Synthesis of high surface area Al-containing mesoporous silica from calcined and acid leached kaolinites as the precursors

Al-containing mesoporous silicas were synthesized by hydrothermal treatment of microporous silica prepared by selectively acid leached metakaolinites with Si/Al = 3.9-92.5 mixed with a surfactant of cetyltrimethylammonium bromide (CTABr). The specific surface area of the products increased with higher surfactant/microporous silica (surf/Si) ratio and Si/Al ratio of the microporous silica, reaching about 1400 m2/g at CTABr/Si 0.1 and Si/Al 40. The XRD patterns of these products show a hexagonal (100) peak with the lattice parameter a0=4.2-4.3 nm and the N2 adsorption isotherms show steep increase of adsorption between relative pressure of 0.3 and 0.4. Hexagonal mesoporous microstructure is observed by high resolution TEM. The pore size distributions of the products show a sharp peak at 2.8 nm by the BJH method. The high specific surface area of the present mesoporous samples is attributed to the lower matrix density and surface roughness of mesopore wall. The highest specific surface area of the products reached up to 1420 m2/g and this value is apparently higher than those reported in hexagonal mesoporous silicas. A unique microporous structure of the starting material is thought to be related to achieve such a high specific surface area of the products.     

Six new indole alkaloids from Gelsemium sempervirens Ait. f.

One new yohimbane and five new sarpagine-type indole alkaloids were isolated from the radix of Gelsemium sempervirens Ait. f., and their structures were determined by spectroscopic analysis, chemical conversion or total synthesis. It was found that 2-acyl sarpagine-type alkaloids possessing an N_b-methyl group take a keto-amino structure or a transannular form in solution depending on the solvent.     

Synthesis of chiral oligopeptides by means of catalytic asymmetric hydrogenation of dehydropeptides

Asymmetric hydrogenations of Ac-ΔTyr(Ac)-(S)-Ala-Gly-OMe (6), Ac-ΔTyr(Ac)-(R)-AlaGly-(S)-Phe-OMe (7), Ac-ΔPhe-NH-CH(R) CH₂-OCH₂Ph (10), HCO-ΔPhe-(S)-Leu-OMe (16), X-AA-ΔPhe-AA'-OMe (5: X ^tBOC, CBZ, CF₃CO; AA, AA' = α-amino acid), and ^tBOC-AA-ΔPhe-AA'-NH-Y (21: Y=H, NH-AA'-ΔPhe-AA-^tBOC, NHPh), catalyzed by cationic Rh complexes, [L*Rh(NBD)]⁺ClO₄ (L* = chiral diphosphine), were performed to give the corresponding chiral oligopeptides with high stereoselectivities. It was found that the nature of the N-protecting group of dehydrotripeptides (5) exerted a significant influence on the asymmetric induction as well as catalyst efficiency. The chiral centers in AA' and AA' amino acid residues in 5 were also found to have some influence on the catalytic asymmetric induction. Possible mechanism which can accommodate these effects are discussed. Asymmetric reduction of RCOCO-AA-OMe (13) via hydrosilylation was carried out to give chiral depsipeptide units. The asymmetric hydrogenation of dehydropeptides was successfully applied to the synthesis of enkephalin analogs, Ac-(R)Tyr-(R) -Ala-Gly-(S)-Phe-(S)-Leu-OMe (23) and Ac-(S)Tyr-(R) -Ala-Gly-(S)-Phe-(S)- Leu-OMe (29)     

Reduction of carbonyl compounds via hydrosilylation: V. Synthesis of optically active allylic alcohols via regioselective asymmetric hydrosilylation

Regioselective asymmetric reduction of prochiral α,β-unsaturated ketones to optically active allylic alcohols was performed via hydrosilylation catalyzed by a rhodium(I) complex with (+)-BMPP, (+)-DIOP and (?)-DIOP as chiral ligands. The allylic alcohols with optical purity up to 69% e.e. were obtained in good yields. The extent of asymmetric induction was found to depend on the stereo-electronic matching of the chiral ligand, ketone and hydrosilane employed. In the asymmetric reduction of (R)-carvone, leading to carveol, the extent of asymmetric induction was found to depend markedly on the ligand/rhodium ratio. Either trans-(5R,1S)-carveol or cis-(5R,1R)-carveol was obtained with good stereoselectivity by using (?)-DIOP or (+)-DIOP as chiral ligand, and it turned out that the chiral center present in carvone had only a slight influence on the asymmetric induction by the chiral catalysts.     

Induced effects and technological innovation with strategic environmental policy

This paper investigates an environmental policy designed to reduce the emission of pollutants under uncertainty, where the agents’ problem is formulated as an optimal stopping problem. We first analyze the single-agent’s case according to Pindyck [Pindyck, R.S., 2002. Optimal timing problems in environmental economics. Journal of Economic Dynamics and Control 26, 1677–1697]. We then extend the model to the case in which there are two competing agents. Therefore, we consider the external economic effects that are peculiar to an agent’s environmental policy decision. Finally, we consider the effect of technological innovation. The results of the analysis suggest that if there are two competing agents, they implement environmental policy simultaneously. Furthermore, the threshold for implementing environmental policy is higher when there are two agents, and how long these two agents take to implement environmental policy depends on the magnitude of the external economic effect. Furthermore, when we consider the effect of technological innovation, we show that the incentive to be the leader occurs if an additional condition is satisfied.     

Hydration and dehydration behavior of <Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide gel particles

Thermal response of N-isopropylacrylamide (NiPAM) gel particles of submicron size was investigated by means of ultrasonic velocity and density focusing on the hydration and dehydration behavior. Hydration number, defined as the number of water molecules bound to one NiPAM monomer unit, was quantitatively evaluated in the course of the volume phase transition. Hydration numbers at low and high temperatures were about 7.5 (20 °C) and 3 (40 °C), respectively. Hydration number decreases markedly near the volume phase transition temperature, and the decrease is responsible to the formation of hydrophobic bonding and dehydration. The hydration number is independent both of the size and the composition of gel particles in the shrunken state, although there exists a composition dependence in the swollen state. It was also found that the self-assemblies formed by hydrophobic interaction are more bulky compared to those in the hydrated state.     

Effects of water and alcohol on the formation of inclusion complexes of d-limonene and cyclodextrins

Abstract

Systematic studies have been carried out on the role of water and alcohol in the formation of inclusion complexes between d-limonene and α-, β- and γ-cyclodextrin (CD) by a micro-aqueous method. The inclusion complex was barely formed at zero water content for all CDs. Above the specific water content for each CD, formation of the inclusion complex correlated well with an equation which was derived on the autocatalytic assumption for the inclusion phenomenon. The inclusion complex correlated well with an equation which was derived on the autocatalytic assumption for the inclusion phrnomenon. The minimum water content, which was defined as 1% of the maximum concentration of the inclusion complex formed, coincided with the number of water molecules inside the cavity of the CD. In the presence of ethanol, a significant amount of the inclusion complex was formed for β- and γ-CD/limonene systems, particularly at lower moisture content. However, for α-CD the inclusion fraction decreased significantly in the presence of ethanol. This means that ethanol inhibits the formation of the inclusion complex between x-CD and d-limonene. For other linear alcohols, the formation of the inclusion complex between d-limonene and β-CD increased with decreasing alkyl chain length. This suggests that the more hydrophilic and the smaller (in molecular size) the alcohol is, the more enhanced is the inclusion of d-limonene to β-CD.     

Transmission positron images using imaging plates

As an image recording medium for transmission positron microscopes, imaging plates are quite useful and powerful. Imaging plates are also quite sensitive and the photon-stimulated luminescence (PSL) is linearly proportional to the positron intensity in six digits (10⁶). No bulky or expensive equipment is necessary to accommodate in vacuum. Imaging plates can be set under bright lights, this is different from the photographic films. Darkness is only required during exposure and transfer to a reader. Slow Positron Facility at KEK, Japan was used to study the effect of “mono-chromatic” positron beam. Specimens were set just in front of an imaging plate. After a certain time of exposure, the imaging plates were processed by a reader. Used imaging plates can be used repeatedly after erased by ultra-violet lights. Images through samples can be obtained. Similar experiments using non-monochromatic (white) positrons and electrons have been performed at Teikyo University of Science and Technology (TUST) and Research Reactor Institute, Kyoto Univ. (RRI). Sealed ²²Na positron source can be conveniently used for non-destructive tests.