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61.
Over the last several decades, researchers have achieved remarkable progress in the field of organometallic chemistry. The development of metal-catalyzed cross-coupling reactions represents a paradigm shift in chemical synthesis, and today synthetic chemists can readily access carbon-carbon and carbon-heteroatom bonds from a vast array of starting compounds. Although we cannot understate the importance of these methods, the required prefunctionalization to carry out these reactions adds cost and reduces the availability of the starting reagents. The use of C-H bond activation in lieu of prefunctionalization has presented a tantalizing alternative to classical cross-coupling reactions. Researchers have met the challenges of selectivity and reactivity associated with the development of C-H bond functionalization reactions with an explosion of creative advances in substrate and catalyst design. Literature reports on selectivity based on steric effects, acidity, and electronic and directing group effects are now numerous. Our group has developed an array of C-H bond functionalization reactions that take advantage of a chelating directing group, and this Account surveys our progress in this area. The use of chelation control in C-H bond functionalization offers several advantages with respect to substrate scope and application to total synthesis. The predictability and decreased dependence on the inherent stereoelectronics of the substrate generally result in selective and high yielding transformations with broad applicability. The nature of the chelating moiety can be chosen to serve as a functional handle in subsequent elaborations. Our work began with the use of Rh(I) catalysts in intramolecular aromatic C-H annulations, which we further developed to include enantioselective transformations. The application of this chemistry to the simple olefinic C-H bonds found in α,β-unsaturated imines allowed access to highly substituted olefins, pyridines, and piperidines. We observed complementary reactivity with Rh(III) catalysts and developed an oxidative coupling with unactivated alkenes. Further studies on the Rh(III) catalysts led us to develop methods for the coupling of C-H bonds to polarized π bonds such as those in imines and isocyanates. In several cases the methods that we have developed for chelation-controlled C-H bond functionalization have been applied to the total synthesis of complex molecules such as natural products, highlighting the utility of these methods in organic synthesis. 相似文献
62.
Dr. Youness Touati-Jallabe Dr. Thibault Tintillier Dr. Elodie Mauchauffée Dr. Jean-Luc Boucher Jérémy Leroy Booma Ramassamy Dr. Abdallah Hamzé Dr. Karima Mezghenna Amine Bouzekrini Claudia Verna Jean Martinez Dr. Anne-Dominique Lajoix Dr. Jean-François Hernandez 《ChemMedChem》2020,15(6):517-531
More than 160 arginine analogues modified on the C-terminus via either an amide bond or a heterocyclic moiety (1,2,4-oxadiazole, 1,3,4-oxadiazole and 1,2,4-triazole) were prepared as potential inhibitors of NO synthases (NOS). A methodology involving formation of a thiocitrulline intermediate linked through its side-chain on a solid support followed by modification of its carboxylate group was developed. Finally, the side-chain thiourea group was either let unchanged, S-alkylated (Me, Et) or guanidinylated (Me, Et) to yield respectively after TFA treatment the corresponding thiocitrulline, S-Me/Et-isothiocitrulline and N-Me/Et-arginine substrate analogues. They all were tested against three recombinant NOS isoforms. Several compounds containing a S-Et- or a S-Me-Itc moiety and mainly belonging to both the dipeptide-like and 1,2,4-oxadiazole series were shown to inhibit nNOS and iNOS with IC50 in the 1–50 μM range. Spectral studies confirmed that these new compounds interacted at the heme active site. The more active compounds were found to inhibit intra-cellular iNOS expressed in RAW264.7 and INS-1 cells with similar efficiency than the reference compounds L-NIL and SEIT. 相似文献
63.
Polyamide‐12 was blended with butyl rubber, bromobutyl rubber, and chlorobutyl rubber with and without a sulfur curing system. Mechanical properties for dynamically vulcanized blends generally exceed those made with no vulcanization. Chlorobutyl‐containing blends prepared by dynamic vulcanization have higher tensile strength and elongation at break values in comparison to those made from other butyl rubbers. For a variety of polyamide/rubber blends made by dynamic vulcanization, there is very little effect of rubber percentage unsaturation and Mooney viscosity on the mechanical properties of the blends. In chlorobutyl‐containing blends prepared by dynamic vulcanization, the swelling index values attributed to the rubber portion decrease as rubber content decreases, and it is likely that the polyamide phase completely surrounds the rubber particles at compositions exceeding approximately 25% polyamide. Swelling index results can be correlated with elongation at break values for similar blends. The results of differential scanning calorimetry suggest that the polyamide phase is not a neutral component in high shear mixing with butyl rubbers with or without curing agents. Rheological studies indicate strong non‐Newtonian behavior for all blends of polyamide‐12 with butyl rubbers. Scanning electron microscopy on polyamide‐12/butyl rubber blends indicates compatibility for butyl rubbers in the order of chlorobutyl > bromobutyl > butyl rubber. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1423–1435, 2004 相似文献
64.
Thermal treatments, such as combustion, gasification, and pyrolysis, have been proven to be a convenient alternative to conventional sludge disposal technologies. Today, process development implies scaling up and so improving the reactor's design. In continuously operated reactors, fresh sewage sludge is in contact with solid residues (reacted material rich in mineral matter and char). Mineral matter has been reported to catalyze the thermo-chemical reactions involved but few works focus on this aspect. In this work, sewage sludge residues were added to fresh sewage sludge. Non-isothermal thermo-gravimetric analysis (TGA) coupled with infrared spectrometry (FTIR) showed that added residues reduce the characteristic reaction temperatures during char combustion and gasification (air, air-N2, and CO2 atmospheres). However, any considerable influence of residues was observed during pyrolysis experiments (N2 atmosphere). The analysis of gas produced during those experiments revealed further details about the solid decomposition, showing considerable differences between different atmospheres. 相似文献
65.
Amédée Djemai Etienne Balan Guillaume Morin Giancarlo Hernandez Jean Claude Labbe Jean Pierre Muller 《Journal of the American Ceramic Society》2001,84(5):1017-1024
Kaolinites with various degrees of structural order and iron content were heated and subsequently analyzed via electron paramagnetic resonance. Iron was present in two different states in the heated materials, either as dilute structural Fe3+ ions or in concentrated Fe3+ phases. During metakaolinization, the environment of dilute Fe3+ ions changed, following modifications of the Al3+ coordination, and the Fe3+ concentration increased. With the breakdown of metakaolinite, the diffusion of Fe3+ ions induced their exsolution in superparamagnetic iron-rich domains (Fe3+ clusters in γ-Al2 O3 and/or Fe3+ oxide nanophases), which produced a decrease in the dilute Fe3+ concentration. The subsequent breakdown of γ-Al2 O3 and the formation of mullite made the dilute Fe3+ concentration increase again, because of the incorporation of Fe3+ ions in the mullite structure. 相似文献
66.
Lipid‐like Peptides can Stabilize Integral Membrane Proteins for Biophysical and Structural Studies 下载免费PDF全文
Katharina Veith Maria Martinez Molledo Yasser Almeida Hernandez Dr. Inokentijs Josts Julius Nitsche Dr. Christian Löw Prof. Dr. Henning Tidow 《Chembiochem : a European journal of chemical biology》2017,18(17):1735-1742
A crucial bottleneck in membrane protein structural biology is the difficulty in identifying a detergent that can maintain the stability and functionality of integral membrane proteins (IMPs). Detergents are poor membrane mimics, and their common use in membrane protein crystallography may be one reason for the challenges in obtaining high‐resolution crystal structures of many IMP families. Lipid‐like peptides (LLPs) have detergent‐like properties and have been proposed as alternatives for the solubilization of G protein‐coupled receptors and other membrane proteins. Here, we systematically analyzed the stabilizing effect of LLPs on integral membrane proteins of different families. We found that LLPs could significantly stabilize detergent‐solubilized IMPs in vitro. This stabilizing effect depended on the chemical nature of the LLP and the intrinsic stability of a particular IMP in the detergent. Our results suggest that screening a subset of LLPs is sufficient to stabilize a particular IMP, which can have a substantial impact on the crystallization and quality of the crystal. 相似文献
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69.
Dr. Asifa Munawar Dr. James W. Marshall Prof. Russell J. Cox Dr. Andy M. Bailey Dr. Colin M. Lazarus 《Chembiochem : a European journal of chemical biology》2013,14(3):388-394
FSN1, a gene isolated from the sugar‐cane pathogen Fusarium sacchari, encodes a 4707‐residue nonribosomal peptide synthetase consisting of three complete adenylation, thiolation and condensation modules followed by two additional thiolation and condensation domain repeats. This structure is similar to that of ferricrocin synthetase, which makes a siderophore that is involved in intracellular iron storage in other filamentous fungi. Heterologous expression of FSN1 in Aspergillus oryzae resulted in the accumulation of a secreted metabolite that was identified as ferrirhodin. This siderophore was found to be present in both mycelium and culture filtrates of F. sacchari, whereas ferricrocin is found only in the mycelium, thus suggesting that ferricrocin is an intracellular storage siderophore in F. sacchari, whereas ferrirhodin is used for iron acquisition. To our knowledge, this is the first report to characterise a ferrirhodin synthetase gene functionally. 相似文献
70.
Michael I. Cotterell Gareth P. Ward Alastair P. Hibbins Andy Wilson Jim M. Haywood Justin M. Langridge 《Aerosol science and technology》2013,47(10):1128-1148
AbstractPhotoacoustic spectroscopy (PAS) measures aerosol absorption in a noncontact manner, providing accurate absorption measurements that are needed to improve aerosol optical property representations in climate models. Central to PAS is resonant amplification of the acoustic pressure wave generated from laser-heated aerosol transferring heat to surrounding gas by a photoacoustic cell. Although this cell amplifies pressure sources from aerosol absorption (signal), it also amplifies noise and background sources. It is important to maximize the cell signal-to-background ratio (SBR) for sensitive absorption measurements. Many researchers have adopted the two-resonator cell design described by Lack et al. (2006). We show that the uncertainty in PAS measurements of aerosol absorption using this two-resonator cell is significantly degraded by its large sensitivity to background contributions from laser scattering and absorption at the cell windows. In Part 1, we described the use of a finite element method (FEM) to predict cell acoustic properties, validated this framework by comparing model predictions to measurements, and used FEM to test various strategies applied commonly to single-resonator cell optimization. In this second part, we apply FEM to understand the excitation of resonant modes of the two-resonator cell, with comparison measurements demonstrating accurate predictions of acoustic response. We perform geometry optimization studies to maximize the SBR and demonstrate that the laser–window interaction background is reduced to undetectable levels for an optimal cell. This optimized two-resonator cell will improve the sensitivity and accuracy of future aerosol absorption measurements. 相似文献