13C nmr study of α- and β-anomeric pairs of d-mannopyranosides and l-rhamnopyranosides

¹³C NMR spectra for a variety of α and β-anomeric series of d-mannopyranosides and l-rhamnopyranosides are presented and analyzed in comparison with those of D-glucopyranosides. The results obtained in the present study are valuable for the structure studies of plant-glycosides as well as carbohydrates, especially for determination of anomeric configurations of mannosides and rhamnosides which has been extremely difficult by other classical techniques.     

Cyclotron damping of the space charge wave of a beam in a nonuniform magnetic field region

The space charge wave of an electron beam excited by the reactive medium instability in a uniform magnetic field region is observed to propagate into the region of increasing magnetic field. When the wave passes through the cyclotron resonance region, it suffers heavy cyclotron damping.     

Neutron-proton radius differences and isovector deformations from π+ and π− inelastic scattering from 18O

π⁺ and π^? elastic and inelastic scattering from ¹⁸O have been measured at T(π)=164 MeV. Consistent with the results at 230 MeV, it is found that the ratio $\text{σ(π}{}^{\mathrm{?}}\text{)}\text{σ(π}{}^{\mathrm{+}}\text{)}$ for the 2₁⁺ state is 1.86(16), while for the 3₁^? state it is 0.89(6). These results are interpreted as indicating differences in neutron and proton deformations characterizing the 2₁⁺ transition and partial neutron blocking for the 3₁^? transition. Optical model analysis of elastic scattering leads to the conclusion that $\text{〈r}{}_{\mathrm{<mtext>n</mtext>}}{}^2\text{〉}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{?〈r}{}_{\mathrm{<mtext>p</mtext>}}{}^2\text{〉}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{=0.03(3)}\text{fm}$.     

Wechselwirkung zwischen Farbstoffen und Polyelektrolyten, 5. Mitt. Einfluß von organischen und anorganischen Salzen auf die Metachromasie von Methylenblau

Ohne Zusammenfassung     

Synthesis of lipid A analogues containing glucose instead of glucosamine and their LPS-antagonistic activities

Lipid A analogues containing glucose in substitution for glucosamine on the reducing end were synthesized, and the inhibitory activities on LPS-induced TNFα production (LPS-antagonistic activity) in vitro using human whole blood cells were measured. The IC₅₀ values (nM) of these ten compounds, 8, 14, 21, 31, 40, 51, 57, 62, 67 and 72, were 11.2, 15.4, 2.7, 0.1, 0.4, 1.3, 3.2, 3.2, 1.4 and 14.4, respectively. And also inhibitory activities (ID₅₀) on TNFα production toward galactosamine loaded C3H/HeN mice in vivo of compounds 21, 31, 57, 62 and 67 were measured. The values of these compounds were 0.29, 0.50, 0.61, not dose-dependent and 0.33 mg/kg, respectively.     

Feeding attractants for the muricid gastropod Drupella cornus, a coral predator

The muricid gastropods genus Drupella are known to be voracious coral predator. Outbreaks of them have accelerated significant destruction on coral reefs, but its precise mechanism is poorly understood. Here, we describe the identification of montiporic acids C (1) and A (2) isolated from sea water extracts of the coral Montipora sp., which showed potent feeding-attractant activity toward D. cornus.     

Ion association dynamics in aqueous solutions of sulfate salts as studied by Raman band shape analysis

A new perspective is shown on the interaction between the sulfate ion and its counter cation in aqueous solutions. We propose the dynamic exchange model of ion association instead of the conventional static equilibrium model. The concentration dependence of the Raman band shape of the totally symmetric (a(1)) SO stretch mode of the sulfate ion is investigated systematically for four sulfate ions, MgSO(4), (NH(4))(2)SO(4), K(2)SO(4), and Li(2)SO(4). The concentration dependence of the a(1) Raman band shape in the MgSO(4) system is successfully reproduced by the analysis based on the dynamic exchange model. As a result, quantitative information about the extremely dynamic nature of the ion association has been obtained: the mean time between associations is a few picoseconds and the mean lifetime of association is several hundred femtoseconds.     

A new method to reconstruct three-dimensional spatial distribution function from radial distribution function in solvation structure

Three-dimensional spatial distribution function (SDF) of solvent is a fundamental quantity for analysis of solvation. However, its calculation has been very limited because long computational time is required. We here developed a novel and robust method to construct approximated SDFs of solvent sites from radial distribution functions. In this method, the expansion of SDFs in real solid harmonics around atoms of solute leads to a linear equation, from which SDFs are evaluated with reasonable computational time. This method is applied to the analysis of the solvation structure of liquid water, as an example. The successful results clearly show that this method is very powerful to investigate solvation structure.     

Tests of the homogeneous nucleation theory with molecular-dynamics simulations. I. Lennard-Jones molecules

Two kinds of the homogeneous nucleation theory exist at the present: the classical nucleation theory and the semiphenomenological model. To test them, we performed molecular-dynamics (MD) simulations of nucleation from vapor to liquid with 5000-20,000 Lennard-Jones-type molecules. Simulations were done for various values of supersaturation ratios (from 2 to 10) and temperatures (from 80 to 120 K). We compared the size distribution of clusters in MD simulations with those in the theoretical models because the number density of critical clusters governs the nucleation rate. We found that the semiphenomenological model achieves excellent agreements in size distributions of the clusters with all MD simulations we done. The classical theory underestimates the number density of the clusters in the temperature range of 80-100 K, but overestimates in 100-120 K. The semiphenomenological model also predicts well the nucleation rate in MD simulations, while the classical nucleation theory does not. Our results confirmed the validity of the semiphenomenological model for Lennard-Jones-type molecules.     

Organocatalytic asymmetric direct alkylation of alpha-diazoester via C-H bond cleavage

A new variant of phosphoric acid-catalyzed C-C bond forming reaction, direct alkylation of alpha-diazoester, via C-H bond cleavage is presented. The resulting products, beta-amino-alpha-diazoesters, are highly functionalized and useful synthetic precursors for various types of beta-amino acids.