High-dynamic-range bulk-elastic-wave correlator

The nonlinear interaction between two bulk elastic waves of different polarisations is used to generate a propagating elastic wave carrying a correlation of the two input waveforms. Measurements show the high efficiency and dynamic range of the device and a variable-delay capability is demonstrated.     

Practical aspects of shimming a high resolution magic angle spinning probe

High resolution magic angle spinning (HRMAS) has become an extremely versatile tool to study heterogeneous systems. HRMAS relies on magic angle spinning of the sample to average out to zero magnetic susceptibility differences in the sample and to obtain resonance linewidths approaching those of liquid state NMR. Shimming such samples therefore becomes an important issue. By analyzing the different sources of magnetic field perturbations present in a sample under MAS conditions, we propose a simple protocol to obtain optimum shim settings in HRMAS. In the case of aqueous samples, we show that the lock level cannot be used as a reliable indicator of the quality of the shims at high spinning speeds. This effect is explained by the presence of temperature gradients imparted by the sample rotation.     

Stepwise and concerted electron-transfer/bond breaking reactions. solvent control of the existence of unstable pi ion radicals and of the activation barriers of their heterolytic cleavage

Available data from various sources seem to indicate an important role of solvation in the cleavage rates of intermediate pi ion radicals, in the passage from concerted to stepwise electron-transfer/bond breaking reaction pathways and even in the very existence of pi ion radicals. After preliminary computations treating the solvent as dielectric continuum, these expectations are examined with the help of a simple model system involving the anion radical of ONCH(2)Cl and two molecules of water, which allows the application of advanced computational techniques and a treatment of these solvent effects that emphasizes the role of solvent molecules that sit close to the charge centers of the molecule. A pi ion radical minimum indeed appears upon introduction of the two water molecules, and cleavage is accompanied by their displacement toward the leaving anion, thus offering a qualitative mimicry of the experimental observations.     

Photoinduction of surface-relief gratings during all-optical poling of polymer films

Using the all-optical poling method, we observed the formation of a surface-relief grating (SRG) in an amorphous polymer film containing azo dye molecules in side chain positions. The experiment consists of a seeding-type process. We used a recently described experimental setup that permits a periodic nonlinear pattern to be produced by the index dispersion of glass. The particular configuration permits photoinduced translation diffusion of the azo chromophores to be observed as the origin of the SRG formation. Analyses of the gratings recorded by use of s (TE) and p (TM) polarization of the writing beams are conducted by atomic-force microscopy. The effect is attributed to mass transport from regions of high isomerization activity to regions of lower activity.     

Activation barriers in the homolytic cleavage of radicals and ion radicals

As revealed by several experimental examples, radicals and ion radicals may, in contrast with closed-shell molecules, undergo exothermic homolytic cleavages (.A..B --> A: +.B) with substantial activation barriers. A two-state semiclassical model is proposed for explaining the existence of the barrier and estimating its magnitude. It is based on the intersection of the potential energy surfaces characterizing the dissociation of a bonding state, .A..B -->.A. +.B, on one hand, and the approach to bonding distance of a repulsive state, A: +.B --> A therefore B, on the other. After inclusion of the bond cleavage and formation as Morse curves in the normal-mode analysis, a simple activation driving force relationship is obtained, the two main ingredients of the intrinsic barrier being the triplet excitation energy of the A moiety and the pi*--> sigma* excitation energy in .A-B. The model is then tested by quantum chemical calculations, first on a simplified system to evaluate the calculation techniques and then on a real system. A comparison of the model predictions with experiment is finally performed using the rate data recently gathered for the cleavage of 4-cyanophenyl alkyl ether anion radicals, which cover a respectable range of driving forces, showing satisfactory agreement between theoretical predictions and experimental data.     

The analysis of elliptic families

In this paper we specialize the results obtained in [BF1] to the case of a family of Dirac operators. We first calculate the curvature of the unitary connection on the determinant bundle which we introduced in [BF1].We also calculate the odd Chern forms of Quillen for a family of self-adjoint Dirac operators and give a simple proof of certain results of Atiyah-Patodi-Singer on êta invariants.We finally give a heat equation proof of the holonomy theorem, in the form suggested by Witten [W 1, 2].     

Novel chemico-mechanical approach towards long-term implantable glucose sensing

The proof of concept of a continuously sensing affinity device based on the glucose-dependent viscosity of a sensitive solution containing dextran and Concanavalin A has been successfully demonstrated. The biosensor incorporates a piezoelectric diaphragm and a flow-resisting microchannel for viscosity detection, and a free-standing Anodic Alumina Oxide (AAO) porous nano-membrane as glucose selective interface. Extensive in vitro glucose measurements between two physiologically relevant glucose concentrations, 2 mM and 9 mM (respectively hypo- and hyperglycemia), were successfully performed during 4 days. To the best of our knowledge, such reversibility and stability of glucose measurement over time had not been reported yet.