Structural and thermodynamic properties of water–membrane interphases: Significance for peptide/membrane interactions

Water appears as a common intermediary in the mechanisms of interaction of proteins and polypeptides with membranes of different lipid composition. In this review, how water modulates the interaction of peptides and proteins with lipid membranes is discussed by correlating the thermodynamic response and the structural changes of water at the membrane interphases.     

Influence of the chemical structure of water-soluble cryptophanes on their overall chiroptical and binding properties

The synthesis and the chiroptical properties of the two enantiomers of the hexacarboxylic acid cryptophane-A derivative, 1, are described in this article. The chiroptical and binding properties of 1 toward achiral and chiral guests have been investigated in water under basic conditions by polarimetry, electronic circular dichroism (ECD), vibrational circular dichroism (VCD), and (1)H NMR spectroscopy. These experiments reveal that the (1)H NMR spectra of 1 are very sensitive to the nature of the guest trapped in its cavity whereas ECD and VCD spectra remain unchanged. We also show that the two enantiomers of 1 are able to distinguish between the two enantiomers of a series of small chiral epoxides. The enantiodiscrimination increases with the size of the chiral guest whereas the corresponding binding constants decrease. In contrast to what was observed for other water-soluble cryptophanes, the molecular recognition process is found independent of the nature of the counterions surrounding host 1, shedding light on the importance of the chemical structure of cryptophanes on their binding and chiroptical properties.     

Improvement of lithium battery performance through composite electrode microstructure optimization

The lithium trivanadate Li_1.2V₃O₈ has been investigated during the past decade as a very promising positive electrode material for lithium batteries due to its high theoretical capacity of 360 mAh/g. However, the experimental capacity remains generally much lower than (about half) the theoretical value. To increase electrode cycling performance in batteries, most researchers generally focus their work on the active material optimisation. Here we show that the polymeric binder of the composite electrode may have an important role on the electrode performance. We describe a new tailored polymeric binder combination with controlled polymer-filler (carbon black) interactions that allows the preparation of new and more efficient electrode architecture. Using this polymeric binder, composite electrodes based on Li_1.2V₃O₈ display a room-temperature cycling capacity of 280 mAh/g (C/5 rate, 3.3-2V) instead of 180 mAh/g using a Bellcore-type composite electrode (PLIon^TM technology). We have coupled SEM observations, galvanostatic cycling and electrochemical impedance spectroscopy in order to define and understand the impact of the microstructure of the composite electrode on its electrochemical performance. Derived from these studies, the main key factors that provide efficient charge carrier collection within the composite electrode complex medium will be discussed. Present findings open up new and attractive prospects for electrode performance optimisation. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14–18, 2004.     

Kinetic Theory of Jet Dynamics in the Stochastic Barotropic and 2D Navier-Stokes Equations

We discuss the dynamics of zonal (or unidirectional) jets for barotropic flows forced by Gaussian stochastic fields with white in time correlation functions. This problem contains the stochastic dynamics of 2D Navier-Stokes equation as a special case. We consider the limit of weak forces and dissipation, when there is a time scale separation between the inertial time scale (fast) and the spin-up or spin-down time (large) needed to reach an average energy balance. In this limit, we show that an adiabatic reduction (or stochastic averaging) of the dynamics can be performed. We then obtain a kinetic equation that describes the slow evolution of zonal jets over a very long time scale, where the effect of non-zonal turbulence has been integrated out. The main theoretical difficulty, achieved in this work, is to analyze the stationary distribution of a Lyapunov equation that describes quasi-Gaussian fluctuations around each zonal jet, in the inertial limit. This is necessary to prove that there is no ultraviolet divergence at leading order, in such a way that the asymptotic expansion is self-consistent. We obtain at leading order a Fokker–Planck equation, associated to a stochastic kinetic equation, that describes the slow jet dynamics. Its deterministic part is related to well known phenomenological theories (for instance Stochastic Structural Stability Theory) and to quasi-linear approximations, whereas the stochastic part allows to go beyond the computation of the most probable zonal jet. We argue that the effect of the stochastic part may be of huge importance when, as for instance in the proximity of phase transitions, more than one attractor of the dynamics is present.     

Chalcone JAI‐51 improves efficacy of synchrotron microbeam radiation therapy of brain tumors

Microbeam radiation therapy (MRT), a preclinical form of radiosurgery, uses spatially fractionated micrometre‐wide synchrotron‐generated X‐ray beams. As MRT alone is predominantly palliative for animal tumors, the effects of the combination of MRT and a newly synthesized chemotherapeutic agent JAI‐51 on 9L gliosarcomas have been evaluated. Fourteen days (D14) after implantation (D0), intracerebral 9LGS‐bearing rats received either MRT, JAI‐51 or both treatments. JAI‐51, alone or immediately after MRT, was administered three times per week. Animals were kept up to ～20 weeks after irradiation or sacrificed at D16 or D28 after treatment for cell cycle analysis. MRT plus JAI‐51 increased significantly the lifespan compared with MRT alone (p = 0.0367). JAI‐51 treatment alone had no effect on rat survival. MRT alone or associated with JAI‐51 induced a cell cycle blockade in G2/M (p < 0.01) while the combined treatment also reduced the proportion of G0/G1 cells. At D28 after irradiation, MRT and MRT/JAI‐51 had a smaller cell blockade effect in the G2/M phase owing to a significant increase in tumor cell death rate (<2c) and a proportional increase of endoreplicative cells (>8c). The combination of MRT and JAI‐51 increases the survival of 9LGS‐bearing rats by inducing endoreduplication of DNA and tumor cell death; further, it slowed the onset of tumor growth resumption two weeks after treatment.     

Increase of lifespan for glioma‐bearing rats by using minibeam radiation therapy

This feasibility work assesses the therapeutic effectiveness of minibeam radiation therapy, a new synchrotron radiotherapy technique. In this new approach the irradiation is performed on 9L gliosarcoma‐bearing rats with arrays of parallel beams of width 500–700 µm. Two irradiation configurations were compared: a lateral unidirectional irradiation and two orthogonal arrays interlacing at the target. A dose escalation study was performed. A factor of three gain in the mean survival time obtained for some animals paves the way for further exploration of the different possibilities of this technique and its further optimization.     

Reduction Des Groupes Fonctionnels Nitroaromatiques Par L'Hydrogene en Presence de Palladium Sur Charbon

Abstract

En utilisant la méthode de réduction habituelle ?hydrogénation catalysée par le palladium sur charbon sur des composés nitroaromatiques, nous nous sommes aperçus que la vitesse ?absorption ?hydrogène décroissait en fonction du temps et que ces réactions n'étaient qu'exceptionnelement complètes. Certains auteurs¹ signalent que cette réaction est plus rapide et plus sélective en milieu neutre qu'en milieu acide ou basique.     

Synthesis and Properties of a 2-Diazohistidine Derivative: A New Photoactivatable Aromatic Amino-Acid Analog

N^α[(tert-Butoxy)carbonyl]-2-diazo-L -histidine methyl ester 1 was synthesized starting from the corresponding L-histidine derivative. The physico-chemical properties of this new photoactivatable amino-acid derivative were established. The synthetic precursor of 1 , 2-amino-L -histidine derivative 3 , was best isolated and characterized as 2-amino-N^α-[(tert-butoxy)carbonyl]-N^τ-tosyl-L -histidine methyl ester ( 4 ). Selective deprotections of 4 (N^α-Boc, N^α-Tos, COOMe) were achieved, thus allowing the use of the corresponding products in peptide synthesis. The optically active dipeptides 8 and 9 were synthesized by coupling 2-amino-N^τ-tosyl-L -histidine methyl ester ( 5 ) with N-[(tert-butoxy)carbonyl]-L -alanine and N^α-[(tert-butoxy)carbonyl]-N^τ-tosyl-L -histidine ( 6 ) with L-alanine methyl ester, respectively. The question of selective diazotization of a 2-aminohistidine residue in a synthetic peptide was studied using competitive diazotizations between 2-amino-1H-imidazole and several amino-acid derivatives susceptible to undergo nitrosylation. The results show that synthetic photoactivatable peptides incorporating a 2-diazohistidine residue might become useful photoaffinity probes.