Method of kinetic analysis of photodegradation: nifedipine in solutions

A rate equation for photodegradation was derived from Lambert-Beer's law and Grotthus-Draper's law: -dc/dt=k1(1-exp(-(k2c+k3(c0-c))))k2c/(k2c+k3(c0-c)) where c is the concentration of reactant, c0 is the initial concentration of reactant, t is time, k1 is the rate constant, and k2 and k3 are the absorption coefficient of reactant and its photodegradation product, respectively. In a case where the photodegradation products have no photoabsorption, k3 assumes the value of zero in the above general equation. In a case where the photodegradation products have the same spectrum and molar absorptivity as that of the reactant, k3 assumes the value of k2, and hence the photodegradation is not a first-order reaction; however, the equation itself gives the pseudo-first-order reaction rate equation. In a case where the concentration of reactant is high enough, the equation approaches a zero-order reaction rate equation. The photodegradation rate of nifedipine in solutions under a germicidal lamp, near an ultraviolet fluorescent lamp and a fluorescent lamp was analyzed using the above equation. The photodegradation rate was directly proportional to the amount of light absorbed, and fitted well with the equation. The above theoretical equation was substantiated by the photodegradation of nifedipine, and hence is expected to apply to other photosensitive drugs.     

Self-crosslinkable polymers. I. Copolymerization of glycidyl methacrylate with 2-vinylpyridine and 2-vinyl-5-ethylpyridine

A soluble and self-crosslinkable linear copolymer with pendant epoxy and pyridyl groups was obtained from glycidyl methacrylate (M₁) and 2-vinylpyridine (M₂) or 2-vinyl-5-ethylpyridine (M₂) by the action of azobisisobutyronitrile. The monomer reactivity ratios were determined in tetrahydrofuran at 60°C: r₁ = 0.510, r₂ = 0.620 with 2-vinylpyridine and r₁ = 0.57, r₂ = 0.62 with 2-vinyl-5-ethylpyridine. These were consistent with the calculated values with the reported Q and e values for these monomers. The intrinsic viscosities of the copolymers with 2-vinylpyridine and with 2-vinyl-5-ethylpyridine were found to be 0.17–0.19 and 0.26–0.38, respectively, in tetrahydrofuran at 30°C; they were independent of the copolymer composition. The copolymers were amorphous, had no clear melting points, and became insoluble crosslinked polymers under heating without further addition of any curing agents.     

Block copolymer from α,ω-dihydroxyl polystyrene and polyethylene glycol

α,ω-Dihydroxyl polystyrene was synthesized by the addition of styrene oxide to polystyryl dianion initiated with sodium naphthalene. Diglyme was found to be an unsuitable solvent for the preparation of low molecular weight compounds. Block copolymerization of the α,ω-dihydroxyl polystyrenes (M?_n = 2250, 3140, and 6200) with poly(ethylene glycols) (M?_n = 404, 1960, and 5650) was pursued by introducing urethane linkages with 4,4′-diphenylmethane diisocyanate. The mechanical, thermal, and viscoelastic properties, solution viscosity, molecular weight distribution, and moisture absorption of the block copolymers obtained were examined. Incorporation of styrene blocks was found to disturb the crystallization and fusion of poly(ethylene glycol) blocks. Films cast from benzene solution were soft and elastic and absorbed up to 5.8% moisture.     

Reaction of poly(vinyl chloride) with magnesium and grignard reagents

Reaction of poly(vinyl chloride) with magnesium under various conditions was attempted, but poly(vinyl chloride) did not react with magnesium. The reactions of poly(vinyl chloride) with benzylmagnesium chloride and allylmagnesium chloride as Grignard reagents were carried out in tetrahydrofuran at reflux temperature. It was found that the chlorine atoms in the poly(vinyl chloride) were replaced by benzyl and allyl groups by the coupling reaction, and a small amount of Grignard reagent of poly(vinyl chloride) was formed by the magnesium–halogen exchange reaction. The extent of the substitution increased with increasing reaction time and concentration of the Grignard reagent.     

A Theoretical Study of ãA2 CH2

The potential energy surface and dipole moment surfaces of the ã⁴A₂ electronic state of CH₂⁺ are calculated ab initio using an augmented correlation-consistent polarized valence quadruple-ζ (aug-cc-pVQZ) basis set, with the incorporation of dynamical correlation using the coupled cluster method with single and double excitations and perturbatively connected triple excitations [CCSD(T)]. We use these surfaces in the MORBID program system to calculate rotation and rotation-vibration term values for ã-state CH₂⁺, CD⁺₂, and CHD⁺ and to simulate the rotation and rotation-vibration absorption spectrum of CH₂⁺ in the ã⁴A₂ electronic state. Our work is motivated by studies of CH₂⁺ that use the Coulomb explosion imaging technique and by the goal of predicting spectra that may be obtained from discharge sources. Although the ã state is the lowest-lying excited state above the X?/Ã ground state pair, it turns out to be relatively high-lying, and we determine that T_e(ã)=30447.5 cm⁻¹. The equilibrium bond angle for ã-state CH₂⁺ is only 77.1°; as a result the asymmetric top κ value is close to 0, and the molecule is equally far from the oblate and prolate symmetric top limits in this electronic state.     

Evolutionary construction of geographical networks with nearly optimal robustness and efficient routing properties

Robust and efficient design of networks on a realistic geographical space is one of the important issues for the realization of dependable communication systems. In this paper, based on a percolation theory and a geometric graph property, we investigate such a design from the following viewpoints: (1) network evolution according to a spatially heterogeneous population, (2) trimodal low degrees for the tolerant connectivity against both failures and attacks, and (3) decentralized routing within short paths. Furthermore, we point out the weakened tolerance by geographical constraints on local cycles, and propose a practical strategy by adding a small fraction of shortcut links between randomly chosen nodes in order to improve the robustness to a similar level to that of the optimal bimodal networks with a larger degree for the network size N. These properties will be useful for constructing future ad hoc networks in wide-area communications.     

Rapid sea-level change in the Late Guadalupian (Permian) on the Tethyan side of South China: litho- and biostratigraphy of the Chaotian section in Sichuan

The Capitanian (Late Guadalupian) Maokou Formation at Chaotian in northern Sichuan, South China, is composed mainly of shallow marine shelf carbonates deposited on the Tethyan side of South China. By detailed field mapping and scientific drilling, we newly found out unique fossil assemblages and a sharp lithologic change in the upper part of the Maokou Formation. The main part of the Maokou Formation (over 130 m thick) is composed of algal packstone with Wordian-Capitanian large-tested fusulines, rugose corals and other sessile benthos, whereas the Uppermost Member (13 m thick) is composed of black limy mudstone/chert with Capitanian offshore biota (ammonoids, radiolarians, and conodonts). The topmost Capitanian conodont zones are missing; however, the Maokou Formation is disconformably overlain by 260+/-4 Ma volcanic ash (Wangpo bed) and the Early Lopingian Wujiaping Formation with plant-bearing coaly mudstone and shallow marine carbonates (packstone). The newly identified facies change indicates that northern Sichuan has experienced rapid sea-level changes in the late Guadalupian, i.e., first a transgression in the mid-Capitanian and then a regression across the Guadalupian-Lopingian boundary. As the end-Guadalupian is characterized by a global regression, such a volatile sea-level fluctuation, in particular the sea-level rise, is unique to the Tethyan side of South China. The newly recognized relatively deep-water late Guadalupian sequence adds new paleo-environmental information and further provides a paleotectonic interpretation of the low-latitude eastern Tethyan margin immediately before the end-Guadalupian mass extinction.     

Chirality sensitive effect on surface states in chiral p-wave superconductors

We study the local density of states at the surface of a chiral p-wave superconductor in the presence of a weak magnetic field. As a result, the formation of low-energy Andreev bound states is either suppressed or enhanced by an applied magnetic field, depending on its orientation with respect to the chirality of the p-wave superconductor. Similarly, an Abrikosov vortex, which is situated not too far from the surface, leads to a zero-energy peak of the density of states, if its chirality is the same as that of the superconductor, and to a gap structure for the opposite case. We explain the underlying principle of this effect and propose a chirality sensitive test on unconventional superconductors.     

Electronic state on the surface in the strongly correlated electron systems

In order to clarify the tunneling spectroscopy in high-T_c cuprates, we study electronic state of the surface in the strongly correlated electron systems. First, we obtain Green's function of strongly correlated normal bulk system using the fluctuation exchange (FLEX) approximation. Next, we insert infinite potential into the bulk system and obtain Green's function of surface. We find that the density of states (DOS) in strongly correlated bulk systems are different from that on the surface, and the difference decreases as the magnitude of Coulomb interaction (U) increases.     

Rapid reduction of titanium dioxide nano-particles by reduction with a calcium reductant

Micro-, submicron-, and nano-scale titanium dioxide particles were reduced by reduction with a metallic calcium reductant in calcium chloride molten salt at 1173 K, and the reduction mechanism of the oxides by the calcium reductant was explored. These oxide particles, metallic calcium as a reducing agent, and calcium chloride as a molten salt were placed in a titanium crucible and heated under an argon atmosphere. Titanium dioxide was reduced to metallic titanium through a calcium titanate and lower titanium oxide, and the materials were sintered together to form a micro-porous titanium structure in molten salt at high temperature. The reduction rate of titanium dioxide was observed to increase with decreasing particle size; accordingly, the residual oxygen content in the reduced titanium decreases. The obtained micro-porous titanium appeared dark gray in color because of its low surface reflection. Micro-porous metallic titanium with a low oxygen content (0.42 wt%) and a large surface area (1.794 m² g⁻¹) can be successfully obtained by reduction under optimal conditions.