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21.
Friedel–Crafts Reaction of Benzyl Fluorides: Selective Activation of CF Bonds as Enabled by Hydrogen Bonding 下载免费PDF全文
Pier Alexandre Champagne Yasmine Benhassine Justine Desroches Prof. Jean‐François Paquin 《Angewandte Chemie (International ed. in English)》2014,53(50):13835-13839
A Friedel–Crafts benzylation of arenes with benzyl fluorides has been developed. The reaction produces 1,1‐diaryl alkanes in good yield under mild conditions without the need for a transition metal or a strong Lewis acid. A mechanism involving activation of the C? F bond through hydrogen bonding is proposed. This mode of activation enables the selective reaction of benzylic C? F bonds in the presence of other benzylic leaving groups. 相似文献
22.
We study a vectorial approximation problem based on thin plate splines with tension involving two positive parameters: one for the control of the oscillations and the other for the control of the divergence and rotational components of the field. The existence and uniqueness of the solution are proved and the solution is explicitly given. As special cases, we study the limit problems as the parameter controlling the divergence and the rotation converges to zero or infinity. The divergence-free and the rotation-free approximation problems are also considered. The convergence in Sobolev space is studied. 相似文献
23.
Dr. Antoine Debuigne Aurélie N. Morin Dr. Anthony Kermagoret Dr. Yasmine Piette Dr. Christophe Detrembleur Prof. Christine Jérôme Prof. Rinaldo Poli 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(40):12834-12844
This work reveals the preponderance of an intramolecular metal chelation phenomenon in a controlled radical polymerization system involving the reversible trapping of the radical chains by a cobalt complex bis(acetylacetonato)cobalt(II). The cobalt‐mediated radical polymerization (CMRP) of a series of N‐vinyl amides was considered with the aim of studying the effect of the cobalt chelation by the amide moiety of the last monomer unit of the chain. The latter reinforces the cobalt? polymer bond in the order N‐vinylpyrrolidone<N‐vinyl caprolactam<N‐methyl‐N‐vinyl acetamide, and is responsible for the optimal control of the polymerizations observed for the last two monomers. Such a double linkage between the controlling agent and the polymer, through a covalent bond and a dative bond, is unique in the field of controlled radical polymerization and represents a powerful opportunity to fine tune the equilibrium between latent and free radicals. Possible hydrogen bond formation is also taken into account in the case of N‐vinyl acetamide and N‐vinyl formamide. These results are essential for understanding the factors influencing Co? C bond strength in general, and the CMRP mechanism in particular, but also for developing a powerful platform for the synthesis of new precision poly(N‐vinyl amide) materials, which are an important class of polymers that sustain numerous applications today. 相似文献
24.
Hanieh Kargarzadeh Ishak Ahmad Ibrahim Abdullah Alain Dufresne Siti Yasmine Zainudin Rasha M. Sheltami 《Cellulose (London, England)》2012,19(3):855-866
Cellulose nanocrystals (CNC) were first isolated from kenaf bast fibers and then characterized. The raw fibers were subjected
to alkali treatment and bleaching treatment and subsequent hydrolysis with sulfuric acid. The influence of the reaction time
on the morphology, crystallinity, and thermal stability of CNC was investigated. Fourier transform infrared spectroscopy showed
that lignin and hemicellulose were almost entirely removed during the alkali and bleaching treatments. The morphology and
dimensions of the fibers and acid-released CNC were characterized by field emission scanning electron microscopy and transmission
electron microscopy. X-Ray diffraction analysis revealed that the crystallinity first increases upon hydrolysis and then decreases
after long durations of hydrolysis. The optimal extraction time was found to be around 40 min during hydrolysis at 45 °C with
65% sulfuric acid. The thermal stability was found to decrease as the hydrolysis time increased. The electrophoretic mobility
of the CNC suspensions was measured using the zeta potential, and it ranged from −8.7 to −95.3 mV. 相似文献
25.
In this paper, we present a convergence analysis of the inexact Newton method for solving Discrete-time algebraic Riccati equations (DAREs) for large and sparse systems. The inexact Newton method requires, at each iteration, the solution of a symmetric Stein matrix equation. These linear matrix equations are solved approximatively by the alternating directions implicit (ADI) or Smith?s methods. We give some new matrix identities that will allow us to derive new theoretical convergence results for the obtained inexact Newton sequences. We show that under some necessary conditions the approximate solutions satisfy some desired properties such as the d-stability. The theoretical results developed in this paper are an extension to the discrete case of the analysis performed by Feitzinger et al. (2009) [8] for the continuous-time algebraic Riccati equations. In the last section, we give some numerical experiments. 相似文献
26.
Agglomerate aerosols in a turbulent flow may be subjected to very high turbulent shear rates which through the generation of lift and drag can overcome the adhesive forces binding the constituents of an agglomerate together and cause it to break-up. This paper presents an analysis of the experimental measurements of the breakup of agglomerates between 0.1?C10???m in size, in a turbulent pipe flow followed by an expansion zone with a Reynolds numbers in the range 105 to 107. The analysis shows that even in wall bounded turbulence, the high turbulent shear stresses associated with the small scales of turbulence in the core can be the main source of breakup preceding any break-up that may occur by impaction at the wall. More importantly from these results, a computationally fast and efficient solution is obtained for the General Dynamic Equation (GDE) for agglomerate transport and breakup in highly turbulent flow. Furthermore the solution for the evolution of the aerosol size distribution is consistent with the experimental results. In the turbulent pipe flow section, the agglomerates are exposed continuously to turbulent shear stresses and experience more longer term breakup than in the expansion zone (following the pipe flow) where the exposure time is much less and break-up occurs instantaneously under the action of very high local turbulent shear stresses. The validity of certain approximations made in the model is considered. In particular, the inertia of the agglomerates characterised by a Stokes Number from 0.001 for the smallest particles up to 10 for 10???m particles and the fluctuations of the turbulent shear stresses are important physical phenomena which are not accounted for in the model. 相似文献
27.
Leonhard H. Urner Maiko Schulze Yasmine B. Maier Waldemar Hoffmann Stephan Warnke Idlir Liko Kristin Folmert Christian Manz Carol V. Robinson Rainer Haag Kevin Pagel 《Chemical science》2020,11(13):3538
Mass spectrometry enables the in-depth structural elucidation of membrane protein complexes, which is of great interest in structural biology and drug discovery. Recent breakthroughs in this field revealed the need for design rules that allow fine-tuning the properties of detergents in solution and gas phase. Desirable features include protein charge reduction, because it helps to preserve native features of protein complexes during transfer from solution into the vacuum of a mass spectrometer. Addressing this challenge, we here present the first systematic gas-phase study of azobenzene detergents. The utility of gas-phase techniques for monitoring light-driven changes of isomer ratios and molecular properties are investigated in detail. This leads to the first azobenzene detergent that enables the native mass spectrometry analysis of membrane proteins and whose charge-reducing properties can be tuned by irradiation with light. More broadly, the presented work outlines new avenues for the high-throughput characterization of supramolecular systems and opens a new design strategy for detergents in membrane protein research.Here, L. H. Urner and co-workers identify a new detergent design strategy for the non-denaturing structural analysis of membrane proteins by studying the gas-phase properties of azobenzene-based oligoglycerol detergents. 相似文献
28.
Qi Wang Qile Wang Yuexiang Zhang Yasmine M. Mohamed Carlos Pacheco Nan Zheng Richard N. Zare Hao Chen 《Chemical science》2021,12(3):969
Although synthetic organic electrochemistry (EC) has advanced significantly, net redox neutral electrosynthesis is quite rare. Two approaches have been employed to achieve this type of electrosynthesis. One relies on turnover of the product by the reactant in a chain mechanism. The other involves both oxidation on the anode and reduction on the cathode in which the radical cation or the radical anion of the product has to migrate between two electrodes. Herein, a home-built electrochemistry/mass spectrometry (EC/MS) platform was used to generate an N-cyclopropylaniline radical cation electrochemically and to monitor its reactivity toward alkenes by mass spectrometry (MS), which led to the discovery of a new redox neutral reaction of intermolecular [3 + 2] annulation of N-cyclopropylanilines and alkenes to provide an aniline-substituted 5-membered carbocycle via direct electrolysis (yield up to 81%). A chain mechanism, involving the regeneration of the substrate radical cation and the formation of the neutral product, is shown to be responsible for promoting such a redox neutral annulation reaction, as supported by experimental evidence of EC/MS.We report the use of an online electrochemistry/mass spectrometry platform to develop a redox neutral electrosynthesis of 5-membered rings via [3 + 2] annulation of N-cyclopropylanilines and alkenes, without additional oxidant, reductant or catalyst. 相似文献
29.
Antigen binding forces of single antilysozyme Fv fragments explored by atomic force microscopy 总被引:4,自引:0,他引:4
Berquand A Xia N Castner DG Clare BH Abbott NL Dupres V Adriaensen Y Dufrêne YF 《Langmuir : the ACS journal of surfaces and colloids》2005,21(12):5517-5523
We used atomic force microscopy (AFM) to explore the antigen binding forces of individual Fv fragments of antilysozyme antibodies (Fv). To detect single molecular recognition events, genetically engineered histidine-tagged Fv fragments were coupled onto AFM tips modified with mixed self-assembled monolayers (SAMs) of nitrilotriacetic acid- and tri(ethylene glycol)-terminated alkanethiols while lysozyme (Lyso) was covalently immobilized onto mixed SAMs of carboxyl- and hydroxyl-terminated alkanethiols. The quality of the functionalization procedure was validated using X-ray photoelectron spectroscopy (surface chemical composition), AFM imaging (surface morphology in aqueous solution), and surface plasmon resonance (SPR, specific binding in aqueous solution). AFM force-distance curves recorded at a loading rate of 5000 pN/s between Fv- and Lyso-modified surfaces yielded a distribution of unbinding forces composed of integer multiples of an elementary force quantum of approximately 50 pN that we attribute to the rupture of a single antibody-antigen pair. Injection of a solution containing free Lyso caused a dramatic reduction of adhesion probability, indicating that the measured 50 pN unbinding forces are due to the specific antibody-antigen interaction. To investigate the dynamics of the interaction, force-distance curves were recorded at various loading rates. Plots of unbinding force vs log(loading rate) revealed two distinct linear regimes with ascending slopes, indicating multiple barriers were present in the energy landscape. The kinetic off-rate constant of dissociation (k(off) approximately = 1 x 10(-3) s(-1)) obtained by extrapolating the data of the low-strength regime to zero force was in the range of the k(off) estimated by SPR. 相似文献
30.
The syntheses of a series of chiral ureas containing the redox-active ferrocene group are described. Each of these bind chiral carboxylates in organic solvents through hydrogen-bonding interactions, as evidenced by spectroscopic and cyclic voltammetry measurements, the latter allowing these guests to be electrochemically sensed in solution. The enantioselectivity in the complexation of the protected amino acid N-benzenesulfonylproline by a ferrocenylbenzyl host is high enough to allow opposite enantiomers to be distinguished by electrochemical means. 相似文献