Gamma-p-toluenesulfonyl-alpha,beta-epoxysilane: a new and practical acrolein beta-anion equivalent

[reaction: see text] Reaction of gamma-p-toluenesulfonyl-alpha,beta-epoxysilane with alkyl halides and aldehydes followed by treatment with n-Bu4NF affords alpha,beta-unsaturated aldehydes via a Brook rearrangement-mediated tandem process under extremely mild conditions.     

Formation of M+. ions under matrix fast atom bombardment conditions: Does charge exchange reaction occur?

The formation of molecular ions, M^+., under fast atom bombardment (FAB) conditions using a liquid matrix was examined by using a new type of synthesized compounds in which preferential M^+. peaks appear in their FAB spectra. The FAB spectra were compared with the corresponding mass spectra obtained by the electron impact (EI) ionization, chemical ionization (CI) and charge-exchange ionization (CEI) methods. All of the spectra showed preferential peaks of M^+. ion and a characteristic intense fragment ion peak originating from a β-fission. The FAB spectra were similar in the fragment ions appearing in the EI spectra and were very similar in the fragmentation pattern to the CEI spectra using Ar^+. and Xe^+. as the reagent ions. Further, the FAB spectra did not show any doubly charged ion peaks, while the 70 eV EI spectra showed the peaks of doubly charged molecular and/or fragment ions. The isobutane CI spectra of the synthesized compounds suggested that the formation of M^+. ions occurred through the CE reaction with isobutane ion, C₄H₁₀^+., and the CI spectra showed a marked intense fragment ion peak originating from the β-fission which seemed to occur characteristically in CEI processes. The results obtained suggested that the formation of M^+. ions under matrix FAB conditions occurred mainly by CE reactions between the analytes M and matrix molecular ions B^+. and/or fragment ions b^+..     

Synthesis and central nervous system stimulant activity of 5,8-methanoquinazolines fused with imidazole,thiadiazole, pyrimidine and 1,3,5-triazine

5,8-Methanoquinazolines fused with imidazoles 4a-4b , thiadiazoles 5–6 , pyrimidines 7, 9, 11 and 12 , and 1,3,5-triazine 13 were prepared starting from (5R,8S)-2-amino-8,9,9-trimethyl-5,6,7,8-tetrahydro-5,8-methanoquinazoline 3 . Most compounds possessed central nervous system stimulant activities.     

New Finding of the Glass Transition Phenomenon in Surfactant Gel Phase: The Binary System of Water and Dioctadecyldimethyl-Ammonium Chloride

Differential scanning calorimetry on the two-component system of dioctadecyldimethylammonium chloride (DOAC)–water was carried out in the temperature region from 80 °C down to -100 °C. As the result, a new type of glassy state was found around at -40 °C for the supercooled complete gel phase.     

Large Deviations for Countable to One Markov Systems

In this paper, we study large deviation properties for countable to one Markov systems associated to weak Gibbs measures for non-Hölder potentials. Furthermore, we establish multifractal large deviation laws for countable to one piecewise conformal Markov systems, which are derived systems constructed over hyperbolic regions for certain nonhyperbolic systems exhibiting intermittency. We apply our results to higher-dimensional number theoretical transformations.     

Preparation of carbon nitride film by cryogenic laser processing

Laser irradiation of solid nitrogen containing cyanuric triazide (C₃N₁₂) could generate highly reactive carbon nitride species, NCN and dicyanocarbodiimide. These species were generated in the solid nitrogen at 20 K. After laser photolysis, generated reactive species were concentrated by removal of nitrogen, and converted into a film-like product. Thus, the obtained product was characterized by means of FTIR, SEM, and XPS measurements. The product was assigned to amorphous carbon nitride with relatively high nitrogen content (N/C=0.91.3). PACS 81.15.Fg; 82.33.-z; 68.55.Nq     

XPS and LEED study of Pd and Au growth on alumina/Cu-Al surface

Metal-insulator-metal system was prepared using the single-crystalline Cu-9at.% Al(1 1 1) support. Oxidation of the substrate under well-controlled conditions at elevated temperature leads to the formation of well-ordered aluminium oxide layer. The Pd-Au topmost layer was prepared by a step-by-step deposition of both metals afterwards on the oxide layer at room temperature. Low energy electron diffraction (LEED) measurement did not confirm epitaxial growth of the metal overlayer and gave only a rise of diffuse background after each deposition step. The growth of Pd-Au overlayer exhibited Stranski-Krastanov mode influenced by intermetallic interaction between those metals. No binding energy shifts were visible for the core-level photoelectron peaks of the substrate and the oxide using X-ray photoelectron spectroscopy (XPS). In contrast, the binding energy shifts of Pd 3d and Au 4f photoelectron levels in both directions were observed during all depositions. Bimetallic interactions between the metals as well as size effects are further discussed.     

Catalytic asymmetric alkylation of α-cyanocarboxylates and acetoacetates using a phase-transfer catalyst

The catalytic asymmetric alkylation of α-cyanocarboxylates and acetoacetates with an alkyl halide was performed under phase-transfer conditions to afford compounds which have a chiral quaternary carbon with up to 97% and 94% ee, respectively. As applications of this method, chiral 2-oxindole derivatives and a β-lactam derivative were synthesized.     

Fast and Robust Nanocellulose Width Estimation Using Turbidimetry

The dimensions of nanocelluloses are important factors in controlling their material properties. The present study reports a fast and robust method for estimating the widths of individual nanocellulose particles based on the turbidities of their water dispersions. Seven types of nanocellulose, including short and rigid cellulose nanocrystals and long and flexible cellulose nanofibers, are prepared via different processes. Their widths are calculated from the respective turbidity plots of their water dispersions, based on the theory of light scattering by thin and long particles. The turbidity‐derived widths of the seven nanocelluloses range from 2 to 10 nm, and show good correlations with the thicknesses of nanocellulose particles spread on flat mica surfaces determined using atomic force microscopy.