Reversible water uptake by a stable imine-based porous organic cage

A crystalline porous organic cage molecule, CC3, is shown to adsorb up to 20.1 wt% water reversibly. This was confirmed by both gravimetric sorption and by crystallographic analysis. Crystals of CC3 are stable in boiling water for at least 4 h. The surprising chemical and supramolecular stability of these imine-based molecular crystals suggests scope for practical applications in humid environments.     

Synthesis of self‐healing supramolecular rubbers from fatty acid derivatives,diethylene triamine,and urea

We describe the synthesis of supramolecular self‐healing elastomers from vegetable oil fatty acid derivatives, diethylene triamine, and urea. Our strategy to obtain materials that are self‐healing but do not flow relies on the use of a wide molecular distribution of randomly branched oligomers equipped with self‐complementary and complementary hydrogen bonding groups. We prepared such oligomers with a two steps procedure. In the first step, diethylene triamine was condensed with dimer acids. In the second step, the oligomers obtained were allowed to react with urea. The molecules were characterized by NMR and IR spectroscopies and Monte‐Carlo simulations were used to analyze the molecular size distribution. The sensitivity to small variations of the experimental conditions has been examined and the robustness of the synthetic procedure optimized. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7925–7936, 2008     

Synthesis of new [2]rotaxane including a macrocyclic receptor and a photochromic unit

The novel photochromic [2]rotaxane based on chromene molecule introduced into a crown-containing macrocyclic receptor was synthesized. The photochemical properties of rotaxane could be modified by the complexation of the crown ether moiety.     

Chemical-genetic screen identifies riluzole as an enhancer of Wnt/β-catenin signaling in melanoma

To identify new protein and pharmacological regulators of Wnt/β-catenin signaling, we used a cell-based reporter assay to screen a collection of 1857 human-experienced compounds for their ability to enhance activation of the β-catenin reporter by a low concentration of WNT3A. This identified 44 unique compounds, including the FDA-approved drug riluzole, which is presently in clinical trials for treating melanoma. We found that treating melanoma cells with riluzole in?vitro enhances the ability of WNT3A to regulate gene expression, to promote pigmentation, and to decrease cell proliferation. Furthermore riluzole, like WNT3A, decreases metastases in a mouse melanoma model. Interestingly, siRNAs targeting the metabotropic glutamate receptor, GRM1, a reported indirect target of riluzole, enhance β-catenin signaling. The unexpected regulation of β-catenin signaling by both riluzole and GRM1 has implications for the future uses of this drug.     

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 .     

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.     

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.