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991.
Stabilization of a Chiral Dirhodium Carbene by Encapsulation and a Discussion of the Stereochemical Implications 下载免费PDF全文
Dr. Christophe Werlé Dr. Richard Goddard Petra Philipps Dr. Christophe Farès Prof. Alois Fürstner 《Angewandte Chemie (International ed. in English)》2016,55(36):10760-10765
For the first time, the stereochemical course of an asymmetric cyclopropanation can be discussed on the basis of experimental structural information on a pertinent chiral dirhodium carbene intermediate. Key to success was the formation of racemic single crystals of a heterochiral [Rh2{(S*)‐PTTL}4{=C(Ar)COOMe}][Rh2{(R*)‐PTTL}4] (Ar=MeOC6H4; PTTL=N‐phthaloyl‐tert‐leucinate) capsule, which has been characterized by X‐ray diffraction. NMR spectroscopic data confirm that the obtained structural portrait is also relevant in solution and provide additional information about the dynamics of this species. The chiral binding pocket is primarily defined by the conformational preferences of the N‐phthaloyl‐protected amino acid ligands and reinforced by a network of weak interligand interactions that get stronger when chlorinated phthalimide residues are used. 相似文献
992.
Raimund Bürger Christophe Chalons Luis Miguel Villada 《Bulletin of the Brazilian Mathematical Society》2016,47(1):187-200
This paper focuses on the numerical approximation of the solutions of multi-species kinematic flow models. These models are strongly coupled nonlinear first-order conservation laws with various applications like sedimentation of a polydisperse suspension in a viscous fluid, or traffic flow modeling. Since the eigenvalues and eigenvectors of the corresponding flux Jacobian matrix have no closed algebraic form, this is a challenging issue. A new class of simple schemes based on a Lagrangian- Eulerian decomposition (the so-called Lagrangian-remap (LR) schemes) was recently advanced in [4] for traffic flow models with nonnegative velocities, and extended to models of polydisperse sedimentation in [5]. These schemes are supported by a partial numerical analysis when one species is considered only, and turned out to be competitive in both accuracy and efficiency with several existing schemes. Since they are only first-order accurate, it is the purpose of this contribution to propose an extension to second-order accuracy using quite standard MUSCL and Runge-Kutta techniques. Numerical illustrations are proposed for both applications and involving eleven species (sedimentation) and nine species (traffic) respectively. 相似文献
993.
Farges B Poughon L Creuly C Cornet JF Dussap CG Lasseur C 《Applied biochemistry and biotechnology》2008,151(2-3):686-699
Manmade ecosystems differ from their prototype biosphere by the principle of control. The Earth Biosphere is sustainable by stochastic control and very large time constants. By contrast, in a closed ecosystem such as the micro-ecological life support system alternative (MELiSSA system) developed by the European Space Agency for space exploration, a deterministic control is a prerequisite of sustainable existence. MELiSSA is an integrated sum of interconnected biological subsystems. On one hand, all unit operations in charge of the elementary functions constitutive of the entire life support system are studied until a thorough understanding and mathematical modelling. On the other hand, the systemic approach of complex, highly branched systems with feedback loops is performed. This leads to study in the same perspective, with the same degree of accuracy and with the same language, waste degradation, water recycling, atmosphere revitalisation and food production systems prior to the integration of knowledge-based control models. This paper presents the mathematical modelling of the MELiSSA system and the interface between the control strategy of the entire system and the control of the bioreactors. 相似文献
994.
Aronica C Chastanet G Zueva E Borshch SA Clemente-Juan JM Luneau D 《Journal of the American Chemical Society》2008,130(7):2365-2371
A series of compounds (cat)[V6O6(OCH3)8(calix)(CH3OH)] was obtained under anaerobic conditions and solvothermal reaction of VOSO4 with p-tert-butylcalix[4]arene (calix) in methanol using different types of bases (Et4NOH, NH4OH, pyridine, Et3N). All compounds contain the same polyoxo(alkoxo)hexavanadate anion [V6O6(OCH3)8(calix)(CH3OH)]- (1) exhibiting a mixed valence {VIIIVIV5O19} core with the so-called Lindqvist structure coordinated to a calix[4]arene macrocycle and cocrystallizing with the conjugated acid of the base (cat = Et4N+, NH4(+), pyridinium, Et3NH+) involved in the synthesis process. The structures have been fully established from X-ray diffraction on single crystals and the mixed valence state has been confirmed by bond valence sum calculations. The magnetic behavior of all compounds are the same because of the polyalkoxohexavanadate anion [V6O6(OCH3)8(calix)(CH3OH)]- (1) and have been interpreted by DFT calculations. Thus the V(III)...V(IV) interactions are found to be weakly ferromagnetic (<5.5 cm(-1)) while the V(IV)...V(IV) are antiferromagnetic (-17.6; -67.6 cm(-1)). The set of the coupling exchange parameters allows a good agreement with the magnetic experimental data. 相似文献
995.
Tanguy Amodeo Christophe Dutouquet François Tenegal Benoît Guizard Hicham Maskrot Olivier Le Bihan Emeric Fréjafon 《Spectrochimica Acta Part B: Atomic Spectroscopy》2008
Laser-Induced Breakdown Spectroscopy (LIBS) was employed for on-line and real time process monitoring during nanoparticle production by laser pyrolysis. Laser pyrolysis has proved to be a reliable and versatile method for nanoparticle production. However, an on-line and real time monitoring system could greatly enhance the process optimization and accordingly improve its performances. For this purpose, experiments aiming at demonstrating the feasibility of an on-line monitoring system for silicon carbide nanoparticle production using the LIBS technique were carried out. Nanosecond laser pulses were focused into a cell through which part of the nanoparticle flux diverted from the production process was flowed for LIBS analysis purposes. The nanoparticles were vaporized within the laser-induced plasma created in argon used as background gas in the process. Temporally-resolved emission spectroscopy measurements were performed in order to monitor nanoparticle stoichiometry. Promising results were obtained and on-line Si/Cx stoichiometry was successfully observed. These results put forward the possibility of real time correction of the nanoparticle stoichiometry during the production process. 相似文献
996.
Schatz C Smith EG Armes SP Wanless EJ 《Langmuir : the ACS journal of surfaces and colloids》2008,24(15):8325-8331
The well-established ability of copolymer micelles to encapsulate and release hydrophobic molecules has been investigated following their adsorption onto silica particles. Here, a pH-responsive copolymer, poly(2-(dimethylamino)ethyl methacrylate)- b-poly(2-(diethylamino)ethyl methacrylate) (PDMA(106)- b-PDEA(25)), has been used to study the formation and dissociation of adsorbed micelles through pH variation. This copolymer behaves as free unimers in aqueous solutions below pH 8 and forms micelles 29 nm in hydrodynamic diameter above this pH. Encapsulation and release of a model hydrophobic compound (pyrene) by in situ adjustment of the solution pH has been compared for both free and adsorbed micelles using fluorescence spectrophotometry, epifluorescence microscopy, and zeta potential measurements. At basic pH values, pyrene is solubilized within the cores of micelles adsorbed on silica particles: addition of acid leads to micelle dissociation and release of the pyrene into the bulk aqueous solution. Micelle adsorption does not appear to hinder the extent of pyrene uptake/release. Moreover, this pH-responsive behavior is both reversible and reproducible over multiple pH cycles. 相似文献
997.
Deraeve C Boldron C Maraval A Mazarguil H Gornitzka H Vendier L Pitié M Meunier B 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(2):682-696
Fourteen different ligands have been synthesized with two covalently linked 8-hydroxyquinoline motifs that favor metal complexation. These bis-chelators include different bridges at the C2 positions and different substituents to modulate their physicochemical properties. They can form metal complexes in a ratio of one ligand per metal ion with Cu II and Zn II, two metal ions involved in the formation of amyloid aggregates of the toxic Abeta-peptides in the Alzheimer disease. The apparent affinity of all bis-8-hydroxyquinoline ligands for Cu II and Zn II are similar with logK Cu II approximately 16 and logK Zn II approximately 13 and are 10,000 times more efficient than for the corresponding 8-hydroxyquinoline monomers. Their strong chelating capacities allow them to inhibit more efficiently than the corresponding monomers the precipitation of Abeta-peptides induced by Cu II and Zn II and also to inhibit the toxic formation of H2O2 due to copper complexes of Abeta. The best results were obtained with a one-atom linker between the two quinoline units. X-ray analyses of single-crystals of Cu II, Zn II or Ni II complexes of 2,2'-(2,2-propanediyl)-bis(8-hydroxyquinoline), including a one-atom linker, showed that all heteroatoms of the bis-8-hydroxyquinoline ligand chelate the same metal ion in a distorted square-planar geometry. The Cu II and Zn II complexes include a fifth axial ligand and are pentacoordinated. 相似文献
998.
999.
Stavrakakis C Colin R Héquet V Faur C Le Cloirec P 《Journal of AOAC International》2008,91(1):237-246
This paper presents an analytical method applied to the determination of 3 natural steroid hormones, estrone, 17 beta-estradiol, and 16 alpha-hydroxyestrone, and the contraceptive estrogen, 17 alpha-ethynylestradiol, at the sub-ng/L level in water samples [surface water and wastewater treatment plant (WWTP) samples]. The solid-phase extraction conditions were optimized using C18 cartridges. Identification and quantification were performed using a column liquid chromatographic/tandem mass spectrometric system with electrospray ionization in the negative mode. Before analyzing steroids in complex matrixes, statistical tools permitted a fine validation of the analytical method, and performance was evaluated for spring water in terms of recovery, specificity, trueness, repeatability, and intralaboratory reproducibility. The results showed the accuracy of the method, and limits of detection (LOD) ranged between 0.02 and 0.21 ng/L. The determination of steroids in WWTP effluents, which contain high levels of organic matter, required an additional purification step on silica cartridges. The high efficiency of the purification was proved with LOD < 0.3 ng/L from 200 mL sample. Specificity of the entire analytical procedure was shown by repeatable recoveries at low and high levels of the calibration range. 相似文献
1000.
Díaz-Moscoso A Balbuena P Gómez-García M Ortiz Mellet C Benito JM Le Gourriérec L Di Giorgio C Vierling P Mazzaglia A Micali N Defaye J García Fernández JM 《Chemical communications (Cambridge, England)》2008,(17):2001-2003
Self-assembled cyclodextrin (CD)-DNA nanoparticles (CDplexes) exhibiting transfection efficiencies significantly higher than PEI-based polyplexes have been prepared from homogeneous seven-fold symmetric polyaminothiourea amphiphiles constructed on a beta-cyclodextrin scaffold. 相似文献