Complexation of poly(vinyl alcohol)–congo red aqueous solutions. 3. Dynamic light scattering study

Mesoscopic structures of poly(vinyl alcohol)(SINGLEBOND)Congo red (PVA(SINGLEBOND) CR) complexes in aqueous solutions were investigated in terms of dynamic light scattering (DLS) technique. The intensity-intensity time correlation function, g⁽²⁾(t), was analyzed with an equation including a single and a stretched exponential function. Two diffusion coefficients, D_f (fast) and D_s (slow) were evaluated. D_f was converted to the apparent correlation length, ξ_app, via the mode-mode coupling hypothesis. The estimated ξ_app was insensitive to the sol(SINGLEBOND)to(SINGLEBOND)gel transition but decreased with CR concentration. This change may be related to the electrostatic screening effect. On the other hand, D_s oscillates with increasing CR concentration at a specific PVA concentration range. This explains well the reentrant sol(SINGLEBOND)gel(SINGLEBOND)sol(SINGLEBOND)gel transition behavior observed in the PVA(SINGLEBOND)CR systems. D_s seems to represent the mobility of the PVA(SINGLEBOND)CR complexes, which annihilates at the gel point. © 1996 John Wiley & Sons, Inc.     

Simultaneous detection of ammonia and humidity using transmission surface plasmon resonance technique

Abstract

Gas sensing by using the transmission surface plasmon resonance (T-SPR) technique was demonstrated. Polyacrylic acid (PAA)/5-nm-thick gold/40-nm-thick silver/polycarbonate grating substrate structure (Sensor A) responded to ammonia; however, it exhibited a strong humidity dependence. Polyvinyl alcohol (PVA)/5-nm-thick gold/40-nm-thick silver/polycarbonate grating substrate structure (Sensor B) as the sensing material was also prepared and it mainly responded to humidity. The T-SPR properties of Sensors A and B were observed simultaneously by a stacking arrangement that enabled us to obtain the responses by using a single spectrophotometer. The ammonia concentration under various humidity conditions could be accurately obtained by simultaneous measurement of Sensors A and B.     

Spin-projected QM/MM Free Energy Simulations for Oxidation Reaction of Guanine in B−DNA by Singlet Oxygen

Guanine is the most susceptible base to oxidation damage induced by reactive oxygen species including singlet oxygen (¹O₂, ¹Δ_g). We clarify whether the first step of guanine oxidation in B−DNA proceeds via either a zwitterionic or a diradical intermediate. The free energy profiles are calculated by means of a combined quantum mechanical and molecular mechanical (QM/MM) method coupled with the adaptive biasing force (ABF) method. To describe the open-shell electronic structure of ¹O₂ correctly, the broken-symmetry spin-unrestricted density functional theory (BS−UDFT) with an approximate spin projection (AP) correction is applied to the QM region. We find that the effect of spin contamination on the activation and reaction free energies is up to ∼8 kcal mol⁻¹, which is too large to be neglected. The QM(AP−ULC−BLYP)/MM-based free energy calculations also reveal that the reaction proceeds through a diradical transition state, followed by a conversion to a zwitterionic intermediate. Our computed activation energy of 5.2 kcal mol⁻¹ matches experimentally observed range (0∼6 kcal mol⁻¹).     

Enantioselective synthesis of (−)-elenolic acid and (−)-ajmalicine

A secoiridoid monoterpene (?)-elenolic acid and a representative heteroyohimbine alkaloid (?)-ajmalicine have been synthesized enantio- and stereoselectively using L-ethyl lactate as a chiral starting material.     

Isolation, identification and pharmacological studies on three toxic metabolites from a mushroom, Hebeloma spoliatum.

Three metabolites, tentatively named HS-A, -B and -C, were isolated from a mushroom, Hebeloma spoliatum, as the fatal toxic principles to mice. HS-A was identified as 3-acetyl-2-(3'-hydroxy-3'-methyl)glutarylcrustulinol, which has been isolated from Hebeloma crustuliniforme and H. sinapizans as a cytotoxic principle. HS-B and -C were deduced to be 3,21-diacetyl-2-(3'-hydroxy-3'-methyl)glutarylcrustulinol and 3-acetyl-2-(3'-hydroxy-3'-methyl)glutarylanhydrocrustulinol, respectively, from their chemical and spectral data. Intraperitoneal administration of HS-A, -B and -C at a dose of 100 mg/kg caused death after paralysis of the limbs in mice. The compounds caused relaxation of mouse small intestine contracted by acetylcholine chloride or barium chloride treatment in vitro. They appear to exhibit a papaverine-like relaxation effect.     

Statistical manifolds with almost contact structures and its statistical submersions

In this paper, we discuss statistical manifolds with almost contact sturctures. We define a Sasaki-like statistical manifold. Moreover, we consider Sasaki-like statistical submersions, and we study Sasaki-like statistical submersion with the property that the curvature tensor with respect to the affine connection of the total space satisfies the condition (2.12).     

Fast polarimetry system for the application to spin quantum non-demolition measurement

We report the development of a fast pulse polarimeter for the application to quantum non-demolition measurement of atomic spin (spin QND). The developed system was tunable to the atomic resonance of a ytterbium atom and has narrow laser line width suitable for spin QND. Using the developed polarimeter, we successfully demonstrated the measurement of the vacuum noise, with 10⁶ to 10⁷ photon number per pulse. PACS 42.25.Ja; 42.50.Lc; 42.55.Px     

Positron annihilation in synthetic zeolites

Both lifetime and angular correlation of positron annihilation have been measured for a series of synthetic zeolites for which the void structures are known fairly well. All of the zeolites had long lifetime components and a narrow momentum component which are ascribable to o-Ps and p-Ps annihilations in the voids, respectively. The correlation between the width of the p-Ps narrow component and the size of the largest voids showed a remarkable agreement with a theoretical estimate based on the spherical potential well model. The measurement of p-Ps momentum thus appears to be prospective as a tool to determine the size of voids of materials. The lifetime of the long lifetime component, on the other hand, showed a poor correlation with the void size even from a qualitative viewpoint, suggesting that factors other than the simple void size effect are dominant in determining the o-Ps lifetimes. Discussion is made on the cause of the different dependences of o-Ps and p-Ps annihilation parameters on the void size. It has also been found that p-Ps fraction is always larger than one third of the o-Ps fraction in all the zeolites studied. A discussion is presented on this point, too.Formerly, RIISOM