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121.
Solène Morand Prof. Philippe Jubault Prof. Jean-Philippe Bouillon Dr. Samuel Couve-Bonnaire 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(69):17273-17292
gem-Heteroatom-substituted fluoroalkenes have received little attention despite their great potential in medicinal chemistry or in fine chemistry. Indeed, due to the electronic and steric similarity between the fluoroalkene moiety and the amide bond as well as the high strength of the carbon-fluorine bond, these gem-heteroatom-substituted fluoroalkenes could be envisioned as stable mimics of various important organic functions, such as phosphates, carbamates, S-thiocarbamates and ureas. We present herein an overview describing the syntheses over the last decade of heteroatom-substituted fluoroalkenes in geminal position. This review will be divided into several sections covering each the common following heteroatom: oxygen-, nitrogen-, sulfur-, phosphorus-, boron- and silicon-substituted fluoroalkenes. 相似文献
122.
Dr. Quentin Bonnin Tereza Edlová Dr. E. Daiann Sosa Carrizo Prof. Dr. Paul Fleurat-Lessard Dr. Stéphane Brandès Dr. Hélène Cattey Dr. Philippe Richard Prof. Dr. Pierre Le Gendre Dr. Adrien T. Normand 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(72):18175-18187
Cationic amidotitanocene complexes [Cp2Ti(NPhAr)][B(C6F5)4] (Cp=η5-C5H5; Ar=phenyl ( 1 a ), p-tolyl ( 1 b ), p-anisyl ( 1 c )) were isolated. The bonding situation was studied by DFT (Density Functional Theory) using EDA-NOCV (Energy Decomposition Analysis with Natural Orbitals for Chemical Valence). The polar Ti−N bond in 1 a–c features an unusual inversion of σ and π bond strengths responsible for the balance between stability and reactivity in these coordinatively unsaturated species. In solution, 1 a–c undergo photolytic Ti−N cleavage to release Ti(III) species and aminyl radicals ⋅ NPhAr. Reaction of 1 b with H3BNHMe2 results in fast homolytic Ti−N cleavage to give [Cp2Ti(H3BNHMe2)][B(C6F5)4] ( 3 ). 1 a–c are highly active precatalysts in olefin hydrogenation and silanes/amines cross-dehydrogenative coupling, whilst 3 efficiently catalyzes amine-borane dehydrogenation. The mechanism of olefin hydrogenation was studied by DFT and the cooperative H2 activation key step was disclosed using the Activation Strain Model (ASM). 相似文献
123.
This study compares the physicochemical properties of six electrolytes comprising of three salts: LiFTFSI, NaFTFSI and KFTFSI in two solvent mixtures, the binary (3EC/7EMC) and the ternary (EC/PC/3DMC). The transport properties (conductivity, viscosity) as a function of temperature and concentration were modeled using the extended Jones-Dole-Kaminsky equation, the Arrhenius model, and the Eyring theory of transition state for activated complexes. Results are discussed in terms of ionicity, solvation shell, and cross-interactions between electrolyte components. The application of the six formulated electrolytes in symmetrical activated carbon (AC)//AC supercapacitors (SCs) was characterized by cyclic voltammetry (CV), galvanostatic cycling with potential limitation (GCPL), electrochemical impedance spectroscopy (EIS) and accelerated aging. Results revealed that the geometrical flexibility of the FTFSI anion allows it to access and diffuse easily in AC whereas its counter ions (Li+, Na+ or K+) can remain trapped in porosity. However, this drawback was partially resolved by mixing LiFTFSI and KFTFSI salts in the electrolyte. 相似文献
124.
Lukas Rochlitz Keith Searles Darryl F. Nater Scott R. Docherty Domenico Gioffrè Christophe Copéret 《Helvetica chimica acta》2021,104(7):e2100078
Propane dehydrogenation is an important field of research due to an increasing world-wide demand of propene while classical production routes through naphtha cracking are in decline. In that context, silica-supported Ga(III) sites, synthesized from surface organometallic chemistry principles, show high selectivity and stability in the propane dehydrogenation reaction. This performance is in significant contrast to the reported fast deactivation and lower selectivity of most Ga2O3 and CrO3 based materials. The Ga-catalyzed propane dehydrogenation reaction is proposed to proceed through the formation of Ga alkyl intermediates for which it would be desirable to have detailed structural and spectroscopic information. Here, we prepare a consistent series of Ga(III) molecular complexes with varying numbers of alkyl and siloxide ligands; they are characterized by single crystal X-Ray diffraction and X-Ray Absorption Near Edge Structure analysis, which is known to be highly sensitive to the Ga coordination environment. We report in particular the structure and the spectroscopic signatures of [Ga(iPr)(OSi(OtBu)3)2(HOSi(OtBu)3)], a molecular mimic of the key proposed reaction intermediates in the Ga-catalyzed PDH reaction. 相似文献
125.
Dr. Saida Majdoub Dr. Zoltán Garda Alexandre C. Oliveira Dr. Inga Relich Agnès Pallier Dr. Sara Lacerda Dr. Christelle Hureau Dr. Carlos F. G. C. Geraldes Dr. Jean-François Morfin Dr. Éva Tóth 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(6):2009-2020
Metal chelates targeted to amyloid peptides are widely explored as diagnostic tools or therapeutic agents. The attachment of a metal complex to amyloid recognition units typically leads to a decrease in peptide affinity. We show here that by separating a macrocyclic GdL chelate and a PiB targeting unit with a long hydrophobic C10 linker, it is possible to attain nanomolar affinities for both Aβ1-40 (Kd=4.4 nm ) and amylin (Kd=4.5 nm ), implicated, respectively in Alzheimer's disease and diabetes. The Scatchard analysis of surface plasmon resonance data obtained for a series of amphiphilic, PiB derivative GdL complexes indicate that their Aβ1-40 or amylin binding affinity varies with their concentration, thus micellar aggregation state. The GdL chelates also affect peptide aggregation kinetics, as probed by thioflavin-T fluorescence assays. A 2D NMR study allowed identifying that the hydrophilic region of Aβ1-40 is involved in the interaction between the monomer peptide and the Gd3+ complex. Finally, ex vivo biodistribution experiments were conducted in healthy mice by using 111In labeled analogues. Their pancreatic uptake, ∼3 %ID g−1, is promising to envisage amylin imaging in diabetic animals. 相似文献
126.
Jouini Houda Mejri Imène Rhimi Baker Mhamdi Mourad Blasco Teresa Delahay Gérard 《Research on Chemical Intermediates》2021,47(7):2901-2915
Research on Chemical Intermediates - Fe–Cu–ZSM-5 and Ce–Fe–Cu–ZSM-5 solids prepared using solid-state ion exchange method (SSIE) were tested in the NH3–SCR of NO... 相似文献
127.
There is a need for a better characterization of sludges from wastewater treatment plants which are destined to be spread on agricultural lands. Inorganic pollutants are regularly controlled but organic pollutants have received few attention up to now. On this paper, we have been interested on the analysis of the 16 polycyclic aromatic hydrocarbons (PAHs) listed in the US Environmental Protection Agency (US EPA) priority list and more particularly of the six PAHs listed in the European community list (fluoranthene, benzo[b and k]fluoranthene, benzo[a]pyrene, benzo[ghi]perylene, indeno[1,2,3-cd]pyrene). The analysis step consists on liquid chromatography with both fluorescence and UV detections as described in the EPA Method 8310. As for the extraction step, several techniques such as supercritical fluid extraction, pressurized liquid extraction, focused microwave extraction in open vessels, Soxhlet and ultrasonic extractions are compared after optimization of the experimental conditions (solvent nature and quantity, temperature, pressure, duration, ... ) and validation with certified sludges. When optimized, these five extraction techniques are as much efficient with similar relative standard deviation. Whatever the extraction techniques used, the whole analysis protocol permits to quantify PAHs in the range of 0.09 to 0.9 mg/kg of dried sludges. 相似文献
128.
Lahcène Ouahab Stéphane Golhen Yukihiro Yoshida Gunzi Saito 《Journal of Cluster Science》2003,14(3):193-204
The synthesis, structural and magnetic characterizations of a new charge transfer salt (BEDT-TTF)4[Cr(OH)6Mo6O18]2H2O based on the planar paramagnetic Anderson–Evans polyoxometalate are reported. Structural parameters: T=293 K, triclinic (P
), a=5.9545(2) Å, b=16.3767(6) Å, c=21.8643(6) Å, =110.829(2)°, =91.262(2)°, =98.129(1)°, Z=1, R=0.0540. The crystal structure is characterized by a face-to-face stacking of the anions giving rise to a one-dimensional inorganic chain which develops along the a direction. The organic layers contain two crystallographically independent BEDT-TTF dimers that form alternating stacks along the b direction. This organic chain is perpendicular to the inorganic chains. The charges on BEDT-TTF dimers are deduced to +1.2(1) and +1.7(1) on the basis of the intramolecular bond lengths. The EPR spectrum at 2.5 K is characterized by the superposition of BEDT-TTF+ and [CrIII(OH)6Mo6O18]3– signals. The static susceptibility can be fitted by the Curie–Weiss law down to 1.9 K and the magnetic moment at 300 K is estimated to 4.21
B
, suggesting the uncorrelated spin system with BEDT-TTF+ (S=1/2) and CrIII (S=3/2) ions. This interpretion is consistent with the charge disproportionation on BEDT-TTF dimers along the stack, which is supported by the refined molecular structure and is closely related to the insulating behavior (<10–9Scm–1 at RT). 相似文献
129.
130.
Nowaczyk S Alayrac C Metzner P Averbuch-Pouchot MT 《The Journal of organic chemistry》2002,67(19):6852-6855
The alkylation of the lithium enolate of enantiopure alpha-cyclohexylsulfinyl thioacetamide 1 with allyl bromides 5 possessing an electron-withdrawing group at the vinylic position does not occur at the sulfur center - as expected in the sulfur series - but at the carbon center through conjugate addition followed by bromide elimination. The modest to excellent 1,2-asymmetric induction achieved by the alkylsulfinyl group (dr up to 100:0) is explained by an electronic model. 相似文献