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.

Development of a new modelling framework to estimate the C footprint from Basque dairy farms

19 p.

New climate scenario framework implementation in the GCAM integrated assessment model

48 p.

A primeira reforma psiquiátrica : uma história do tratamento moral

A presente dissertação tem como objetivo descrever o Tratamento Moral desenvolvido por Philippe Pinel no período que se estende do final do século XVIII ao início do século XIX em Paris. Trata-se de um novo método de tratamento da loucura baseado na normatização e em uma atitude mais humana de cuidado com o louco. O asilo torna-se símbolo desse modelo, hegemônico por mais de um século. Neste estudo, pretendemos descrever o que foi o Tratamento Moral, quais os fundamentos deste método e, principalmente quais as mudanças que engendrou na prática do cuidado da loucura. Para tanto, faremos uma breve descrição do tipo de tratamento dado ao louco no período que antecede o surgimento do Tratamento Moral em Paris. Com o Tratamento Moral, nasce a Psiquiatria como especialidade médica, surgem o alienista e o alienado, o asilo transforma-se em local de cura da loucura e a relação médico-paciente da seus primeiros passos. A partir de uma análise bibliográfica de fontes primárias e secundárias buscamos oferecer aos interessados neste tema dados sobre as bases e as práticas do tratamento iniciado por Pinel, parte da história da psiquiatria e da loucura que são constituintes da realidade psiquiátrica atual.

A retrofitting framework for pre-Northridge steel moment-frame buildings

In the 1994 M_w 6.7 Northridge and 1995 M_w 6.9 Kobe earthquakes, steel moment-frame buildings were exposed to an unexpected flaw. The commonly utilized welded unreinforced flange, bolted web connections were observed to experience brittle fractures in a number of buildings, even at low levels of seismic demand. A majority of these buildings have not been retrofitted and may be susceptible to structural collapse in a major earthquake.

This dissertation presents a case study of retrofitting a 20-story pre-Northridge steel moment-frame building. Twelve retrofit schemes are developed that present some range in degree of intervention. Three retrofitting techniques are considered: upgrading the brittle beam-to-column moment resisting connections, and implementing either conventional or buckling-restrained brace elements within the existing moment-frame bays. The retrofit schemes include some that are designed to the basic safety objective of ASCE-41 Seismic Rehabilitation of Existing Buildings.

Detailed finite element models of the base line building and the retrofit schemes are constructed. The models include considerations of brittle beam-to-column moment resisting connection fractures, column splice fractures, column baseplate fractures, accidental contributions from ``simple'' non-moment resisting beam-to-column connections to the lateral force-resisting system, and composite actions of beams with the overlying floor system. In addition, foundation interaction is included through nonlinear translational springs underneath basement columns.

To investigate the effectiveness of the retrofit schemes, the building models are analyzed under ground motions from three large magnitude simulated earthquakes that cause intense shaking in the greater Los Angeles metropolitan area, and under recorded ground motions from actual earthquakes. It is found that retrofit schemes that convert the existing moment-frames into braced-frames by implementing either conventional or buckling-restrained braces are effective in limiting structural damage and mitigating structural collapse. In the three simulated earthquakes, a 20% chance of simulated collapse is realized at PGV of around 0.6 m/s for the base line model, but at PGV of around 1.8 m/s for some of the retrofit schemes. However, conventional braces are observed to deteriorate rapidly. Hence, if a braced-frame that employs conventional braces survives a large earthquake, it is questionable how much service the braces provide in potential aftershocks.

The EC Water Framework Directive and its implications for the Environment Agency

The bulk of the European Community's water policy legislation was developed between the mid 1970s and the early 1990s. These directives addressed specific substances, sources, uses or processes but caused problems with differing methods definitions and aims. The Water Framework Directive (WFD) aims to resolve the piecemeal approach. The Environemnt Agency (EA) welcomes and supported the overall objective of establishing a coherent legislative framework. The EA has been discussing the implications of the WFD with European partners and has developed a timetable for the implementation and a special team will commission necessary research.

Preparation for implementing the proposed EC Water Framework Directive in Finland

Finland reorganised its environmental administration in 1995 when thirteen Regional Environmental Centres (RECs) and one national agency called the Finnish Environment Institute (FEI) were created. The REC's and the FEI have been entrusted with functions related to water resources management. RECs and FEI together with the Ministry of Agriculture and Foresty have appointed a steering group which will supervise the implementation of the EC Water Framework Directive in Finland

Monitoring fish populations in Lower Lough Erne, Northern Ireland: applicability of current methods and implications for future monitoring under the EC Water Framework Directive

The proposed EC Water Framework Directive (WFD) will require member states to monitor both biotic and abiotic components of lake environments. With adoption of the WFD some measurement of fish populations will also be required. This paper describes work carried out since 1971, and particularly since 1991, on the status of fish populations in Lower Lough Erne, Northern Ireland, with an emphasis on defining change over time due to human impacts on the lake. This offers a reasonable starting point from which to develop a monitoring programme suitable for the needs of the WFD in this lake. The implications for as yet unmonitored fish populations in lakes are also determined.