Recension d’ouvrage : Pour une éthique ouverte à l’inattendu. Libérer la face lumineuse de l’incertitude. Avec Guy Bourgeault

The synthesis and the separation of the four stereoisomers of 2,4,6,8,10-pentamethylundecane (PMU) are described together with their characterization by Raman spectroscopy. In parallel, theoretical calculations of the Raman and vibrational Raman optical activity (VROA) spectra are reported and analyzed in relation with the recorded spectra. A very good agreement is found between the experimental and theoretical spectra. The Raman spectra are also shown to be less affected by the change of configuration than the VROA spectra. Nevertheless, by studying the overlap between the theoretical Raman spectra, we show clear relationships between the spectral fingerprints and the structures displaying a mixture of the TGTGTGTG conformation of the (4R,6s,8S)-PMU (isotactic compound) with the TTTTTTTT conformation of the (4R,6r,8S)-PMU (syndiotactic compound). Then, the fingerprints of the VROA spectra of the five conformers of the (4R,8R)-PMU have been related to the fingerprints of the regular (TG)(N) isotactic compound as a function of the torsion angles. Since the (TT)(N) syndiotactic compound has no VROA signatures, the VROA spectroscopy is very sensitive to the helical structures, as demonstrated here

Self-assembly of Microcapsules via Colloidal Bond Hybridization and Anisotropy

Particles with directional interactions are promising building blocks for new functional materials and may serve as models for biological structures. Mutually attractive nanoparticles that are deformable due to flexible surface groups, for example, may spontaneously order themselves into strings, sheets and large vesicles. Furthermore, anisotropic colloids with attractive patches can self-assemble into open lattices and colloidal equivalents of molecules and micelles. However, model systems that combine mutual attraction, anisotropy, and deformability have---to the best of our knowledge---not been realized. Here, we synthesize colloidal particles that combine these three characteristics and obtain self-assembled microcapsules. We propose that mutual attraction and deformability induce directional interactions via colloidal bond hybridization. Our particles contain both mutually attractive and repulsive surface groups that are flexible. Analogous to the simplest chemical bond, where two isotropic orbitals hybridize into the molecular orbital of H2, these flexible groups redistribute upon binding. Via colloidal bond hybridization, isotropic spheres self-assemble into planar monolayers, while anisotropic snowman-like particles self-assemble into hollow monolayer microcapsules. A modest change of the building blocks thus results in a significant leap in the complexity of the self-assembled structures. In other words, these relatively simple building blocks self-assemble into dramatically more complex structures than similar particles that are isotropic or non-deformable

Spin Transition Sensors Based on β-Amino-Acid 1,2,4-Triazole Derivative

A β-aminoacid ester was successfully derivatized to yield to 4H-1,2-4-triazol-4-yl-propionate (βAlatrz) which served as a neutral bidentate ligand in the 1D coordination polymer [Fe(βAlatrz)3](CF3SO3)2·0.5H2O (1·0.5H2O). The temperature dependence of the high-spin molar fraction derived from 57Fe Mossbauer spectroscopy recorded on cooling below room temperature reveals an exceptionally abrupt single step transition between high-spin and low-spin states with a hysteresis loop of width 4 K (Tc↑ = 232 K and Tc↓ = 228 K) in agreement with magnetic susceptibility measurements. The material presents striking reversible thermochromism from white, at room temperature, to pink on quench cooling to liquid nitrogen, and acts as an alert towards temperature variations. The phase transition is of first order, as determined by differential scanning calorimetry, with transition temperatures matching the ones determined by SQUID and Mössbauer spectroscopy. The freshly prepared sample of 1·0.5H2O, dried in air, was subjected to annealing at 390 K, and the obtained white compound [Fe(βAlatrz)3](CF3SO3)2 (1) was found to exhibit a similar spin transition curve however much temperature was increased by (Tc↑ = 252 K and Tc↓ = 248 K). The removal of lattice water molecules from 1·0.5H2O is not accompanied by a change of the morphology and of the space group, and the chain character is preserved. However, an internal pressure effect stabilizing the low-spin state is evidenced

Synthesis of Ï-aminodithioesters

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A practical synthesis of 2,2-difluoro-3-amino-propanoic acid (α,α-difluoro-β-alanine)

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Synthesis and Biological Evaluation of Functionalized Epoxides Structurally Related To the Carbapenem Family

Epoxides (6) and (7), topologically related to the carbapenem antibiotics, were designed as potential alkylating inhibitors of the bacterial D,D-peptidases. The olefinic precursors (8-9) were readily prepared, in three steps, by coupling the Wittig reagent (13) with the aldehyde synthons (10) or (11) resulting from diastereoselective aldol condensations. Epoxide (7) showed a weak anti-beta-lactamase activity

Imidazolidinones structurally-related to penicillins: synthesis, molecular modeling and biological evaluation.

Several bicyclic imidazolidinones structurally-related to penicillins have been prepared from penam precursors. The compounds were compared to benzylpenicillin as active reference, using the methods of theoretical chemistry. Structures 7 and 8, in which the acyl group of the side-chain was anchored, via a "one-atom spacer", at position N-7 of the imidazolidinone ring, appeared as good penicillin mimics. However, they were found devoid of significant antibacterial activity

Protection of peroxide-treated fish erythrocytes by coelenterazine and coelenteramine.

European seabass (Dicentrarchus labrax) erythrocytes treated with tert-butyl hydroperoxide (t-BHP) showed decreasing levels of reduced glutathione, increased lipid peroxidation and DNA damage, and ultimately underwent haemolysis. The addition of the marine luciferin coelenterazine (CLZn) markedly delayed the onset of the haemolytic process induced by t-BHP as well as lipid peroxidation and glutathione oxidation. CLZn also protected the red blood cells' DNA against t-BHP-triggered damage. CLZn's oxidation product coelenteramine (CLM) also delayed the lysis of the cells as well as the occurrence of oxidative stress indicators but it did not offer protection against DNA damage. Both compounds proved more efficient than the vitamin E analogue Trolox C at similar doses. These results demonstrate the ability of CLZn and CLM to protect fish cells against oxidative stress, providing further support to the evolutionary model suggesting that CLZn's first physiological role was that of an antioxidant in fish thriving in surface layers of the ocean, later evolving into its light-emitting function in deep-sea species

Synthesis of N-Protected 3,3-Difluoroazetidin-2-ones

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