Computational Insights of Selective Intramolecular O-atom Transfer Mediated by Bioinspired Copper Complexes

The stereoselective copper-mediated hydroxylation of intramolecular C−H bonds from tridentate ligands is reinvestigated using DFT calculations. The computational study aims at deciphering the mechanism of C−H hydroxylation obtained after reaction of Cu(I) precursors with dioxygen, using ligands bearing either activated ( L¹ ) or non-activated ( L² ) C−H bonds. Configurational analysis allows rationalization of the experimentally observed regio- and stereoselectivity. The computed mechanism involves the formation of a side-on peroxide species ( P ) in equilibrium with the key intermediate bis-(μ-oxo) isomer ( O ) responsible for the C−H activation step. The P/O equilibrium yields the same activation barrier for the two complexes. However, the main difference between the two model complexes is observed during the C−H activation step, where the complex bearing the non-activated C−H bonds yields a higher energy barrier, accounting for the experimental lack of reactivity of this complex under those conditions.     

Isolated singularities of polyharmonic inequalities

We study nonnegative classical solutions u of the polyharmonic inequality

     

Improvements for ground-based remote sensing of atmospheric aerosol properties by additional polarimetric measurements

We discuss the improvements in the aerosol properties characterization resulting from the additional multi-wavelength polarization measurements measured by a new CIMEL polarized sun/sky-photometer, CE318-DP. In order to process direct-sun, sky and polarization measurements in a wide spectral range (340–1640 nm), we developed new calibration methods and strategies, e.g. using the Langley plot method to calibrate both direct-sun irradiance and sky radiance, as well as combining laboratory facilities with a vicarious method to calibrate the polarized sky measurements. For studying the impact of new polarimetric measurements on the retrievals of aerosol properties, we have processed an extensive record of field measurements using an updated Dubovik and King retrieval algorithm [Dubovik O, Sinyuk A, Lapyonok T, Holben BN, Mishchenko MI, et al. Application of spheroid models to account for aerosol particle nonsphericity in remote sensing of desert dust. J Geophys Res 2006;111:D11208.]. A preliminary analysis shows that adding polarization in the inversion can reduce possible errors (notably for about 30% of our field cases) in the fine mode size distribution, real part of refractive index and particle shape parameter retrievals, especially for small particles.     

Predicted binding rate of new cephalosporin antibiotics by a 3D-QSAR method: a new approach

Abstract  

Antibiotics are chemotherapeutic agents with activity against microorganisms, for example bacteria, fungi, or protozoa, used for the treatment of many types of diseases. Binding of antibiotics to serum proteins in human plasma is a major determinant of their pharmacodynamic and pharmacokinetic behavior and, consequently, can affect their systemic distribution in the body. Here, the predicted binding rates of ceftazidime and 13 other pharmacological agents classified as antibiotics to plasma proteins (percentage fraction bound; PFB) were evaluated by use of 3D-QSAR models. We attempted to establish the contribution of hydrogen bond donor/acceptor and hydrophobic properties supplied by electrostatic fields to the PFB. Significant cross-validated correlation q ² (0.5–0.7) and the fitted correlation r ² (0.7–0.97) coefficients revealed that these models have reasonable power to predict the design 19 new antibiotics using ceftazidime as template, these compounds being our suggestion for further studies.     

A note on Besov regularity of layer potentials and solutions of elliptic PDE's

Let be a second order, (variable coefficient) elliptic differential operator and let , , 0$">, satisfy in the Lipschitz domain . We show that can exhibit more regularity on Besov scales for which smoothness is measured in with . Similar results are valid for functions representable in terms of layer potentials.

     

The first coordination compound containing three different types of spin carriers: 2p-3d-4f (TCNQ.-, Cu2+ and Gd3+)

A novel heterospin system, [(CuL)2Gd(TCNQ)2].TCNQ-.CH3OH.2CH3CN, is obtained by reacting the mononuclear complex, [CuL], with gadolinium(III) nitrate, followed by the substitution of the nitrato ions with anionic organic radicals.     

Using conjoined rigid body/torsion angle simulated annealing to determine the relative orientation of covalently linked protein domains from dipolar couplings

A simple and robust method for determining the relative orientations of covalently linked protein domains using conjoined rigid body/torsion angle dynamics simulated annealing on the basis of residual dipolar couplings is presented. In this approach each domain is treated as a rigid body and the relevant degrees of conformational freedom are restricted to the backbone torsion angles (phi, psi) of the linker between the domains. By this means translational information afforded by the presence of an intact linker is preserved. We illustrate this approach using the domain-swapped dimer of the HIV-inactivating protein cyanovirin-N as an example.     

Convergence of Appell Polynomials of Long Range Dependent Moving Averages in Martingale Differences

We study limit distribution of partial sums S_N,k(t) = _{s = 1} ^{[N t]} A_k(X_s) of Appell polynomials of the long-range dependent moving average process X_t> = _{i t} b_{t - i i}, where {_i} is a strictly stationary and weakly dependent martingale difference sequence, and b_i i^{d - 1} (0 < d < 1/2). We show that if k(1-2 d)<1, then suitably normalized partial sums S_N,k(t) converge in distribution to the kth order Hermite process. This result generalizes the corresponding results of Surgailis, and Avram and Taqqu obtained in the case of the i.i.d. sequence { _i}.     

Cyclic Cohomology of étale Groupoids: The General Case

We give a general method for computing the cyclic cohomology of crossed products by étale groupoids, extending the Feigin–Tsygan–Nistor spectral sequences. In particular we extend the computations performed by Brylinski, Burghelea, Connes, Feigin, Karoubi, Nistor, and Tsygan for the convolution algebra C _c (G) of an étale groupoid, removing the Hausdorffness condition and including the computation of hyperbolic components. Examples like group actions on manifolds and foliations are considered.