New Cu-Based Catalysts Supported on TiO2 Films for Ullmann SNAr-Type C-O Coupling Reactions

New routes for the preparation of highly active TiO2-supported Cu and CuZn catalysts have been developed for C-O coupling reactions. Slurries of a titania precursor were dip-coated onto glass beads to obtain either structured mesoporous or non-porous titania thin films. The Cu and CuZn nanoparticles, synthesized using a reduction by solvent method, were deposited onto calcined films to obtain a Cu loading of 2 wt%. The catalysts were characterized by inductively coupled plasma (ICP) spectroscopy, temperature-programmed oxidation/reduction (TPO/TPR) techniques, Cu-63 nuclear magnetic resonance (NMR) spectroscopy, X-ray diffraction (XRD), scanning and transmission electron microscopy (S/TEM-EDX) and X-ray photo-electron spectroscopy (XPS). The activity and stability of the catalysts obtained have been studied in the C-O Ullmann coupling of 4-chloropyridine and potassium phenolate. The titania-supported nanoparticles retained catalyst activity for up to 12 h. However, catalyst deactivation was observed for longer operation times due to oxidation of the Cu nanoparticles. The oxidation rate could be significantly reduced over the CuZn/TiO2 catalytic films due to the presence of Zn. The 4-phenoxypyridine yield was 64% on the Cu/nonporous TiO2 at 120 degrees C. The highest product yield of 84% was obtained on the Cu/mesoporous TiO2 at 140 degrees C, corresponding to an initial reaction rate of 104 mmol g(cat)(-1) s(-1). The activation energy on the Cu/mesoporous TiO2 catalyst was found to be (144 +/- 5) kJ mol(-1), which is close to the value obtained for the reaction over unsupported CuZn nanoparticles (123 +/- 3 kJ mol(-1)) and almost twice the value observed over the catalysts deposited onto the non-porous TiO2 support (75 +/- 2 kJ mol(-1)).

Supported Housing for People with Severe Mental Disorders

Background There has been a significant reduction in the number of people with severe mental illness who spend extended periods in long-stay hospitals. District health authorities, local authorities, housing associations and voluntary organisations are jointly expected to provide support for people with severe mental disorder/s. This 'support' may well involve some kind of special housing. Objectives To determine the effects of supported housing schemes compared with outreach support schemes or 'standard care' for people with severe mental disorder/s living in the community. Search methods For the 2006 update we searched the Cochrane Schizophrenia Group Trials Register (April 2006) and the Cochrane Central Register of Controlled Trials (CENTRAL, 2006 Issue 2). Selection criteria We included all relevant randomised, or quasi-randomised, trials dealing with people with 'severe mental disorder/s' allocated to supported housing, compared with outreach support schemes or standard care. We focused on outcomes of service utilisation, mental state, satisfaction with care, social functioning, quality of life and economic data. Data collection and analysis We reliably selected studies, quality rated them and undertook data extraction. For dichotomous data, we would have estimated relative risks (RR), with the 95% confidence intervals (CI). Where possible, we would have calculated the number needed to treat statistic (NNT). We would have carried out analysis by intention-to-treat and would have summated normal continuous data using the weighted mean difference (WMD). We would have presented scale data for only those tools that had attained pre-specified levels of quality and undertaken tests for heterogeneity and publication bias. Main results Although 139 citations were acquired from the searches, no study met the inclusion criteria. Authors' conclusions Dedicated schemes whereby people with severe mental illness are located within one site or building with assistance from professional workers have potential for great benefit as they provide a 'safe haven' for people in need of stability and support. This, however, may be at the risk of increasing dependence on professionals and prolonging exclusion from the community. Whether or not the benefits outweigh the risks can only be a matter of opinion in the absence of reliable evidence. There is an urgent need to investigate the effects of supported housing on people with severe mental illness within a randomised trial.

A probabilistic modelling scheme for analysis of long-term failure of cemented femoral joint replacements

Reliable prediction of long-term medical device performance using computer simulation requires consideration of variability in surgical procedure, as well as patient-specific factors. However, even deterministic simulation of long-term failure processes for such devices is time and resource consuming so that including variability can lead to excessive time to achieve useful predictions. This study investigates the use of an accelerated probabilistic framework for predicting the likely performance envelope of a device and applies it to femoral prosthesis loosening in cemented hip arthroplasty.
A creep and fatigue damage failure model for bone cement, in conjunction with an interfacial fatigue model for the implant–cement interface, was used to simulate loosening of a prosthesis within a cement mantle. A deterministic set of trial simulations was used to account for variability of a set of surgical and patient factors, and a response surface method was used to perform and accelerate a Monte Carlo simulation to achieve an estimate of the likely range of prosthesis loosening. The proposed framework was used to conceptually investigate the influence of prosthesis selection and surgical placement on prosthesis migration.
Results demonstrate that the response surface method is capable of dramatically reducing the time to achieve convergence in mean and variance of predicted response variables. A critical requirement for realistic predictions is the size and quality of the initial training dataset used to generate the response surface and further work is required to determine the recommendations for a minimum number of initial trials. Results of this conceptual application predicted that loosening was sensitive to the implant size and femoral width. Furthermore, different rankings of implant performance were predicted when only individual simulations (e.g. an average condition) were used to rank implants, compared with when stochastic simulations were used. In conclusion, the proposed framework provides a viable approach to predicting realistic ranges of loosening behaviour for orthopaedic implants in reduced timeframes compared with conventional Monte Carlo simulations.

Synthesis of mesoporous tungsten carbide-supported platinum and its electrocatalytic activity for methanol oxidation

High activity and stability during oxidation of methanol under the relatively anode environment are two main evaluation criterias for an effective anode electrocatalyst in direct methanol fuel cell (DMFC). Mesoporous WC samples with hollow structure were prepared by gas-solid reaction at the atmosphere of CH(4)/H(2) by using airflow spray dried ammonium metatungstate (AMT). The platinum supported on this material by impregnation-vapor phase deoxidation method served as a less expensive electro anode catalyst. XRD and SEM results showed that Pt particles were well dispersed on the surface of WC. The results showed that the Pt/WC-PME exhibited an attractive catalytic activity, and methanol oxidation process in Pt/WC-PME is affected by liquid-phase mass transfer. The results also indicated that the oxidation can be improved by raising temperatures.

Selective Hydrogenation of alpha,beta-Unsaturated Aldehydes and Ketones using Novel Manganese Oxide and Platinum Supported on Manganese Oxide Octahedral Molecular Sieves as Catalysts

The selective hydrogenation of ,-unsaturated aldehydes and ketones has been studied using ketoisophorone and cinnamaldehyde as model substrates using manganese oxide octahedral molecular sieve (OMS-2) based catalysts. For the first time, OMS-2 has been shown to be an efficient and selective hydrogenation catalyst. High selectivities for either the CC or CO double bond at approximate to 100% conversion were achieved by using OMS-2 and platinum supported on OMS-2 catalysts. Density functional theory (DFT) calculations showed that the dissociation of H2 on OMS-2 was water assisted and occurred on the surface Mn of OMS-2(001) that had been modified by an adsorbed H2O molecule. The theoretically calculated activation barrier was in good agreement with the experimentally determined value for the hydrogenation reactions, indicating that H2 dissociation on OMS-2 is likely to be the rate-determining step. A significant increase in the rate of reaction was observed in the presence of Pt as a result of the enhancement of H2 dissociative adsorption and subsequent reaction on the Pt or spillover of the hydrogen to the OMS-2 support. The relative adsorption strengths of ketoisophorone and cinnamaldehyde on the OMS-2 support compared with the Pt were found to determine the product selectivity.

Chiral supported ionic liquid phase (CSILP) catalysts for greener asymmetric hydrogenation processes

Chiral supported ionic liquid phase (CSILP) catalysts were prepared by physical adsorption (within highly porous carbons or mesoporous silica) of Ir, Ru and Rh complexes as IrCl(COD)-(S, S)-BDPP, [IrCl-(S)-BINAP](2), RuCl(p-cymene)[(S, S)-Ts-DPEN], RuOTf(p-cymene)[(S, S)-Ts-DPEN], [Rh(COD)(S, S)-DIPAMP][BF4], and [Rh(COD)(R, R)-Me-DuPHOS][BF4]. For the syntheses of CSILP catalysts [EMIM][NTf2], [BMIM][BF4] and [BMIM][PF6] ionic liquids were used. Comparative homogeneous and heterogeneous experiments were carried out using the asymmetric hydrogenation of double -C N- and -C C- bonds in trimethylindolenine, 2-methylquinoline and dimethylitaconate, respectively. The conversion and enantioselectivity was found to depend on the nature of the complex (metal and ligand), the immobilization method used, nature of the ionic liquid, nature of the support and the experimental conditions. (C) 2012 Elsevier B.V. All rights reserved.

Redispersion of Gold Supported on Oxides

Although many gold heterogeneous catalysts have been shown to exhibit significant activity and high selectivity for a wide range of reactions in both the liquid and gas phases, they are prone to irreversible deactivation. This is often associated with sintering or loss of the interaction of the gold with the support. Herein, we report on the use of methyl iodide as a method of dispersing gold nanoparticles supported on silica, titania, and alumina supports. In the case of titania- and alumina-based catalysts, the gold was transformed from nanometer particles into small clusters and some atomically dispersed gold. In contrast, although there was a drop in the gold particle size on the silica support following CH3I treatment, the size remained in the submicrometer range. The structural changes were correlated with changes in the selectivity and activity for ethanol dehydration and benzyl alcohol oxidation. From these observations, it is clear that this treatment provides a method by which deactivated gold catalysts can be reactivated via redispersion of the gold.