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771.
The total synthesis of enantiopure 4-epi-(+)-codonopsinine was achieved in 10 steps starting from D-ribose as a chiral building block. The key step involved a highly stereoselective nucleophilic addition of a Grignard reagent to a protected ribosylamine. Synthesis of the N-desmethyl derivative and its p-tolyl analogue was also accomplished, and the compounds were assayed against α-fucosidase.  相似文献   
772.
This paper deals with the study of uranium-colloid interactions in a carbonated soil. The work is focused on the immediately available fraction obtained after a leaching process, according to a normalized batch method. In order to characterize the different colloidal carriers, Asymmetrical Flow Field-Flow Fractionation (As-Fl-FFF) coupled to different detectors (UV, Multi Angle Laser Light Scattering (MALLS) and Inductively coupled Plasma-Mass Spectrometry (ICP-MS)) was used. The colloidal carriers are mainly inorganic particles (carbonated particles and clays) mixed with organic substances. Furthermore, dissolved and colloidal uranium species in the leaching solutions were monitored by Capillary Electrophoresis (CE) coupled to ICP-MS, in order to investigate the uranium/colloids interactions. According to the first results, uranium fate in this specific soil is controlled by sorption/desorption phenomena, strongly pH dependent.  相似文献   
773.
Layer-by-Layer (LbL) coatings are promising tools for the biofunctionalization of biomaterials, as they allow stress-free immobilization of proteins. Here, we explore the possibility to immobilize phosvitin, a highly phosphorylated protein viewed as a model of bone phosphoproteins and, as such, a potential promotive agent of surface-directed biomineralization, into biomimetic LbL architectures. Two immobilization protocols are attempted, first, using phosvitin as the polyanionic component of phosvitin/poly-(L-lysine) films and, second, adsorbing it onto preformed chondroitin sulfate/poly-(L-lysine) films. Surprisingly, it is neither possible to embed phosvitin as the constitutive polyanion of the LbL architectures nor to adsorb it atop preformed films. Instead, phosvitin triggers instant massive film disassembly. This unexpected, incidentally detected behavior constitutes the first example of destructive interactions between LbL films and a third polyelectrolyte, a fortiori a protein, which might open a route toward new stimuli-responsive films for biosensing or drug delivery applications. Interestingly, additional preliminary results still indicate a promotive effect of phosvitin-containing remnant films on calcium phosphate deposition.  相似文献   
774.
The addition of trifluoromethyl(trimethyl)silane (TFMTMS) to tartaric acid derived aromatic 1,4-diketones was reported to be highly stereoselective but also chemoselective towards a monoaddition product. This chemoselectivity remained unexplained. Complementary experiments and monitoring of the reaction by electrospray ionization mass spectrometry (ESI-MS) show that: i) the countercation (tetrabutylammonium (TBA(+)) or Cs(+)) associated to the initiator and the charged intermediates in the chain reaction plays a crucial role and ii) in the case of a tetrabutylammonium salt initiator, the second addition on the preformed monoadduct does occur but the resulting bis(trifluoromethyl)carbinolate is unable to evolve through the chain-transfer process and it exhibits an intramolecular Si-O interaction.  相似文献   
775.
The combustion in air of a 100 μm-diameter aluminum droplet is studied by direct Navier–Stokes simulations. The model only considers the gas phase and includes a reduced Al/O2 kinetic scheme with 8 species and 10 reactions. The model is validated against experimental burn time data and appears to be fairly correct despite its simplicity. The unsteady combustion is then investigated by superimposing an acoustic disturbance to the mean flow. The velocity-coupled response is computed for different frequencies and slip Reynolds numbers. A resonance peak is found to occur when the acoustic time scale matches the gas diffusion time scale. For lower frequencies however (typically below a few kHz), a quasi-steady regime seems to hold out which means that assuming quasi-steady combustion (e.g., given by a D2 model) is valid in this case. In this regime, the computed response corresponds with a theoretical expression obtained by a linearization of the Ranz–Marshall correction term. This implies that unsteady aluminum combustion is strongly dependent on convection effects.  相似文献   
776.
Fabien Paillusson 《Molecular physics》2018,116(21-22):3196-3213
ABSTRACT

The so-called Gibbs’ paradox is a paradigmatic narrative illustrating the necessity to account for the N! ways of permuting N identical particles when summing over microstates. Yet, there exist some mixing scenarios for which the expected thermodynamic outcome depends on the viewpoint one chooses to justify this combinatorial term. After a brief summary on Gibbs’ paradox and what is the standard rationale used to justify its resolution, we will allow ourself to question from a historical standpoint whether the Gibbs’ paradox has actually anything to do with Gibbs’ work. In so doing, we also aim at shedding a new light with regards to some of the theoretical claims surrounding its resolution. We will then turn to the statistical thermodynamics of discrete and continuous mixtures and introduce the notion of composition entropy to characterise these systems. This will enable us to address, in a certain sense, a ‘curiosity” pointed out by Gibbs in a paper published in 1876. Finally, we will finish by proposing a connexion between the results we propose and a recent extension of the Landauer bound regarding the minimum amount of heat to be dissipated to reset one bit of memory.  相似文献   
777.
The infrared (IR) spectra of protonated water clusters encode precise information on the dynamics and structure of the hydrated proton. However, the strong anharmonic coupling and quantum effects of these elusive species remain puzzling up to the present day. Here, we report unequivocal evidence that the interplay between the proton transfer and the water wagging motions in the protonated water dimer (Zundel ion) giving rise to the characteristic doublet peak is both more complex and more sensitive to subtle energetic changes than previously thought. In particular, hitherto overlooked low-intensity satellite peaks in the experimental spectrum are now unveiled and mechanistically assigned. Our findings rely on the comparison of IR spectra obtained using two highly accurate potential energy surfaces in conjunction with highly accurate state-resolved quantum simulations. We demonstrate that these high-accuracy simulations are important for providing definite assignments of the complex IR signals of fluxional molecules.

We reveal the intricate dynamics of the proton shuttling motion in the Zundel ion by computing 900 high-accuracy vibrational eigenstates. We show how very subtle energetic changes in the vibrational modes lead to vastly different infrared spectra.  相似文献   
778.
This paper summarizes investigations on the radical polymerization of cationic vinyl monomers with respect to the peculiarities of the reaction in aqueous solution, the synthesis of model polymers and polyelectrolytes with regular structure as well as to a new process of stabilized precipitation polymerization. The rate of polymerization depends on the ionic strength of the solution. Random copolymers of diallyldimethylammonium chloride and acrylamide with variable charge density but equal molecular weight were synthesized by a feeding technique. Block copolymers consisting of charged and uncharged monomelic units with different hydrophilicity are available using macroazoinitiators. The novel polymers are powerful stabilizers in the precipitation polymerization of water soluble cationic vinyl monomers in aqueous salt solution leading to a dispersion of fine polymer particles. Polyampholytes with alternating positively and negatively charged monomelic units in the backbone were obtained by cyclocopolymerization of diallylanmine compounds and derivatives of maleic acid.  相似文献   
779.
780.
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