Perthamides C-F, potent human antipsoriatic cyclopeptides

Two new cyclopeptides, perthamides E and F were isolated from the polar extracts of the sponge Theonella swinhoei. The new structures, featuring an unprecedented β-amino acid unit (AHMOA), were determined by interpretation of NMR and MS data. The absolute configuration of the AHMOA residue was proposed on the basis of quantum chemical calculation of NMR chemical shifts. Perthamides were proved to inhibit TNF-α and IL-8 release in primary human keratinocytes cells and therefore could represent potentially leads for the treatment of psoriasis.     

Modular optimization of enantiopure epoxide-derived P,S-ligands for rhodium-catalyzed hydrogenation of dehydroamino acids

The optimization of P,S-ligands derived from enantiopure (2S,3S)-phenylglycidol for asymmetric rhodium-catalyzed hydrogenation of dehydroamino esters is described. The exceptionally high modular character of the (2S,3S)-phenylglycidol platform is demonstrated by systematic modification of the ether and thioether moieties, the skeletal aryl substituent and the stereo and regiochemistry of the ligands. An experimentally useful method for the monitoring of hydrogenation reactions is also described and used for obtaining relevant data of the catalytic systems studied.     

Wigner’s “Unreasonable Effectiveness of Mathematics”, Revisited

A famous essay by Wigner is reexamined in view of more recent developments around its topic, together with some remarks on the metaphysical character of its main question about mathematics and natural sciences.     

(E)-2-Benzylidenebenzocyclanones: Part VII. Investigation of the conjugation reaction of two cytotoxic cyclic chalcone analogues with glutathione: an HPLC–MS study

Abstract  

The non-enzyme-catalyzed reaction of reduced glutathione (GSH) with two tumor cell cytotoxic cyclic chalcone analogues was investigated by reversed-phase high-performance liquid chromatography (RP-HPLC). HPLC analysis of the reaction mixtures indicated the formation of two diastereomeric chalcone–GSH adducts in each case, whose structural assignments were supported by MALDI-TOF-MS and HPLC–MS with electrospray ionization (ESI) measurements. Such reactivity accounts for the previously observed effect of the two cyclic chalcone analogues on the in vivo cellular thiol level of Jurkat T cells.     

Resolvent metric and the heat kernel estimate for random walks

In this paper we introduce the resolvent metric, the generalization of the resistance metric used for strongly recurrent walks. By using the properties of the resolvent metric we show heat kernel estimates for recurrent and transient random walks.     

A perturbation-method-based a posteriori estimator for the planewave discretization of nonlinear Schrödinger equations

In this Note, we propose a new method, based on perturbation theory, to post-process the planewave approximation of the eigenmodes of periodic Schrödinger operators. We then use this post-processing to construct an accurate a posteriori estimator for the approximations of the (nonlinear) Gross–Pitaevskii equation, valid at each step of a self-consistent procedure. This allows us to design an adaptive algorithm for solving the Gross–Pitaevskii equation, which automatically refines the discretization along the convergence of the iterative process, by means of adaptive stopping criteria.     

A Framework for Characterizing Structural Uncertainty in Large-Eddy Simulation Closures

Motivated by the sizable increase of available computing resources, large-eddy simulation of complex turbulent flow is becoming increasingly popular. The underlying filtering operation of this approach enables to represent only large-scale motions. However, the small-scale fluctuations and their effects on the resolved flow field require additional modeling. As a consequence, the assumptions made in the closure formulations become potential sources of incertitude that can impact the quantities of interest. The objective of this work is to introduce a framework for the systematic estimation of structural uncertainty in large-eddy simulation closures. In particular, the methodology proposed is independent of the initial model form, computationally efficient, and suitable to general flow solvers. The approach is based on introducing controlled perturbations to the turbulent stress tensor in terms of magnitude, shape and orientation, such that propagation of their effects can be assessed. The framework is rigorously described, and physically plausible bounds for the perturbations are proposed. As a means to test its performance, a comprehensive set of numerical experiments are reported for which physical interpretation of the deviations in the quantities of interest are discussed.