energy minimization calculations can predict the detailed geometries of the complexes. Differences in thermodynamic properties between different conformers are well reproduced. Aspherical distribution of 3d electrons in transition metal complexes was detected for the first time in crystals of [Co(NH3)₆][Co(CN)₆] in 1973. Such an accurate electron density study provides important information on the d electrons placed in a ligand field. The high-spin and low-spin states can be distinguished unequivocally. In spite of a very small valence/total electron ratio, the asphericity of 4d and 5d electrons in a ligand field can be detected. The crystal structures of a series of dimeric copper(II) carboxylate adducts of the general formula [Cu(RCOO)₂L]₂ have been determined or redetermined as accurately as possible. The temperature dependent magnetic susceptibility of these crystals indicated that the isolated pairs of Cu(II) ions interact strongly through exchange forces. Molecular orbital calculations revealed that the electron population in the carbon atom of the bridging OCO group plays an important role in determining the strength of the spin superexchange interaction. In the crystals of some cobaloxime complexes, racemization of chiral groups bonded to Co proceeds on X-ray exposure without degradation of crystallinity. Several intermediate stages could be determined by X-ray analysis. Various reaction pathways were recognized and the reaction rate could be correlated with the atomic arrangement in the crystal.     

Assembly of a Benzo-Fused Bridged Ketone Scaffold from 1,5,10-Enediynes through One-Pot Ruthenium-Catalyzed Cyclization/Iodine-Mediated Oxidative Ring Expansion

In the presence of a cationic Ru catalyst, 1,6-diynes bearing a terminal styryl moiety underwent [2+2+2] cyclization to produce dehydrobiphenylenes fused with a five-membered ring. Although the cycloadducts were unstable toward purification, their one-pot iodine-mediated ring expansion successfully afforded unprecedented bridged ketone products containing a benzo-fused bicyclo[3.2.1] framework.     

Synthese makrocyclischer Lactone durch Ringerweiterung. Vorläufige Mitteilung

Synthesis of Macrocyclic Lactones by Ring Enlargement Reaction Treatment of 3-(1-nitro-2-oxocyclohexyl)propanal ( 1 ) prepared by Michael addition of 2-nitrocyclohexanon and acrylaldehyde with methyltri (2-propoxy)tita-nium yielded a mixture of 2 and 3 which was converted into 6-nitro-9-decanolide ( 4 ).     

Shrinkage estimators for large covariance matrices in multivariate real and complex normal distributions under an invariant quadratic loss

The problem of estimating large covariance matrices of multivariate real normal and complex normal distributions is considered when the dimension of the variables is larger than the number of samples. The Stein–Haff identities and calculus on eigenstructure for singular Wishart matrices are developed for real and complex cases, respectively. By using these techniques, the unbiased risk estimates for certain classes of estimators for the population covariance matrices under invariant quadratic loss functions are obtained for real and complex cases, respectively. Based on the unbiased risk estimates, shrinkage estimators which are counterparts of the estimators due to Haff [L.R. Haff, Empirical Bayes estimation of the multivariate normal covariance matrix, Ann. Statist. 8 (1980) 586–697] are shown to improve upon the best scalar multiple of the empirical covariance matrix under the invariant quadratic loss functions for both real and complex multivariate normal distributions in the situation where the dimension of the variables is larger than the number of samples.     

Estimation of normal covariance matrices parametrized by irreducible symmetric cones under Stein's loss

In this paper the problem of estimating a covariance matrix parametrized by an irreducible symmetric cone in a decision-theoretic set-up is considered. By making use of some results developed in a theory of finite-dimensional Euclidean simple Jordan algebras, Bartlett's decomposition and an unbiased risk estimate formula for a general family of Wishart distributions on the irreducible symmetric cone are derived; these results lead to an extension of Stein's general technique for derivation of minimax estimators for a real normal covariance matrix. Specification of the results to the multivariate normal models with covariances which are parametrized by complex, quaternion, and Lorentz types gives minimax estimators for each model.     

Hölder continuity of discrete Morse flows to the Alt–Caffarelli variational problem generating free boundaries

The present paper shows Hölder continuity of discrete Morse flows to a regularized Alt–Caffarelli variational functional generating free boundaries; the continuity is uniform with respect to the discrete Morse flows and the regularizations. The uniformity enables to construct Morse flows to the Alt–Caffarelli functional, which shall be dealt with in another paper.     

Direct and stepwise energy transfer from excitons to plasmons in close-packed metal and semiconductor nanoparticle monolayer films

We studied the dynamics of photoluminescence (PL) and energy transfer in close-packed monolayer films of CdSe and Au nanoparticles (NPs) assembled using the Langmuir-Blodgett technique. The PL intensity and dynamics depended on the ratio of CdSe to Au NPs in the mixed films. The PL quenching of CdSe NPs occurs through rapid energy transfer from excitons in CdSe NPs to plasmons in Au NPs. The PL decay curves of the mixed NPs monolayers are determined by three decay rates: the direct energy transfer between the nearest-neighbor CdSe and Au NPs (CdSe-->Au), the stepwise energy transfer from CdSe to CdSe to Au NPs (CdSe-->CdSe-->Au), and the radiative recombination in CdSe NPs.