Improvement in Solubility of Poorly Water Soluble Drug by Cogrinding with Highly Branched Cyclic Dextrin

We investigated the enhancement of the solubility of glibenclamide (GCM), a poorly water soluble anti-diabetes drug, by cogrinding it with highly branched cyclic dextrin (HBCD) using a ball mill. Highly branched cyclic dextrin (HBCD) is a novel cyclic glucan produced from waxy corn starch by the cyclization reaction of a branching enzyme. When GCM crystals were coground with HBCD for 2 h, the solubility of GCM was improved to 12.4 μg/ml, while the concentration of HBCD was 5.0 mg/ml. Additionally, the GCM solubilized with HBCD was chemically stable in aqueous solution for at least 1 week at room temperature. The peak intensity assigned to crystalline GCM disappeared after cogrinding it by observing its powder X-ray diffraction pattern, which means that the crystalline structure of GCM could be disrupted. In the DSC measurement, the ground mixture showed a single endothermic peak, even though a temperature depression of the endothermic peak due to GCM crystal was observed. After the cogrinding, two sharp peaks assigned to sulfonylurea and benzoyl carbonyl stretching bands varied to broaden the peak to around 1640 cm⁻¹ in the C=O stretching region. These results suggested the formation of solid dispersion between GCM and HBCD.     

Polybasic polyhedra: structure of polyhedra with edge vectors of support size at most 2

It has widely been recognized that submodular set functions and base polyhedra associated with them play fundamental and important roles in combinatorial optimization problems. In the present paper, we introduce a generalized concept of base polyhedron. We consider a class of pointed convex polyhedra in R^V whose edge vectors have supports of size at most 2. We call such a convex polyhedron a polybasic polyhedron. The class of polybasic polyhedra includes ordinary base polyhedra, submodular/supermodular polyhedra, generalized polymatroids, bisubmodular polyhedra, polybasic zonotopes, boundary polyhedra of flows in generalized networks, etc. We show that for a pointed polyhedron PR^V, the following three statements are equivalent:

(1) P is a polybasic polyhedron.

(2) Each face of P with a normal vector of the full support V is obtained from a base polyhedron by a reflection and scalings along axes.

(3) The support function of P is a submodular function on each orthant of R^V.

This reveals the geometric structure of polybasic polyhedra and its relation to submodularity.     

A nonaqueous potentiometric titration study of the dissociation of t-butyl methacrylate-methacrylic acid copolymers.

The dissociation of t-butyl methacrylate-methacrylic acid copolymers in dimethyl sulfoxide was analyzed by a nonaqueous potentiometric titration technique. The negative logarithm of the dissociation constant of the monomer unit of a methacrylic acid (MAA) monotonously increased with the increasing degree of dissociation corresponding to the titrant/MAA amount ratio, and was highly influenced by the copolymerization ratio. The results are discussed in terms of the suppression of the dissociation of MAA by a neighboring charged methacrylate anion unit.     

Plasma Processing Based Synthesis of Functional Nanocarbons

Our recent research has shown that plasma processing techniques, which allow versatile control of both chemical and physical aspects, have considerable potential for the innovative synthesis and functionalization of three varieties of low-dimensional nanocarbons, which show great promise in the development of nanoscience and its applications. In the case of 0-D fullerenes, the mission is the high-yield production of atom (X) encapsulated fullerenes (X@C₆₀). The formation of macro-quantities of charge-exploited Li@C₆₀ and overwhelmingly-high purity spin-exploited N@C₆₀ are realized for the first time by the control of alkali-fullerene and nitrogen double plasmas, respectively. In the case of 1-D carbon nanotubes the challenge is precise structure control, i.e., chirality control of single-walled carbon nanotubes (SWNTs). The extremely narrow-chirality distributed growth of SWNTs is realized with time-programmed and nonmagnetic-catalyzed plasma CVD. As for functionalization of SWNTs, the enhanced p-type C₆₀@SWNTs created under the substrate-bias control in collisionless plasmas are found to be effective for harvesting solar energy in the infrared wavelength range and adapted to the use for multiple exciton generation in solar cells. Concerning 2-D graphene, our aim is to overcome two serious issues for electronics applications. One is the realization of the direct growth of graphene on an insulating (SiO₂) substrate by adjusting the growth parameters using non-equilibrium diffusion plasma CVD. The other is the direct fabrication of field-effect transistor device of a narrow-width (≥20 nm) graphene nanoribbon using a new, simple, and scalable method based on rapid heating plasma CVD, which shows a clear transport gap and a high on/off ratio. Finally the prospects for the above-mentioned results are discussed together with ripple effects of the nanocarbon research on the progress of nanoscience and its applications.     

11B solid-state NMR investigation of the rhamnogalacturonan II-borate complex in plant cell walls.

The boron in plant cell walls, which is water-insoluble and in the solid state, is solubilized by pectinase digestion to give a dimeric rhamnogalacturonan II-borate (dRG-II-B) complex. To clarify the nondestructive structure of boron present in plant cell walls (as represented by sugar beet fiber), we performed 192- and 96-MHz 11B solid state NMR measurements. The use of a high field magnet frequency of 192-MHz enabled us to observe 11B isotropic chemical shifts at -9.7 and -9.6 ppm for dRG-II-B and sugar beet fiber in the solid state, respectively, demonstrating that the boron in isolated dRG-II-B and in plant cell walls is present as a borate-diol ester (1:2). The observation of the magnetic field dependence of the chemical shift and lineshape for the borate-diol ester (1:2) by quadrupolar interaction suggested that the borate complex had a distorted tetrahedral boron structure.     

Asymptotic estimates of multi-dimensional stable densities and their applications

The relation between the upper and lower asymptotic estimates of the density and the fractal dimensions on the sphere of the spectral measure for a multivariate stable distribution is discussed. In particular, the problem and the conjecture on the asymptotic estimates of multivariate stable densities in the work of Pruitt and Taylor in 1969 are solved. The proper asymptotic orders of the stable densities in the case where the spectral measure is absolutely continuous on the sphere, or discrete with the support being a finite set, or a mixture of such cases are obtained. Those results are applied to the moment of the last exit time from a ball and the Spitzer type limit theorem involving capacity for a multi-dimensional transient stable process.

     

Gas permeation through hydrogels : II. Poly(vinylalcohol-co-itaconic acid) membranes

Permeability and diffusion coefficients of O₂, He, CO₂ and C₄H₆ were measured in water,swollen poly(vinylalcohol-co-itaconic acid) membranes having various water contents from 0.48 to 0.83. The permeability coefficients of CO₂ and C₄H₆ were found to depend on the upstream pressure, while the permeability coefficients of O₂ and He were independent of the pressure. With decreasing pressure the permeability coefficients of CO₂ and C₄H₆ increased, and the pressure dependence became larger with decreasing water content of the membranes. A parallel permeation model based on the two states of water in the water-swollen membranes could be applied successfully to CO₂ and C₄H₆.