Reaction of glucose catalyzed by framework and extraframework tin sites in zeolite beta

The isomerization of glucose into fructose is a large-scale reaction for the production of high-fructose corn syrup, and is now being considered as an intermediate step in the possible route of biomass conversion into fuels and chemicals. Recently, it has been shown that a hydrophobic, large pore, silica molecular sieve having the zeolite beta structure and containing framework Sn⁴⁺ (Sn-Beta) is able to isomerize glucose into fructose in aqueous media. Here, I have investigated how this catalyst converts glucose to fructose and show that it is analogous to that achieved with metalloenzymes. Specifically, glucose partitions into the molecular sieve in the pyranose form, ring opens to the acyclic form in the presence of the Lewis acid center (framework Sn⁴⁺), isomerizes into the acyclic form of fructose and finally ring closes to yield the furanose product. Akin to the metalloenzyme, the isomerization step proceeds by intramolecular hydride transfer from C2 to C1. Extraframework tin oxides located within hydrophobic channels of the molecular sieve that exclude liquid water can also isomerize glucose to fructose in aqueous media, but do so through a base-catalyzed proton abstraction mechanism. Extraframework tin oxide particles located at the external surface of the molecular sieve crystals or on amorphous silica supports are not active in aqueous media but are able to perform the isomerization in methanol by a base-catalyzed proton abstraction mechanism. Post-synthetic exchange of Na⁺ with Sn-Beta alters the glucose reaction pathway from the 1,2 intramolecular hydrogen shift (isomerization) to produce fructose towards the 1,2 intramolecular carbon shift (epimerization) that forms mannose. Na⁺ remains exchanged onto silanol groups during reaction in methanol solvent, leading to a near complete shift in selectivity towards glucose epimerization to mannose. In contrast, decationation occurs during reaction in aqueous solutions and gradually increases the reaction selectivity to isomerization at the expense of epimerization. Decationation and concomitant changes in selectivity can be eliminated by addition of NaCl to the aqueous reaction solution. Thus, framework tin sites with a proximal silanol group are the active sites for the 1, 2 intramolecular hydride shift in the isomerization of glucose to fructose, while these sites with Na-exchanged silanol group are the active sites for the 1, 2 intramolecular carbon shift in epimerization of glucose to mannose.

Impact of polarized illumination on high NA imaging in ArF immersion lithography at 45 nm node

Immersion lithography has been considered as the mainstream technology to extend the feasibility of optical lithography to further technology nodes. Using proper polarized illumination in an immersion lithographic tool is a powerful means to enhance the image quality and process capability for high numerical aperture (NA) imaging. In this paper, the impact of polarized illumination on high NA imaging in ArF immersion lithography for 45 nm dense lines and semi-dense lines is studied by PROLITH simulation. The normalized image log slope (NILS) and exposure defocus (ED) window are simulated under various polarized illumination modes, and the impact of polarized illumination on image quality and process latitude is analyzed. (C) 2007 Elsevier GmbH. All rights reserved.

Formation and characterization of tin oxide aerogel derived from sol-gel process based on tetra(n-butoxy)tin(IV)

Transparent and translucent SnO2 aerogels with high specific surface area (>300m(2)/g) have been prepared by sol-gel process using tetra(n-butoxy)tin(IV) as a starting compound, and supercritical drying technique for solvent extraction. Light scattering measurements reveal that the polymeric cluster size distribution in sol system is gradually broadened during sol-gel transition. SEM images show that the aerogels are made up of the cottonlike oxide agglomerates with a large number of Pores. TEM images show that these aerogels seem to be self-similar at different magnifications. Their pore size distribution is pretty wide ranging, from mesopore to macropore especially for that of translucent aerogel. (C) 2004 Elsevier B.V. All rights reserved.

Humoral and protective response of Indian major carps to immersion vaccination with Aeromonas hydrophila

Fry of the Indian major carps, Catta catla (Ham.), Labeo rohita (Ham.) and Cirrhinus mrigala (Ham.) were immunized at 4 and 8 weeks post hatching (wph) by direct immersion in a suspension (10 super(8) cells ml super(-1))of heat inactivated Aeromonas hydrophila. Following the same procedure, booster dose was administered 20 days after the first immersion. Antibodies as well as protective response produced in both the groups after the first and the booster immersion were different and significant (P<0.05). No significant difference was found between the species in the two age groups. The specimens immunized 8 wph showed higher antibody titres and protection than the 4 wph group. C. catla had higher relative percent survival followed by L. rohita and C. mrigala.

Investigations on wooden floating materials: the loss of buoyancy under continuous immersion in water and the rate of its redemption by drying

A wooden fishing float under immersion in water for long periods is liable to absorb water, the quantity of water absorbed possibly being dependent upon the physical factors like the specific gravity and the inherent property of the material, the time of soaking and the pressure acting on it. Consequently a wooden float is likely to become heavy and loss its original buoyancy. However, when the float is removed from water and dried, the lost buoyancy is regained on complete drying. The present paper is an attempt to elucidate these two important characteristics of some of the chief wooden floating materials used on the West Coast of India.

Experimental formulation of an anti fouling paint with tributyl tin oxide as toxic pigment

Results of the experimental formulation of an antifouling paint incorporating TBTO as toxic pigment are presented in this paper. Of the various resins tested, namely, phenolic, cashew nut shell liquid (CNSL), epoxy linseed oil with rosin and limed rosin, the paint composition with limed rosin gave the critical leaching rate of TBTO. Acid alkali test showed dissolution of matrix and visible migration of toxin to the surface. Accelerated corrosion tests had not recorded any signs of corrosion in panels painted with or without barrier coat. Raft exposure studies indicated that the new formulation could resist fouling accumulation on painted panels for 9 months.