Monofluoroalkene-Isostere as a 19F NMR Label for the Peptide Backbone: Synthesis and Evaluation in Membrane-Bound PGLa and (KIGAKI)3

Solid-state ¹⁹F NMR is a powerful method to study the interactions of biologically active peptides with membranes. So far, in labelled peptides, the ¹⁹F-reporter group has always been installed on the side chain of an amino acid. Given the fact that monofluoroalkenes are non-hydrolyzable peptide bond mimics, we have synthesized a monofluoroalkene-based dipeptide isostere, Val-Ψ[(Z)-CF=CH]-Gly, and inserted it in the sequence of two well-studied antimicrobial peptides: PGLa and (KIGAKI)₃ are representatives of an α-helix and a β-sheet. The conformations and biological activities of these labeled peptides were studied to assess the suitability of monofluoroalkenes for ¹⁹F NMR structure analysis.     

Tuning PtII-Based Donor–Acceptor Systems through Ligand Design: Effects on Frontier Orbitals,Redox Potentials,UV/Vis/NIR Absorptions,Electrochromism, and Photocatalysis

Asymmetric platinum donor–acceptor complexes [(pimp)Pt(Q²⁻)] are presented in this work, in which pimp=[(2,4,6-trimethylphenylimino)methyl]pyridine and Q²⁻=catecholate-type donor ligands. The properties of the complexes are evaluated as a function of the donor ligands, and correlations are drawn among electrochemical, optical, and theoretical data. Special focus has been put on the spectroelectrochemical investigation of the complexes featuring sulfonyl-substituted phenylendiamide ligands, which show redox-induced linkage isomerism upon oxidation. Time-dependent density functional theory (TD-DFT) as well as electron flux density analysis have been employed to rationalize the optical spectra of the complexes and their reactivity. Compound 1 ([(pimp)Pt(Q²⁻)] with Q²⁻=3,5-di-tert-butylcatecholate) was shown to be an efficient photosensitizer for molecular oxygen and was subsequently employed in photochemical cross-dehydrogenative coupling (CDC) reactions. The results thus display new avenues for donor–acceptor systems, including their role as photocatalysts for organic transformations, and the possibility to introduce redox-induced linkage isomerism in these compounds through the use of sulfonamide substituents on the donor ligands.     

Modeling of Wormhole Growth in Cold Production

Cold production is a non-thermal process in which sand is intentionally produced with the oil in order to enhance oil recovery. Two experiments were performed to investigate the effect of producing large quantities of sand on the overall permeability of a formation. A large high porosity channel (wormhole) was observed in both experiments. A model of wormhole growth was successfully tested in two sand production experiments simulating the growth of a wormhole from a perforation in a vertical well. The produced volumes of oil, sand and gas, the pressure distribution along the pack and the final length of the wormholes were well predicted. The two sand packs had significantly different cohesive strengths. The strength of the sand did not have a significant effect on the growth of the wormholes. The formation of tensile failure bands at the wormhole surface, as observed in the experiments, may weaken the sand and allow it to be fluidized more easily. This weakening effect would explain the lower pressure gradients calculated at the surface of the wormhole while it developed compared to the critical pressure gradient for sand production predicted by Bratli and Risnes (1981).     

Laser control of molecular excitations in stochastic dissipative media

In the present work, ideas for controlling photochemical reactions in dissipative environments using shaped laser pulses are presented. New time-local control algorithms for the stochastic Schro?dinger equation are introduced and compared to their reduced density matrix analog. The numerical schemes rely on time-dependent targets for guiding the reaction along a preferred path. The methods are tested on the vibrational control of adsorbates at metallic surfaces and on the ultrafast electron dynamics in a strong dissipative medium. The selective excitation of the specific states is achieved with improved yield when using the new algorithms. Both methods exhibit similar convergence behavior and results compare well with those obtained using local optimal control for the reduced density matrix. The favorable scaling of the methods allows to tackle larger systems and to control photochemical reactions in dissipative media of molecules with many more degrees of freedom.     

Spatial pseudoanalytic functions arising from the factorization of linear second order elliptic operators

Biquaternionic Vekua‐type equations arising from the factorization of linear second order elliptic operators are studied. Some concepts from classical pseudoanalytic function theory are generalized onto the considered spatial case. The derivative and antiderivative of a spatial pseudoanalytic function are introduced and their applications to the second order elliptic equations are considered. Copyright © 2011 John Wiley & Sons, Ltd.     

A new class of generalized Apostol–Bernoulli polynomials and some analogues of the Srivastava–Pintér addition theorem

The main purpose of this paper is to introduce and investigate a new class of generalized Apostol–Bernoulli polynomials based on a definition given by Natalini and Bernardini (2003) [22] for the generalized Bernoulli polynomials. We obtain a generalization of the Srivastava–Pintér addition theorem (Srivastava and Pintér (2004) [23]). We also give a list of expressions involving special functions that could be used to obtain some analogues of the Srivastava–Pintér addition theorem. Finally, we give an analogue featuring the new class of generalized Apostol–Bernoulli polynomials.     

Application of a simulation-based dynamic traffic assignment model

The evaluation of on-line intelligent transportation system (ITS) measures, such as adaptive route-guidance and traffic management systems, depends heavily on the use of faster than real time traffic simulation models. Off-line applications, such as the testing of ITS strategies and planning studies, are also best served by fast-running traffic models due to the repetitive or iterative nature of such investigations. This paper describes a simulation-based, iterative dynamic equilibrium traffic assignment model. The determination of time-dependent path flows is modeled as a master problem that is solved using the method of successive averages (MSA). The determination of path travel times for a given set of path flows is the network-loading sub-problem, which is solved using the space-time queuing approach of Mahut. This loading method has been shown to provide reasonably accurate results with very little computational effort. The model was applied to the Stockholm road network, which consists of 2100 links, 1191 nodes, 228 zones, representing and 4964 turns. The results show that this model is applicable to medium-size networks with a very reasonable computation time.     

Applications de la sonde moléculaire aux composites a teneur elevee en solides—I. Determination des temperatures de transition vitreuse et etude des phenomenes de surface

The molecular probe technique has been shown to be useful for measuring the glass transition temperature of a highly-filled composite, or of a polybutadiene prepolymer covering surfaces of varying types. The measured Tg of 193°K is independent of the curing stage as well as of the nature of functional groups. Transitions between 349 and 364°K were detected in a Fe₂O₃-containing composite, showing the general applicability of the technique. Studies of the slope of the curve relating the logarithm of the specific retention volume to the reciprocal of the absolute temperature can lead to useful information concerning the orientation of the polybutadiene prepolymer at the polymer-solid interface.