The importance of attractive three-point interaction in enantioselective surface chemistry: stereospecific adsorption of serine on the intrinsically chiral Cu{531} surface

Both enantiomers of serine adsorb on the intrinsically chiral Cu{531} surface in two different adsorption geometries, depending on the coverage. At saturation, substrate bonds are formed through the two oxygen atoms of the carboxylate group and the amino group (μ3 coordination), whereas at lower coverage, an additional bond is formed through the deprotonated β−OH group (μ4 coordination). The latter adsorption geometry involves substrate bonds through three side groups of the chiral center, respectively, which leads to significantly larger enantiomeric differences in adsorption geometries and energies compared to the μ3 coordination, which involves only two side groups. This relatively simple model system demonstrates, in direct comparison, that attractive interactions of three side groups with the substrate are much more effective in inducing strong enantiomeric differences in heterogeneous chiral catalyst systems than hydrogen bonds or repulsive interactions.

Comparison of different boundary layer surface schemes using single point micrometeorological field data

 In the last decade, a vast number of land surface schemes has been designed for use in global climate models, atmospheric weather prediction, mesoscale numerical models, ecological models, and models of global changes. Since land surface schemes are designed for different purposes they have various levels of complexity in the treatment of bare soil processes, vegetation, and soil water movement. This paper is a contribution to a little group of papers dealing with intercomparison of differently designed and oriented land surface schemes. For that purpose we have chosen three schemes for classification: i) global climate models, BATS (Dickinson et al., 1986; Dickinson et al., 1992); ii) mesoscale and ecological models, LEAF (Lee, 1992) and iii) mesoscale models, LAPS (Mihailović, 1996; Mihailović and Kallos, 1997; Mihailović et al., 1999) according to the Shao et al. (1995) classification. These schemes were compared using surface fluxes and leaf temperature outputs obtained by time integrations of data sets derived from the micrometeorological measurements above a maize field at an experimental site in De Sinderhoeve (The Netherlands) for 18 August, 8 September, and 4 October 1988. Finally, comparison of the schemes was supported applying a simple statistical analysis on the surface flux outputs.

Source splitting via the point source method

We introduce a new algorithm for source identification and field splitting based on the point source method (Potthast 1998 A point-source method for inverse acoustic and electromagnetic obstacle scattering problems IMA J. Appl. Math. 61 119–40, Potthast R 1996 A fast new method to solve inverse scattering problems Inverse Problems 12 731–42). The task is to separate the sound fields uj, j = 1, ..., n of sound sources supported in different bounded domains G1, ..., Gn in from measurements of the field on some microphone array—mathematically speaking from the knowledge of the sum of the fields u = u1 + + un on some open subset Λ of a plane. The main idea of the scheme is to calculate filter functions , to construct uℓ for ℓ = 1, ..., n from u|Λ in the form We will provide the complete mathematical theory for the field splitting via the point source method. In particular, we describe uniqueness, solvability of the problem and convergence and stability of the algorithm. In the second part we describe the practical realization of the splitting for real data measurements carried out at the Institute for Sound and Vibration Research at Southampton, UK. A practical demonstration of the original recording and the splitting results for real data is available online.

Law of large numbers for super-brownian motions with a single point source

We investigate the super-Brownian motion with a single point source in dimensions 2 and 3 as constructed by Fleischmann and Mueller in 2004. Using analytic facts we derive the long time behavior of the mean in dimension 2 and 3 thereby complementing previous work of Fleischmann, Mueller and Vogt. Using spectral theory and martingale arguments we prove a version of the strong law of large numbers for the two dimensional superprocess with a single point source and finite variance.

Tobit estiamtion with unknown point of censoring with an application to milk market participation in the Ethiopian highlands

Data augmentation is a powerful technique for estimating models with latent or missing data, but applications in agricultural economics have thus far been few. This paper showcases the technique in an application to data on milk market participation in the Ethiopian highlands. There, a key impediment to economic development is an apparently low rate of market participation. Consequently, economic interest centers on the “locations” of nonparticipants in relation to the market and their “reservation values” across covariates. These quantities are of policy interest because they provide measures of the additional inputs necessary in order for nonparticipants to enter the market. One quantity of primary interest is the minimum amount of surplus milk (the “minimum efficient scale of operations”) that the household must acquire before market participation becomes feasible. We estimate this quantity through routine application of data augmentation and Gibbs sampling applied to a random-censored Tobit regression. Incorporating random censoring affects markedly the marketable-surplus requirements of the household, but only slightly the covariates requirements estimates and, generally, leads to more plausible policy estimates than the estimates obtained from the zero-censored formulation

Glycogen synthase kinase 3 (GSK3) in the heart: a point of integration in hypertrophic signalling and a therapeutic target? A critical analysis

Glycogen synthase kinase 3 (GSK3, of which there are two isoforms, GSK3alpha and GSK3beta) was originally characterized in the context of regulation of glycogen metabolism, though it is now known to regulate many other cellular processes. Phosphorylation of GSK3alpha(Ser21) and GSK3beta(Ser9) inhibits their activity. In the heart, emphasis has been placed particularly on GSK3beta, rather than GSK3alpha. Importantly, catalytically-active GSK3 generally restrains gene expression and, in the heart, catalytically-active GSK3 has been implicated in anti-hypertrophic signalling. Inhibition of GSK3 results in changes in the activities of transcription and translation factors in the heart and promotes hypertrophic responses, and it is generally assumed that signal transduction from hypertrophic stimuli to GSK3 passes primarily through protein kinase B/Akt (PKB/Akt). However, recent data suggest that the situation is far more complex. We review evidence pertaining to the role of GSK3 in the myocardium and discuss effects of genetic manipulation of GSK3 activity in vivo. We also discuss the signalling pathways potentially regulating GSK3 activity and propose that, depending on the stimulus, phosphorylation of GSK3 is independent of PKB/Akt. Potential GSK3 substrates studied in relation to myocardial hypertrophy include nuclear factors of activated T cells, beta-catenin, GATA4, myocardin, CREB, and eukaryotic initiation factor 2Bvarepsilon. These and other transcription factor substrates putatively important in the heart are considered. We discuss whether cardiac pathologies could be treated by therapeutic intervention at the GSK3 level but conclude that any intervention would be premature without greater understanding of the precise role of GSK3 in cardiac processes.

Comparison of different boundary layer surface schemes using single point micrometeorological field data

 In the last decade, a vast number of land surface schemes has been designed for use in global climate models, atmospheric weather prediction, mesoscale numerical models, ecological models, and models of global changes. Since land surface schemes are designed for different purposes they have various levels of complexity in the treatment of bare soil processes, vegetation, and soil water movement. This paper is a contribution to a little group of papers dealing with intercomparison of differently designed and oriented land surface schemes. For that purpose we have chosen three schemes for classification: i) global climate models, BATS (Dickinson et al., 1986; Dickinson et al., 1992); ii) mesoscale and ecological models, LEAF (Lee, 1992) and iii) mesoscale models, LAPS (Mihailović, 1996; Mihailović and Kallos, 1997; Mihailović et al., 1999) according to the Shao et al. (1995) classification. These schemes were compared using surface fluxes and leaf temperature outputs obtained by time integrations of data sets derived from the micrometeorological measurements above a maize field at an experimental site in De Sinderhoeve (The Netherlands) for 18 August, 8 September, and 4 October 1988. Finally, comparison of the schemes was supported applying a simple statistical analysis on the surface flux outputs.