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81.
Ngoc Q. Bui Pascal Fongarland Franck Rataboul Cyril Dartiguelongue Nadège Charon Christophe Vallee Nadine Essayem 《Comptes Rendus Chimie》2018,21(6):555-562
The objective of this work was to investigate the ability of supercritical (SC) ethanol conditions to attack preferentially the lignin fraction against the carbohydrate fraction and their effects on the product distribution among gases, light products, bio-oils, and chars. In this study, the conversion of each pinewood component was determined by the analysis of solid residues to quantify cellulose, hemicellulose, lignin, and char contents. It is shown that, by tuning the temperature, hemicellulose and lignin are already transformed in subcritical ethanol conditions, lignin being more reactive than hemicellulose. In contrast, native wood cellulose is recalcitrant to liquefaction in SC ethanol near the critical point (Tc = 241 °C and Pc = 61 bar), but 20% of native wood cellulose is converted in SC ethanol at 280 °C. Besides, the severity of the conditions, in terms of temperature and treatment time, does not significantly influence the yields of gases, light products, and bio-oils but strongly enhances char formation. Interestingly, the increase in SC ethanol density does not change the conversion of biomass components but has a marked effect on bio-oil yield and prevents char formation. The optimum fractionation conditions to convert the lignin component, while keeping unattacked the cellulose fraction with a minimum formation of char, are dense SC ethanol, at 250 °C for 1 h, in batch conditions. However, although lignin is more reactive than hemicellulose under these conditions, these fractions are converted, in a parallel way, to around 50% and 60%, respectively. 相似文献
82.
83.
Dr. Esmail Doustkhah Prof. Dr. Jianjian Lin Prof. Dr. Sadegh Rostamnia Prof. Dr. Christophe Len Prof. Dr. Rafael Luque Prof. Dr. Xiliang Luo Prof. Dr. Yoshio Bando Prof. Dr. Kevin C.-W. Wu Dr. Jeonghun Kim Prof. Dr. Yusuke Yamauchi Dr. Yusuke Ide 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(7):1614-1635
Sulfonic acid based mesostructures (SAMs) have been developed in recent years and have important catalytic applications. The primary applications of these materials are in various organic synthesis reactions, such as multicomponent reactions, carbon–carbon bond couplings, protection reactions, and Fries and Beckman rearrangements. This review aims to provide an overview of the recent developments in the field of SAMs with a particular emphasis on the reaction scope and advantages of heterogeneous solid acid catalysts. 相似文献
84.
Dr. Antoine Nitelet Dr. Damien Thevenet Dr. Bruno Schiavi Dr. Christophe Hardouin Dr. Jean Fournier Dr. Rodolphe Tamion Prof. Dr. Xavier Pannecoucke Prof. Dr. Philippe Jubault Prof. Dr. Thomas Poisson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(13):3262-3266
The copper-photocatalyzed borylation of aryl, heteroaryl, vinyl and alkyl halides (I and Br) was reported. The reaction proceeded using a new heteroleptic Cu complex under irradiation with blue LEDs, giving the corresponding boronic-acid esters in good to excellent yields. The reaction was extended to continuous-flow conditions to allow an easy scale-up. The mechanism of the reaction was studied and a mechanism based on a reductive quenching (CuI/CuI*/Cu0) was suggested. 相似文献
85.
Roberto Morales-Cerrada Dr. Christophe Fliedel Dr. Jean-Claude Daran Dr. Florence Gayet Dr. Vincent Ladmiral Dr. Bruno Améduri Prof. Rinaldo Poli 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(1):296-308
Thermal decarbonylation of the acyl compounds [Mn(CO)5(CORF)] (RF=CF3, CHF2, CH2CF3, CF2CH3) yielded the corresponding alkyl derivatives [Mn(CO)5(RF)], some of which have not been previously reported. The compounds were fully characterized by analytical and spectroscopic methods and by several single-crystal X-ray diffraction studies. The solution-phase IR characterization in the CO stretching region, with the assistance of DFT calculations, has allowed the assignment of several weak bands to vibrations of the [Mn(12CO)4(eq-13CO)(RF)] and [Mn(12CO)4(ax-13CO)(RF)] isotopomers and a ranking of the RF donor power in the order CF3<CHF2<CH2CF3≈CF2CH3. The homolytic Mn−RF bond cleavage in [Mn(CO)5(RF)] at various temperatures under saturation conditions with trapping of the generated RF radicals by excess tris(trimethylsilyl)silane yielded activation parameters ΔH≠ and ΔS≠ that are believed to represent close estimates of the homolytic bond dissociation thermodynamic parameters. These values are in close agreement with those calculated in a recent DFT study (J. Organomet. Chem. 2018 , 864, 12–18). The ability of these complexes to undergo homolytic Mn−RF bond cleavage was further demonstrated by the observation that [Mn(CO)5(CF3)] (the compound with the strongest Mn−RF bond) initiated the radical polymerization of vinylidene fluoride (CH2=CF2) to produce poly(vinylidene fluoride) in good yields by either thermal (100 °C) or photochemical (UV or visible light) activation. 相似文献
86.
Dr. Christophe Kahlfuss Dr. Raymond Grüber Prof. Elise Dumont Prof. Guy Royal Floris Chevallier Dr. Saioa Cobo Prof. Eric Saint-Aman Dr. Christophe Bucher 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(6):1573-1580
A dynamic supramolecular approach is developed to promote the π-dimerization of viologen radicals at room temperature and in standard concentration ranges. The approach involves cis- or trans-protected palladium centers serving as inorganic hinges linking two functionalized viologens endowed with metal-ion coordinating properties. Based on detailed spectroscopic, electrochemical and computational data, we show that the one-electron electrochemical reduction of the viologen units in different dynamic metal/ligand mixtures leads to the formation of the same intramolecular π-dimer, regardless of the initial environment around the metallic precursor and of the relative ratio between metal and ligand initially introduced in solution. The large-scale electron-triggered reorganization of the building blocks introduced in solution thus involves drastic changes in the stoichiometry and stereochemistry of the palladium/viologen complexes proceeding in some cases through a palladium centered trans→cis isomerization of the coordinated ligands. 相似文献
87.
Behnaz Ghaffari Jorge Mendes-Burak Ka Wing Chan Prof. Dr. Christophe Copéret 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(61):13869-13873
Manganese, the third most abundant transition-metal element after iron and titanium, has recently been demonstrated to be an effective homogeneous catalyst in numerous reactions. Herein, the preparation of silica-supported MnII sites is reported using Surface Organometallic Chemistry (SOMC), combined with tailored thermolytic molecular precursors approach based on Mn2[OSi(OtBu)3]4 and Mn{N(SiMe3)2}2⋅THF. These supported MnII sites, free of organic ligands, efficiently catalyze numerous reactions: hydroboration and hydrosilylation of ketones and aldehydes as well as the transesterification of industrially relevant substrates. 相似文献
88.
The knowledge of atomic fundamental parameters, such as mass attenuation coefficients or fluorescence yields with low uncertainties, is of decisive importance in elemental quantification involving X-ray fluorescence analysis techniques. Several databases providing the mass attenuation coefficients are accessible and frequently used within a large community of users. These compilations are most often in good agreement for photon energies in the hard X-ray ranges. However, they significantly differ for low photon energies and around the absorption edges of the elements. Mass attenuation coefficients of several elements were determined experimentally in the photon energy range from 100 eV to 35 keV by using monochromatized radiation at the SOLEIL synchrotron (France). The application of high-accuracy experimental techniques resulted in low uncertainty mass attenuation coefficients. The results are compared with tabulated data. 相似文献
89.
90.
Florent Monie Dr. Bruno Grignard Dr. Jean-Michel Thomassin Dr. Raphael Mereau Dr. Thierry Tassaing Prof. Dr. Christine Jerome Dr. Christophe Detrembleur 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(39):17181-17189
Polyurethane (PU) foams are indisputably daily essential materials found in many applications, notably for comfort (for example, matrasses) or energy saving (for example, thermal insulation). Today, greener routes for their production are intensively searched for to avoid the use of toxic isocyanates. An easily scalable process for the simple construction of self-blown isocyanate-free PU foams by exploiting the organocatalyzed chemo- and regioselective additions of amines and thiols to easily accessible cyclic carbonates is described. These reactions are first validated on model compounds and rationalized by DFT calculations. Various foams are then prepared and characterized in terms of morphology and mechanical properties, and the scope of the process is illustrated by modulating the composition of the reactive formulation. With impressive diversity and accessibility of the main components of the formulations, this new robust and solvent-free process could open avenues for construction of more sustainable PU foams, and offers the first realistic alternative to the traditional isocyanate route. 相似文献