Asymmetric hydrogenation of alpha-chloro aromatic ketones catalyzed by eta6-arene/TsDPEN-ruthenium(II) complexes

Asymmetric hydrogenation of various alpha-chloro aromatic ketones with Ru(OTf)(TsDPEN)(eta6-arene) (TsDPEN = N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine) produces the chiral chlorohydrins in up to 98% ee. This reaction can be conducted even on a 206-g scale. The hydrogenation of an alpha-chloro ketone with a phenol moiety has been utilized for the synthesis of (R)-norphenylephrine without protection-deprotection operations. [reaction: see text].     

Effect of thermal treatment on the photocatalytic degradation of ethylene,trichloroethylene, and chloroform

The thermal treatment of TiO₂ pellets prepared by the sol–gel method decreased the photocatalytic activity. The activity divided by the specific surface area of the pellets for the complete mineralization of ethylene or chloroform was maximized at the firing temperature of 400°C. For the photocatalytic degradation of trichloroethylene (TCE), most of them were converted to chlorinated by-products, such as dichloroacetic acid, chloroform, and phosgene, and the stoichiometric ratio of [CO₂]_formed/[TCE]_degraded showed a maximal value at 400°C. The electron spin resonance (ESR) spin-trapping with 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) in the flow injection system indicated that firing at 400°C gave the highest signal intensity of DMPO–OH adducts. These findings indicated that the OH radical was produced most effectively on the TiO₂ fired at 400°C, which would be related to the content of anatase and rutile. Concerning the formation of chlorinated by-products from TCE, more dichloroacetic acid (DCAA) were detected and less CHCl₃ and COCl₂ were formed at lower firing temperatures, suggesting that the branching ratio of chloroethoxy radicals to the formation of DCAA or CHCl₃ and COCl₂ by C–C bond scission depended on the firing temperature.     

Electrospray droplet impact/secondary ion mass spectrometry: cluster ion formation

The electrospray droplets that are sampled through an orifice into the vacuum chamber are accelerated by 10 kV and impact on the stainless steel substrate. The mass and the kinetic energy of electrospray droplets are roughly estimated to be a few 10(6) u and approximately 10(6) eV, respectively. The molecular ion M(+.) and the protonated molecule [M+H](+) are observed as secondary ions for chrysene and coronene deposited on the metal substrate (no matrix used). The ionization may take place in the shock wave generated by the high-momentum coherent collision between the droplet projectile and the solid sample. Cluster ions of H(+)(H(2)O)(n) and CF(3)COO(-)(H(2)O)(n), with n up to approximately 150, were observed as secondary ions formed by the electrospray droplet impact ionization (EDI) for 10(-2) M trifluoroacetic acid (TFA) aqueous solution. This indicates that the charged droplets that collide with the metal substrate with the kinetic energy of approximately 10(6) eV do not vaporize completely but are disintegrated into many tiny microdroplets. The ion signal intensity anomalies (i.e. magic numbers) were observed for the cluster ions of H(3)O(+)(H(2)O)(n) and CF(3)COO(-)(H(2)O)(n) for 10(-2) M TFA aqueous solution and of Cs(+)(H(2)O)(n), I(-)(H(2)O)(n), Cs(+)(CsI)(n), and I(-)(CsI)(n) for 10(-2) M CsI aqueous solution.     

Synthesis and structures of cyclic gold complexes containing diphosphine ligands and luminescent properties of the high nuclearity species

A mixture of cyclic gold(I) complexes [Au(2)(μ-cis-dppen)(2)]X(2) (X = OTf 1, PF(6)3) and [Au(cis-dppen)(2)]X (X = OTf 2, PF(6)4) is obtained from the reaction of [Au(tht)(2)]X (tht = tetrahydrothiophene) with one equivalent of cis-dppen [dppen = 1,2-bis(diphenylphosphino)ethylene]. The analogous reaction with trans-dppen or dppa [dppa = bis(diphenylphosphino)acetylene] affords the cyclic trinuclear [Au(3)(μ-trans-dppen)(3)]X(3) (X = OTf 11, PF(6)12) and tetranuclear [Au(4)(μ-dppa)(4)]X(4) (X = OTf 13, PF(6)14, ClO(4)15) gold complexes, respectively. Recrystallization of 15 from CH(2)Cl(2)/MeOH yielded a crystal of the octanuclear gold cluster [Au(8)Cl(2)(μ-dppa)(4)](ClO(4))(2)16. Attempts to prepare dicationic binuclear gold(II) species from the reaction of a mixture of 3 and 4 with halogens gave a mixture of products, the components of which confirmed to be acyclic binuclear gold(I) [Au(2)X(2)(cis-dppen)] (X = I 5, Br 7) and cyclic mononuclear gold(III) [AuX(2)(cis-dppen)]PF(6) (X = I 6, Br 8) complexes. Complexes 11-14 reveal weak emission in butyronitrile glass at 77 K, but they are non-emissive at room temperature. Ab initio modelling was performed to determine the charge state of the gold atoms involved. Extensive structural comparisons were made to experimental data to benchmark these calculations and rationalize the conformations.     

Evolution of Robustness and Plasticity under Environmental Fluctuation: Formulation in Terms of Phenotypic Variances

The characterization of plasticity, robustness, and evolvability, an important issue in biology, is studied in terms of phenotypic fluctuations. By numerically evolving gene regulatory networks, the proportionality between the phenotypic variances of epigenetic and genetic origins is confirmed. The former is given by the variance of the phenotypic fluctuation due to noise in the developmental process; and the latter, by the variance of the phenotypic fluctuation due to genetic mutation. The relationship suggests a link between robustness to noise and to mutation, since robustness can be defined by the sharpness of the distribution of the phenotype. Next, the proportionality between the variances is demonstrated to also hold over expressions of different genes (phenotypic traits) when the system acquires robustness through the evolution. Then, evolution under environmental variation is numerically investigated and it is found that both the adaptability to a novel environment and the robustness are made compatible when a certain degree of phenotypic fluctuations exists due to noise. The highest adaptability is achieved at a certain noise level at which the gene expression dynamics are near the critical state to lose the robustness. Based on our results, we revisit Waddington’s canalization and genetic assimilation with regard to the two types of phenotypic fluctuations.     

New text indexing functionalities of the compressed suffix arrays

New text indexing functionalities of the compressed suffix arrays are proposed. The compressed suffix array proposed by Grossi and Vitter is a space-efficient data structure for text indexing. It occupies only O(n) bits for a text of length n; however it also uses the text itself that occupies bits for the alphabet . In this paper we modify the data structure so that pattern matching can be done without any access to the text. In addition to the original functions of the compressed suffix array, we add new operations search, decompress and inverse to the compressed suffix arrays. We show that the new index can find occ occurrences of any substring P of the text in O(|P|logn+occlog^εn) time for any fixed 1ε>0 without access to the text. The index also can decompress a part of the text of length m in O(m+log^εn) time. For a text of length n on an alphabet such that , our new index occupies only bits where is the order-0 entropy of the text. Especially for ε=1 the size is bits. Therefore the index will be smaller than the text, which means we can perform fast queries from compressed texts.     

Spatiotemporal chaos and noise

Low-dimensional chaotic dynamical systems can exhibit many characteristic properties of stochastic systems, such as broad Fourier spectra. They are distinguishable from stochastic processes through finite values for their dimension, Lyapunov exponents, and Kolmogorov-Sinai entropy. We discuss how these characteristic observables are modified in spatiotemporal chaotic systems like. coupled map lattices. We analyze with the help of Lyapunov concepts how the stochastic limit is approached and how these properties can be observed directly through local dimension measurements from reconstructed time series. Finally, we discuss the interaction of spatiotemporal attractors with external noise and possible connections to problems of pattern selection and stability.     

GD3- and O-acetylated GD3-gangliosides in the GM2 synthase-deficient mouse brain and their immunohistochemical localization

Gangliosides in the brain of the knockout mouse deficient in the activity of β1,4 N-acetylgalactosaminyl transferase (β1,4 GalNAc-T)(GM2 synthase) consisted of nearly exclusively of GM3- and GD3-gangliosides as expected from the known substrate specificity of the enzyme and in confirmation of the initial reports from two laboratories that generated the mutant mouse experimentally. The total molar amount of gangliosides was approximately 30% higher in the mutant mouse brain than that in the wild-type brain. However, contrary to the initial reports, one-fourth of total GD3-ganglioside was O-acetylated. It reacted positively with an anti-O-acetylated GD3 monoclonal antibody and disappeared with a corresponding increase in GD3-ganglioside after mild alkaline treatment. The absence of O-acetylated GD3 in the initial reports can be explained by the saponification step included in their analytical procedures. Although quantitatively much less and identification tentative, we also detected GT3 and O-acetylated GT3. Anti-GD3 and anti-O-acetylated GD3 monoclonal antibodies gave positive reactions in the brain of mutant mouse as expected from the analytical results. Either antibody barely stained wild-type brain except for immunoreactivity of GD3 in the cerebellar Purkinje cells. The distributions of GD3 and O-acetylated GD3 in the brain of mutant mouse were similar but differential localization was noted in the cerebellar Purkinje cells and cerebral cortex.     

Molecular design,synthesis, and magnetic characterization of poly(phenylacetylene) with pi-toporegulated pendant nitronyl nitroxide radicals as models for organic superpara- and ferromagnets

The present article describes the synthesis and magnetic properties of poly(phenylacetylene) ( 3 ) with pi-toporegulated pendant stable 4,4,5,5-tetramethylimidazolin-3-oxide-1-yloxyl radicals topologically participating in the pi-conjugated system of poly(phenylacetylene). Polyradical 3 was prepared by the condensation reaction of poly(p-ethynylbenzaldehyde) with 2,3-bis(hydroxylamino)-2,3-dimethylbutane followed by oxidation with lead dioxide. The spin concentration of 3 determined by the ESR spectroscopic method was 1.1 × 10²¹ spins/g. This value approximately corresponds to 0.5 unpaired electron spin per the repeating unit. A powder ESR spectrum of 3 gave a 100% Lorentzian single line showing spin-exchange narrowing. The vibrating sample magnetometer (VSM) measurement of 3 afforded a straight line with a positive slope, suggesting that 3 has predominant paramagnetic properties within an experimental error.