Understanding J‐Modulation during Spatial Encoding for Sensitivity‐Optimized Ultrafast NMR Spectroscopy

Ultrafast (UF) NMR spectroscopy is an approach that yields 2D spectra in a single scan. This methodology has become a powerful analytical tool that is used in a large array of applications. However, UF NMR spectroscopy still suffers from an intrinsic low sensitivity, and from the need to compromise between sensitivity, spectral width, and resolution. In particular, the modulation of signal intensities by the spin–spin J‐coupling interaction (J‐modulation) impacts significantly on the intensities of the spectral peaks. This effect can lead to large sensitivity losses and even to missing spectral peaks, depending on the nature of the spin system. Herein, a general simulation package (Spinach) is used to describe J‐modulation effects in UF experiments. The results from simulations match with experimental data and the results of product operator calculations. Several methods are proposed to optimize the sensitivity in UF COSY spectra. The potential and drawbacks of the different strategies are also discussed. These approaches provide a way to adjust the sensitivity of UF experiments for a large range of applications.     

Synergies between operations research and data mining: The emerging use of multi-objective approaches

Operations research and data mining already have a long-established common history. Indeed, with the growing size of databases and the amount of data available, data mining has become crucial in modern science and industry. Data mining problems raise interesting challenges for several research domains, and in particular for operations research, as very large search spaces of solutions need to be explored. Hence, many operations research methods have been proposed to deal with such challenging problems. But the relationships between these two domains are not limited to these natural applications of operations research approaches. The counterpart is also important to consider, since data mining approaches have also been applied to improve operations research techniques. The aim of this article is to highlight the interplay between these two research disciplines. A particular emphasis will be placed on the emerging theme of applying multi-objective approaches in this context.     

Global existence result for thermoviscoelastic problems with hysteresis

We consider viscoelastic solids undergoing thermal expansion and exhibiting hysteresis effects due to plasticity or phase transformations. Within the framework of generalized standard solids, the problem is described in a three-dimensional setting by the momentum equilibrium equation, the flow rule describing the dependence of the stress on the strain history, and the heat transfer equation. Under appropriate regularity assumptions on the data, a local existence result for this thermodynamically consistent system is established, by combining existence results for ordinary differential equations in Banach spaces with a fixed-point argument. Then global estimates are obtained by using both the classical energy estimate and more specific techniques for the heat equation introduced by Boccardo and Gallouët. Finally a global existence result is derived.     

Organocatalyzed enantio- and diastereoselective isomerization of prochiral 1,3-cyclohexanediones into nonalactones bearing distant stereocenters

The lactonization of 2-(2-nitrophenyl)-1,3-cyclohexanediones containing an alcohol side chain and up to three distant prochiral elements is reported by isomerization under the mediation of simple organocatalysts such as quinidine. Through a process of ring expansion, strained nonalactones and decalactone are produced with up to three stereocenters in high er and dr (up to 99 : 1). Distant groups, including alkyl, aryl, carboxylate and carboxamide moieties, were examined.

Nine- and ten-membered lactones with up to three non-vicinal stereocenters (up to 99 : 1 er and dr) were prepared by ring expansion of prochiral alcohols (21 examples) upon exposure to quinidine and derivatives.     

From isocyanides to trichloropyruvamides: application to a new preparation of oxamide derivatives

Isocyanides react readily with trichloroacetic acid anhydride forming stable hydrates of trichloropyruvamides. These compounds are valuable intermediates for obtaining oxamides by reaction with TMSCl/NEt₃ followed by addition of an amine.     

Rational design of lanthanide binding peptides

Lanthanide-binding peptides are very attractive for the design of bioprobes. Indeed, they combine the amazing properties of lanthanide ions, such as their time-resolved luminescence (Eu, Tb) or electronic relaxation (Gd) to the characteristics of the peptide scaffold, such as large solubility in water and ability to recognize biological substrates. Peptides derived from natural amino acids are reviewed in a first section. Some of their lanthanide complexes have already demonstrated their efficiency in determining protein structures and functions. Then, we will show how insertion of chelating unnatural amino acids modulates peptide-lanthanide complexes properties, such as luminescence and stability.     

Selective internal manipulation of a single molecule by scanning tunneling microscopy

We have studied the adsorption of the polyaromatic molecule 1,4"-paratriphenyldimethylacetone, which we have nicknamed Trima. The originality of this linear molecule is that it was designed and synthesized to have two functionalities. First, chemisorb itself to the surface by its two ends rather like a bridge. Second, the central part of the molecule could then be rotated by injecting electrons with the tip of the scanning tunneling microscope (STM). The length of the molecule corresponds exactly to the spacing between five dimers in a row on the Si(100)-2 x 1 surface. We found that the molecule adsorbs as expected on the clean silicon surface by using complementary STM and synchrotron radiation studies. Manipulation of individual molecules with the STM tip showed selective internal modifications that were highly voltage dependent. These manipulations were found to be compatible with an electronic excitation of the pi-pi* transition of the molecule.     

Regiodivergent Cyclobutanone Cleavage: Switching Selectivity with Different Lewis Acids

The exploitation of strain release in small rings as driving force to enable complex transformations is a powerful synthetic tool. Among them, cyclobutanones are particularly versatile substrates that can be elaborated in a wide variety of structurally diverse building blocks. Herein, Lewis acid catalyzed rearrangement reactions are presented that provide selective access to two structurally distinct polycyclic scaffolds, that is, indenylacetic acid derivatives and benzoxabicyclo[3.2.1]octan‐3‐ones. The choice of the Lewis acid fully controls the reaction pathway and the regioselectivity of the cyclobutanone C?C bond cleavage site.     

A Tris(triazolate) Ligand for a Highly Active and Magnetically Recoverable Palladium Catalyst of Selective Alcohol Oxidation Using Air at Atmospheric Pressure

High efficiency and selectivity, easy magnetic recovery and recycling, and use of air as the oxidant at atmospheric pressure are major objectives for oxidation catalysis in terms of sustainable and green processes. A tris(triazolyl) ligand, so far only used in copper‐catalyzed alkyne azide cycloadditions, was found to be extremely efficient in SiO₂/γ‐Fe₂O₃‐immobilized palladium complexes. It was characterized by inductively coupled plasma (ICP) analysis, transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), energy‐dispersive X‐ray spectroscopy (EDX), and X‐ray photoelectron spectra (XPS) and found to fulfill the combined conditions for the selective oxidation of alcohols to aldehydes and ketones.