Solvent effects on oxygen atom transfer reaction between manganese(V)-oxo corrole and alkene

Pseudo-first order reaction rate constants of 5,10,15-tris（pentafluorophenyl）corrole Mn（V）-oxo (F₁₅CMn（V）-oxo),5,15-bis（pentafluorophenyl）-10-（phenyl）corrole Mn（V）-oxo(F₁₀CMn（V）-oxo),5,15- bis（phenyl）-10-（pentafluorophenyl）corrole Mn（V）-oxo（F₅CMn（V）-oxo） and 5,10,15-tris（phenyl）corrole Mn（V）-oxo（F₀CMn（V）-oxo） with a series of alkene substrates in different solvents were determined by UV-vis spectroscopy.The results indicated that the oxygen atom transfer pathway between Mn（V）-oxo corrole and alkene is solvent-dependent.     

The centroid method of numerical integration

Summary The midpoint method of integration of a function of one variable is perhaps the simplest method of numerical integration, although it is often not mentioned in textbooks. It is here generalized to any number of dimensions and the generalization is called thecentroid method. This again is a very simple method and it can be conveniently used, for example, for the integration of a function of several variables over any non-pathological region. The numerical examples include the integration of multinormal integrands.     

β-Octafluorinated tetrakis(ethoxycarbonyl)porphyrin

Tetrakis(alloxycarbonyl)porphyrin and its β-octafluoro-substituted derivatives were synthesized via Lindsey method and transformed to their zinc complexes.Single crystal X-ray structures of corresponding Zn(Ⅱ) porphyrins revealed that β-octafluorination will give more compactness of porphyrin moieties in the crystal structure owing to the hydrogen bonding interactions involving β-fluorine atoms.An unusual six-coordinated Zn(Ⅱ) was found via intramolecular coordination of oxygen atom of meso-substituents with central Zn(Ⅱ).     

Sparsity Inducing Prior Distributions for Correlation Matrices of Longitudinal Data

For longitudinal data, the modeling of a correlation matrix ?R can be a difficult statistical task due to both the positive definite and the unit diagonal constraints. Because the number of parameters increases quadratically in the dimension, it is often useful to consider a sparse parameterization. We introduce a pair of prior distributions on the set of correlation matrices for longitudinal data through the partial autocorrelations (PACs), which vary independently over (?1,1). The first prior shrinks each of the PACs toward zero with increasingly aggressive shrinkage in lag. The second prior (a selection prior) is a mixture of a zero point mass and a continuous component for each PAC, allowing for a sparse representation. The structure implied under our priors is readily interpretable for time-ordered responses because each zero PAC implies a conditional independence relationship in the distribution of the data. Selection priors on the PACs provide a computationally attractive alternative to selection on the elements of ?R or ?R^{? 1} for ordered data. These priors allow for data-dependent shrinkage/selection under an intuitive parameterization in an unconstrained setting. The proposed priors are compared to standard methods through a simulation study and illustrated using a multivariate probit data example. Supplemental materials for this article (appendix, data, and R code) are available online.     

Cell migration and polarity on microfabricated gradients of extracellular matrix proteins

This paper explores the effects of the surface density and concentration profiles of extra cellular matrix proteins on the migration of rat intestinal IEC-6 cells. Microfluidic devices were used to create linear, immobilized gradients of laminin. This study investigated both the impact of the steepness and local concentrations on the directedness of cell migration. The bulk concentrations of proteins in the feed streams in the mixing device determined the gradient profile and the local concentration of laminin in the device. Two sets of gradients were used to explore cell migration directedness: (i) gradients with similar change in local concentration, i.e., the same gradient steepness, and (ii) different gradients with similar local concentrations. Cells migrated up the gradients, independent of the steepness of the gradients used in this study. At the same local laminin concentration, the migration rate was independent of the gradient steepness. However, cell directedness decreased significantly at high laminin densities.     

Covariance Partition Priors: A Bayesian Approach to Simultaneous Covariance Estimation for Longitudinal Data

The estimation of the covariance matrix is a key concern in the analysis of longitudinal data. When data consist of multiple groups, it is often assumed the covariance matrices are either equal across groups or are completely distinct. We seek methodology to allow borrowing of strength across potentially similar groups to improve estimation. To that end, we introduce a covariance partition prior that proposes a partition of the groups at each measurement time. Groups in the same set of the partition share dependence parameters for the distribution of the current measurement given the preceding ones, and the sequence of partitions is modeled as a Markov chain to encourage similar structure at nearby measurement times. This approach additionally encourages a lower-dimensional structure of the covariance matrices by shrinking the parameters of the Cholesky decomposition toward zero. We demonstrate the performance of our model through two simulation studies and the analysis of data from a depression study. This article includes Supplementary Materials available online.     

Unexpected one-pot synthesis of A3-type unsymmetrical porphyrin

The first direct synthesis of A₃-type unsymmetrical porphyrin is achieved via conventional pyrrole–aldehyde condensation in a one-pot procedure in an appreciable yield. Generalization of this approach to a variety of other aldehydes revealed that it is advantageous for highly electron-rich aldehydes giving unsymmetrical porphyrin, while electron-poor aldehydes even failed to cyclize under the same experimental conditions.     

Appended corrole manganese complexes:Catalysis and axial-ligand effect

A series of N-base appended corroles and their manganese complexes were synthesized and their binding constants with three different nitrogenous ligands, triethylamine, N-methylimidazole and pyridine, were evaluated by spectroscopy. Kinetic studies indicated that the presence of appended N- donor ligands may cause a significant enhancement of the rate of oxygen atom transfers （OAT） from （oxo）manganese（V） corrole to alkene, and the stronger axial ligand binding has impact on the rate of the oxidation reaction. Turnover frequency （TOF） for the catalytic oxidation of alkenes by appended manganese corroles varies with the following ligand order： acetamido 〈 pyridyl 〈 imidazolyl. The influence of the external axial ligands on the catalytic epoxidation was investigated by using appended acetamido manganese corrole as catalyst, with the results revealing that N-methylimidazole gave the best enhancement on the yields of total oxidation products among the investigated nitrogenous ligands.     

A review of indirect searches for particle dark matter

The indirect detection of dark matter annihilation and decay using observations of photons, charged cosmic rays and neutrinos offers a promising means of identifying the particle nature of this elusive component of the universe. The last decade has seen substantial advances in observational data-sets, complemented by new insights from numerical simulations, which together have enabled for the first time strong constraints on dark matter particle models, and have revealed several intriguing hints of possible signals. This review provides an introduction to indirect detection methods and an overview of recent results in the field.