Synthesis of 3′-deoxy-3′-iminodiacetic acid and 3′-deoxy-3′-aminodiethanol thymidine analogues and NMR study of their complexation with boronic acids

The iminodiacetic acid and aminodiethanol moieties are known for their ability to generate with boronic acids bicyclic structures having a strong intramolecular NB coordination. We describe here the convergent synthesis of 3′-deoxy-3′-iminodiacetic acid and 3′-deoxy-3′-aminodiethanol thymidine analogues. The abilities of these compounds to form boronate complexes with aliphatic or aromatic boronic acids were established by 1D and 2D ¹H and ¹³C NMR. Moreover, conformational analysis of the newly synthesized compounds revealed a marked preference for an N-type sugar puckering.     

Higher Coverings of Racks and Quandles—Part II

Applied Categorical Structures - This article is the second part of a series of three articles, in which we develop a higher covering theory of racks and quandles. This project is rooted in...     

Quantifying uncertainty with ensembles of surrogates for blackbox optimization

Blackbox optimization tackles problems where the functions are expensive to evaluate and where no analytical information is available. In this context, a tried and tested technique is to build surrogates of the objective and the constraints in order to conduct the optimization at a cheaper computational cost. This work introduces an extension to a specific type of surrogates: ensembles of surrogates, enabling them to quantify the uncertainty on the predictions they produce. The resulting extended ensembles of surrogates behave as stochastic models and allow the use of efficient Bayesian optimization tools. The method is incorporated in the search step of the mesh adaptive direct search (MADS) algorithm to improve the exploration of the search space. Computational experiments are conducted on seven analytical problems, two multi-disciplinary optimization problems and two simulation problems. The results show that the proposed approach solves expensive simulation-based problems at a greater precision and with a lower computational effort than stochastic models.

     

The distribution of tax payments in a Lévy insurance risk model with a surplus-dependent taxation structure

We study the distribution of tax payments in the model of Kyprianou and Zhou [Kyprianou, A.E., Zhou, X., 2009. General tax structures and the Lévy insurance risk model. J. Appl. Probab. (in press)], that is a Lévy insurance risk model with a surplus-dependent tax rate. More precisely, after a short discussion on the so-called tax identity, we derive a recursive formula for arbitrary moments of the discounted tax payments until ruin and we identify the distribution of the tax payments when there is no force of interest.     

95 GHz millimeter wave signal generation using an arrayed waveguide grating dual wavelength semiconductor laser

We report the generation of a 95?GHz carrier frequency by optical heterodyning of two wavelengths from adjacent channels from an arrayed waveguide grating-based multiwavelength laser. The extended cavity structure of the device provides low phase noise and narrow optical linewidth, further enhanced by the intracavity filter effect of the arrayed waveguide grating. We demonstrate that the generated RF beat note, at 95?GHz, has a -3 dB linewidth of 250?kHz. To the best of our knowledge, this is the narrowest RF linewidth generated from a free-running dual-wavelength semiconductor laser. The device is realized as a photonic integrated circuit using active-passive integration technology, and fabricated on a multiproject wafer run, constituting a novel approach for a compact, low-cost dual-wavelength heterodyne source.     

Horizon Entropy

Although the laws of thermodynamics are well established for black hole horizons, much less has been said in the literature to support the extension of these laws to more general settings such as an asymptotic de Sitter horizon or a Rindler horizon (the event horizon of an asymptotic uniformly accelerated observer). In the present paper we review the results that have been previously established and argue that the laws of black hole thermodynamics, as well as their underlying statistical mechanical content, extend quite generally to what we call here causal horizons. The root of this generalization is the local notion of horizon entropy density.     

Reductive cyclizations of hydroxysulfinyl ketones: enantioselective access to tetrahydropyran and tetrahydrofuran derivatives

The stereocontrolled formation of cis-2,5-disubstituted tetrahydrofurans and cis-2,6-disubstituted tetrahydropyrans is achieved from enantiopure ketosulfinyl esters by reduction, Weinreb's amide, and ketone formation, followed by the reductive cyclization (Et3SiH/TMSOTf) of the resulting hydroxysulfinyl ketones. The sulfoxide-bearing heterocycles were transformed into two natural products, (-)-centrolobine (1) and both enantiomers of cis-(6-methyltetrahydropyran-2-yl)acetic acid (2).     

Particle Propagation in Cosmological Backgrounds

We analyse the quantum propagation of interacting particles in cosmological backgrounds. The model we use consists of a doublet of massive scalar fields propagating in an expanding universe filled with massless radiation. The masses are much larger than the Hubble expansion rate, so that the number of massive particles is preserved and the fields adequately described within the adiabatic approximation. We focus on the dissipative effects related to the expansion rate by computing the imaginary part of the self-energy. In the quasi static approximation, we recover the expected result that instantaneous decay rate is governed by the local temperature. We then analyse the long time behavior of the propagator to unravel the secular effects induced by the self-energy. We show that these effects can be expressed in terms of integrals of local quantities. Applications to the trans-Planckian question are briefly discussed.     

Single molecule spectroscopy as a probe for dye-polymer interactions

Experimental (Single Molecule Spectroscopy) and theoretical (quantum-chemical calculations and Monte Carlo and molecular dynamics simulations) techniques are combined to investigate the behavior and dynamics of a polymer-dye molecule system. It is shown that the dye molecule of interest (1,1'-dioctadecyl-3,3,3',3'-tetramethylindo-dicarbocyanine) adopts two classes of conformations, namely planar and nonplanar ones, when embedded in a poly(styrene) matrix. From an in-depth analysis of the fluorescence lifetime trajectories, the planar conformers can be further classified according to the way their alkyl side chains interact with the surrounding poly(styrene) chains.     

Use of Lewis Acids in Free Radical Reactions

The neglect of free radicals over the past few years has been overcome, and they are no longer only considered as interesting reactive intermediates with limited synthetic potential. New opportunities are opened up by performing radical reactions in the presence of Lewis acids. Rate enhancement of radical addition to olefins as well as stereochemical control of such reactions can be achieved in a unique manner. Recent examples of enantioselective radical reactions and perspectives for applications in catalysis are discussed.