Silica-magnesium-titanium Ziegler-Natta catalysts. Part 1: Structure of the pre-catalyst at a molecular level

In this paper, which is the first part of a more extended work, we elucidate the molecular level structure of a highly active SiO2-supported Ziegler-Natta precatalyst obtained by reacting a dehydroxylated silica and a solution of an organomagnesium compound with TiCl4. The synergetic combination of Ti K-edge and Ti L3-edge X-ray Absorption spectroscopy (XAS) and diffuse reflectance UV–Vis spectroscopies, complemented by Density Functional Theory (DFT) simulations, indicate that small TiCl3 clusters similar to β-TiCl3 coexist with isolated monomeric Ti(IV) species. Ti K-edge Extended X-ray Absorption Fine Structure (EXAFS) Spectroscopy allows the quantification of these two phases and demonstrates that the Ti(IV) sites are 6-fold coordinated (either by six chlorine ligands or by five chlorine and one oxygen ligands), but highly distorted, similar to what is modelled for TiCl4-capped MgCl2 nanoplatelets. Finally, IR spectroscopy suggests that the MgCl2 phase has a molecular character (Far-IR) and that the only accessible Mg2+ sites are uncoordinated cations acting as Lewis acid sites (IR of CO adsorbed at 100 K). Based on these experimental findings, we propose the co-existence in the precatalyst of small TiCl3 clusters and of mixed oxo-chloride magnesium-titanium structures deposited at the silica surface. The evolution of the precatalyst in the presence of the activator and of the monomer is discussed in the second part of this work

Population pharmacokinetic and pharmacodynamic properties of intramuscular quinine in Tanzanian children with severe Falciparum malaria.

Although artesunate is clearly superior, parenteral quinine is still used widely for the treatment of severe malaria. A loading-dose regimen has been recommended for 30 years but is still often not used. A population pharmacokinetic study was conducted with 75 Tanzanian children aged 4 months to 8 years with severe malaria who received quinine intramuscularly; 69 patients received a loading dose of 20 mg quinine dihydrochloride (salt)/kg of body weight. Twenty-one patients had plasma quinine concentrations detectable at baseline. A zero-order absorption model with one-compartment disposition pharmacokinetics described the data adequately. Body weight was the only significant covariate and was implemented as an allometric function on clearance and volume parameters. Population pharmacokinetic parameter estimates (and percent relative standard errors [%RSE]) of elimination clearance, central volume of distribution, and duration of zero-order absorption were 0.977 liters/h (6.50%), 16.7 liters (6.39%), and 1.42 h (21.5%), respectively, for a typical patient weighing 11 kg. Quinine exposure was reduced at lower body weights after standard weight-based dosing; there was 18% less exposure over 24 h in patients weighing 5 kg than in those weighing 25 kg. Maximum plasma concentrations after the loading dose were unaffected by body weight. There was no evidence of dose-related drug toxicity with the loading dosing regimen. Intramuscular quinine is rapidly and reliably absorbed in children with severe falciparum malaria. Based on these pharmacokinetic data, a loading dose of 20 mg salt/kg is recommended, provided that no loading dose was administered within 24 h and no routine dose was administered within 12 h of admission. (This study has been registered with Current Controlled Trials under registration number ISRCTN 50258054.)

The legacy of cover crops on the soil habitat and ecosystem services in a heavy clay, minimum tillage rotation

Abstract Cover crops are grown as potential ways to improve soil fertility, soil structure, and biodiversity, while reducing weed/pest burdens. Yet, increased costs (in both time and fuel), farmer knowledge requirements, and yield uncertainty (green bridge effect and variable crop establishment) have led to hesitation among farmers. This study was conducted at the field scale (covering an area of nearly 20 hectares) to determine whether different cover crop mixtures affected soil properties and ecosystem services on a heavy clay soil. Measurements of soil chemistry, physics, biology, weed abundance, and subsequent crop performance were taken within a minimum tillage management system, across three cover crop mixtures (commonly sold to UK farmers). The cover crop mixtures included oats (Avena sativa), radish (Raphanus sativus), phacelia (Phacelia tanacetifolia), vetch (Vicia sativa), legumes, buckwheat (Fagopyrum esculentum) and a bare stubble control followed by a spring oat crop. Soil physics (penetrometer and bulk density) and chemistry (N, P, K, Mg, Ca, and organic matter) varied little across treatments, although there was significantly lower Mg in the cover crop including legumes and an increase in NO3 within this treatment. Soil biology and botanical composition were also assessed, monitoring earthworm and mesofauna abundance; and sown and unsown (weed) biomass. Epigeic earthworms were found to have significantly larger abundance in cover crop mixtures with radish present, although other meso- and macrofauna did not differ. Significant weed suppression was found during both the cover crop growing period and as a legacy in the subsequent crop, leading to significant yield increases and economic benefits in some treatments. Our study confirms that cover crops are providing benefits, even on heavy clay soils, including improvements in nutrient leaching risk reduction, weed suppression, and crop yield, coupled with wider ecosystem benefits. We therefore consider cover crops to have a role in sustainable management of arable rotations

Direct and inverse spectral transform for the relativistic Toda lattice and the connection with Laurent orthogonal polynomials

We introduce a spectral transform for the finite relativistic Toda lattice (RTL) in generalized form. In the nonrelativistic case, Moser constructed a spectral transform from the spectral theory of symmetric Jacobi matrices. Here we use a non-symmetric generalized eigenvalue problem for a pair of bidiagonal matrices (L,M) to define the spectral transform for the RTL. The inverse spectral transform is described in terms of a terminating T-fraction. The generalized eigenvalues are constants of motion and the auxiliary spectral data have explicit time evolution. Using the connection with the theory of Laurent orthogonal polynomials, we study the long-time behaviour of the RTL. As in the case of the Toda lattice the matrix entries have asymptotic limits. We show that L tends to an upper Hessenberg matrix with the generalized eigenvalues sorted on the diagonal, while M tends to the identity matrix.Comment: 24 pages, 9 figure

Effects of repeated annual influenza vaccination on vaccine sero-response in young and elderly adults

Three cohort studies in adults were performed during the period from 1986 to 1989. Eight hundred and eighty-four subjects were, one or more times, immunized with influenza vaccines, and pre- and post-vaccination antibody titres were determined by hemagglutination inhibition tests. One thousand and one hundred and nineteen vaccination events in 681 subjects could be analysed by a comparison, per trial and per influenza (sub)type, between groups with and without influenza vaccination in previous years. Effect size, odds ratio and protection rate difference, were used as effect measures. Subjects with previous vaccination showed higher pre-vaccination antibody than those without. The average change of the post-vaccination proportion of subjects with high antibody titre value to previous vaccination, was +9.4% (95% CI: +5.3 to 13.6%) for A-H3N2 vaccine components, -2.1% (-8.1 to 3.9%, not significant) for A-H1N1 and -10.6% (-16.5% to -4.8%) for B. In a linear regression model, pre-vaccination titres and the status of previous vaccination were identified as factors significantly influencing post-vaccination titres. These findings are discussed in the context of a short review of the literature. It is concluded that the status of previous vaccination should always be addressed as an independent factor in serological vaccination studies