Portable single-sided NMR measurements at variable temperatures: Implementation of a thermo-controlled device and application to the heating of bread dough

A temperature control unit was implemented to vary the temperature of samples studied on a commercial Mobile Universal Surface Explorer nuclear magnetic resonance (MOUSE-NMR) apparatus. The device was miniaturized to fit the maximum MOUSE sampling depth (25 mm). It was constituted by a sample holder sandwiched between two heat exchangers placed below and above the sample. Air was chosen as the fluid to control the temperature at the bottom of the sample, at the interface between the NMR probe and the sample holder, in order to gain space. The upper surface of the sample was regulated by the circulation of water inside a second heat exchanger placed above the sample holder. The feasibility of using such a device was demonstrated first on pure water and then on several samples of bread dough with different water contents. For this, T1 relaxation times were measured at various temperatures and depths and were then compared with those acquired with a conventional compact closed-magnet spectrometer. Discussion of results was based on biochemical transformations in bread dough (starch gelatinization and gluten heat denaturation). It was demonstrated that, within a certain water level range, and because of the low magnetic field strength of the MOUSE, a linear relationship could be established between T1 relaxation times and the local temperature in the dough sample.     

Glyphosate–Exonuclease Interactions: Reduced Enzymatic Activity as a Route to Glyphosate Biosensing

N-phosphonomethyle-glycine (glyphosate) is the most widely used pesticide worldwide due to its effectiveness in killing weeds at a moderate cost, bringing significant economic benefits. However, owing to its massive use, glyphosate and its residues contaminate surface waters. On site, fast monitoring of contamination is therefore urgently needed to alert local authorities and raise population awareness. Here the hindrance of the activity of two enzymes, the exonuclease I (Exo I) and the T5 exonuclease (T5 Exo) by glyphosate, is reported. These two enzymes digest oligonucleotides into shorter sequences, down to single nucleotides. The presence of glyphosate in the reaction medium hampers the activity of both enzymes, slowing down enzymatic digestion. It is shown by fluorescence spectroscopy that the inhibition of ExoI enzymatic activity is specific to glyphosate, paving the way for the development of a biosensor to detect this pollutant in drinking water at suitable detection limits, i.e., 0.6 nm .     

Octonionic representations of Clifford algebras and triality

The theory of representations of Clifford algebras is extended to employ the division algebra of the octonions or Cayley numbers. In particular, questions that arise from the nonassociativity and noncommutativity of this division algebra are answered. Octonionic representations for Clifford algebras lead to a notion of octonionic spinors and are used to give octoninic representations of the respective orthogonal groups. Finally, the triality automorphisms are shown to exhibit a manifest ₃ ×SO(8) structure in this framework.     

Effect of matrices and additives on phosphorylated and ketodeoxyoctonic acid lipids A analysis by matrix‐assisted laser desorption ionization‐mass spectrometry

Lipid A is a major compound of the outer membrane of gram‐negative bacteria and is a key factor of bacterial virulence. As lipid A's structure differs among bacterial species and varies between strains of the same species, knowing its modifications is essential to understand its implications in the infectious process. To analyze these lipids, matrix‐assisted laser desorption ionization‐mass spectrometry (MALDI‐MS) is a well‐suited method that is fast and efficient. However, there are limitations with the matrix and additives used, such as the suppression of signal or prompt fragmentations that could give a false overview of lipid A composition in biological samples. For a comprehensive analysis of the entire lipid A species present in a sample, we tested 16 matrices and 11 additives on two commercial lipids A. The first commercial one contains single phosphorylation group, and the second contains two phosphorylation and two ketodeoxyoctonic acid (KDO) groups. The lipid A containing KDO groups was essentially detected by the 3‐hydroxypicolinic acid (3‐HPA) matrix, whereas the monophosphorylated lipid A could be detected by 13 matrices out of the 16. We also demonstrated that the signal of diphosphorylated lipid A can be enhanced with the use of additives in the matrix. Our study indicated that the best conditions to obtain a clear signal of both lipids A without prompt fragmentation was the use of 3‐HPA with 10mM trifluoroacetic acid (TFA).     

N-Boc-Amides in Cross-Coupling Reactions

Since 2015, the use of amides as electrophilic partners in cross-coupling reactions has experienced exponential growth. Diverse amide derivatives have been studied and among them N-Boc-amides have shown good activities towards various cross-coupling reactions and presents, in our view, an important synthetic usefulness. This review describes the recent developments of these chemical transformations involving N-Boc-amides.     

New progress in the cobalt-catalysed synthesis of aromatic organozinc compounds by reduction of aromatic halides by zinc dust

The experimental conditions of the cobalt-catalysed synthesis of aromatic organozinc species from the corresponding bromides have been optimised. The preparation of numerous aromatic organozinc reagents under these optimised conditions is reported, with yields between 67 and 99%.     

Gravity and Signature Change

The use of proper time to describe classical spacetimes which contain both Euclidean and Lorentzian regions permits the introduction of smooth (generalized) orthonormal frames. This remarkable fact permits one to describe both a variational treatment of Einstein's equations and distribution theory using straightforward generalizations of the standard treatments for constant signature.     

New efficient construction of the ABC core of the taxoids via a sequence of consecutive cobalt(I)-mediated [2 + 2 + 2] and [4 + 2] cyclizations

[reaction: see text] A new and efficient sequence of two consecutive cyclizations, a cobalt(I)-mediated [2 + 2 + 2] cyclotrimerization and a Diels-Alder reaction, is proposed to allow the formation of the ABC core of the taxoids in 65% overall yield, starting from an acyclic polyunsaturated precursor.     

Bis- through Tetrakis-Adducts of C60 by Reversible Tether-Directed Remote Functionalization and systematic investigation of the changes in fullerene properties as a function of degree,pattern, and nature of functionalization

By the tether-directed remote functionalization method, a series of bis- to hexakis-adducts of C₆₀, i.e., 1 – 7 (Fig. 1), had previously been prepared with high regioselectivity. An efficient method for the removal of the tether-reactive-group conjugate was now developed and its utility demonstrated in the regioselective synthesis of bis- to tetrakis(methano)fullerenes ( = di- to tetracyclopropafullerenes-C₆₀-I_h) 9 – 11 starting from 4, 5, and 7, respectively (Schemes 2, 4, and 5). This versatile protocol consists of a ¹O₂ ene reaction with the two cyclohexene rings in the starting materials, reduction of the formed mixture of isomeric allylic hydroperoxides to the corresponding alcohols, acid-promoted elimination of H₂O to cyclohexa-1,3-dienes, Diels-Alder addition of dimethyl acetylenedicarboxylate, retro-Diels-Alder addition, and, ultimately, transesterification. In the series 9 – 11 , all methano moieties are attached along an equatorial belt of the fullerene. Starting from C_2v-symmetrical tetrakis-adduct 15 , transesterification with dodecan-1-ol or octan-1-ol yielded the octaesters 16 and 17 , respectively, as noncrystalline fullerene derivatives (Scheme 3). The X-ray crystal structure of a CHCl₃ solvate of 11 (Fig. 3) showed that the residual conjugated π-chromophore of the C-sphere is reduced to two tetrabenzopyracylene substructures connected by four biphenyl-type bonds (Fig. 5). In the eight six-membered rings surrounding the two pyracylene (= cyclopent[fg]acenaphthylene) moieties, 6–6 and 6–5 bond-length alteration (0.05 Å) was reduced by ca. 0.01 Å as compared to the free C₆₀ skeleton (0.06 Å) (Fig. 4). The crystal packing (Fig. 6) revealed short contacts between Cl-atoms of the solvent molecule and sp²- and sp³-C-atoms of the C-sphere, as well as short contacts between Cl-atoms and O-atoms of the EtOOC groups attached to the methano moieties of 11 . The physical properties and chemical reactivity of compounds 1 - 11 were comprehensively investigated as a function of degree and pattern of addition and the nature of the addends. Methods applied to this study were UV/VIS (Figs. 7–11), IR, and NMR spectroscopy (Table 2), cyclic (CV) and steady-state (SSV) voltammetry (Table 1), calculations of the energies of the lowest uunoccupied mmolecular orbitals (LUMOs) and electron affinities (Figs. 12 and 13), and evaluation of chemical reactivity in competition experiments. It was found that the properties of the fullerene derivatives were not only affected by the degree and pattern of addition but also, in a remarkable way, by the nature of the addends (methano vs. but-2-ene-1, 4-diyl) anellated to the C-sphere. Attachment of multiple thano moieties along an equatorial belt as in the series 8 – 11 induces only a small perturbation of the original fullerene π-chromophore. In general, with increasing attenuation of the conjugated fullerene π-chromophore, the optical (HOMO-LUMO) gap in the UV/VIS spectrum is shifted to higher energy, the number of reversible one-electron reductions decreases, and the first reduction potential becomes increasingly negative, the computed LUMO energy increases and the electron affinity decreases, and the reactivity of the fullerene towards nucleophiles and carbenes and as dienophile in cycloadditions decreases.