Macroplastic transfer dynamics in the Loire estuary: Similarities and specificities with macrotidal estuaries.

The quantification of macroplastic fluxes transferred by rivers toward the pelagic environment requires a better understanding of macrodebris transfer processes in estuarine environments. Following the strategy adopted in the Seine estuary, this study aims to characterize macroplastic trajectories in the Loire estuary. Between January 2020 and July 2021, 35 trajectories were monitored using plastic bottles equipped with GPS-trackers. With total travelled distances between 100 m and 103.6 km, trajectories show great spatiotemporal variability. The various forcing factors (macroplastic buoyancy, estuaries tidal and hydrometeorological conditions, geomorphology and vegetation) lead to chaotic trajectories, preventing accurate predictions in macroplastic transfer and storage/remobilization dynamics. In the Loire estuary like in the Seine one, no tracked bottle reached the Atlantic Ocean. It confirms that macrotidal estuaries under temperate climates constitute accumulation zones and slow pathways for macroplastics, but raises question on the real fluxes transferred from continental areas to oceans.

Kinetic modeling of the thermal destruction of lewisite.

Organoarsenic compounds have been widely used as pesticides and chemical agents. Lewisite (C2H2AsCl3), a blister agent, is a model of such compounds. A comprehensive detailed kinetic mechanism of combustion has been developed based on theoretical investigations. A benchmark allowed to select an appropriate methodology able to deal with such a heavy atom as As with precision and reasonable computational times. The density functional theory (DFT) method ωB97X-D was found to give the best results on target data. Core pseudo potentials were used for arsenic with the cc-pVTZ-PP basis set, whereas Def2-TZVP basis set was used for other atoms. The mechanism of the decomposition of lewisite includes all reactions involved in thermal decomposition and combustion mechanisms, including molecular and radical intermediates, and the decomposition reactions of small species containing arsenic. Simulation shows that lewisite decomposition starts around 700 K and is very little sensitive to the presence of oxygen since the radical reactions involve mainly very reactive Cl-atoms as chain carriers. The main reaction paths have been derived. As experimentally observed, AsCl3 is the main arsenic product produced almost in one-to-one yield, whereas acetylene is an important hydrocarbon product in pyrolysis. In combustion, several arsenic oxides, eventually chlorinated, are produced, which toxicity need to be assessed.

Combustion and Pyrolysis Kinetics of Chloropicrin.

Chloropicrin (CCl3NO2) is widely used in agriculture as a pesticide, weed-killer, fungicide or nematicide. It has also been used as a chemical agent during World War I. The precise understanding of its combustion chemistry for destruction processes or in the event of accidental fire of stored reserves is a major safety issue. A detailed chemical kinetic model for the combustion and pyrolysis of chloropicrin is proposed for the first time. A large number of thermo-kinetic parameters were calculated using quantum chemistry and reaction rate theory. The model was validated against experimental pyrolysis data available in the literature. It was shown that the degradation of chloropicrin is ruled by the breaking of the C-N bond followed by the oxidation of the trichloromethyl radical by NO2 through the formation of the adduct CCl3ONO, which can decompose to NO, chlorine atom, and phosgene. Phosgene is much more stable than chloropicrin and its decomposition starts at much higher temperatures. Combustion and pyrolysis simulations were also compared and demonstrated that the addition of oxygen has very little effect on the reactivity or product distribution due to the absence of hydrogen atoms in chloropicrin.

Quantum Chemical Study of the Thermochemical Properties of Organophosphorous Compounds.

Organophosphorous compounds are involved in many toxic compounds such as fungicides, pesticides, or chemical warfare nerve agents. The understanding of the decomposition chemistry of these compounds in the environment is largely limited by the scarcity of thermochemical data. Because of the high toxicity of many of these molecules, experimental determination of their thermochemical properties is very difficult. In this work, standard gas-phase thermodynamic data, i.e., enthalpies of formation (ΔfH298°), standard entropies (S298°), and heat capacities (Cp°(T)), were determined using quantum chemical calculations and more specifically the CBS-QB3 composite method, which was found to be the best compromise between precision and calculation time among high accuracy composite methods. A large number of molecules was theoretically investigated, involving trivalent and pentavalent phosphorus atoms, and C, H, O, N, S, and F atoms. These data were used to propose 83 original groups, used in the semiempirical group contribution method proposed by Benson. Thanks to these latter group values, thermochemical properties of several nerve agents, common pesticides and herbicides have been evaluated. Bond dissociations energies (BDE), useful for the analysis the thermal stability of the compounds, were also determined in several molecules of interest.

Conformations in solution and bound to bacterial ribosomes of ketolides, HMR 3647 (telithromycin) and RU 72366: a new class of highly potent antibacterials.

The new class of antibiotics called ketolides is endowed with remarkable antibacterial activity against macrolide-resistant strains. Further modifications of the 3 keto-macrolactone backbone led to 11,12-hydrazonocarbamate ketolides with an imidazolyl pyridine chain: the file-leader of ketolide class, HMR 3647 (telithromycin), and its N-bis-demethyl-derivative, RU 72366. The potency of HMR 3647 is higher than that of RU 72366. Stereospecific 1H and 13C resonance assignments of HMR 3647 and RU 72366 have been determined and have allowed a detailed quantitative conformational analysis of the uncomplexed form of the molecules. The comparative conformation of HMR 3647 in solution and its N-bis-demethyl-derivative in D2O has been carried out using different heteronuclear correlation experiments in conjunction with nuclear Overhauser effect experiments and in particular long-range 3J(CH) coupling constants and using molecular dynamics (MD) methods. The study of ketolide ribosome interaction has been investigated using two-dimensional transferred nuclear Overhauser effect spectroscopy (TRNOESY). The database of ribosome-bound ketolide structures has been used to compare the structure(s) of ketolide in ribosome-ketolide complexes with the conformational preferences of free ketolides and to highlight the significant differences between HMR 3647 and RU 72366. A comparison of the conformations bound to ribosome was made with those of other previously studied ketolide (RU 004) and macrolides and would explain the remarkable potencies of HMR 3647 in inhibiting protein synthesis.

Lincomycin and clindamycin conformations. A fragment shared by macrolides, ketolides and lincosamides determined from TRNOE ribosome-bound conformations.

Two important lincosamide antibiotics, lincomycin and clindamycin were studied in the complex state with the bacterial ribosome after a conformational analysis by 1H and 13C NMR spectroscopy and molecular modelling of the unbound molecules. Lincosamide-ribosome interactions were investigated using two-dimensional transferred nuclear Overhauser effect spectroscopy (TRNOESY), resulting in a bound structure compatible with the experimental NMR data. The results compared with the conformational analysis of the substrates in solution indicate that specific conformations are preferred in the bound state. Clindamycin, the more bioactive antibiotic studied, displayed a stronger NMR response than lincomycin showing that in lincosamide-ribosome interactions, a low affinity binding level is associated to the tight binding one and is related to biological activity. This study shows that conformation plays an essential role for the low affinity binding site. Superimposition of lincosamide, macrolide and ketolide bound structures exhibited conformational similarities in a particular fragment which is in agreement with a hypothesis of partial overlapping lincosamide and macrolide binding sites.