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.     

Chemical kinetics at high pressure

Abstract

Numerous studies have demonstrated the importance to include pressure as a kinetic parameter in the elucidation of inorganic reaction mechanisms. These studies have specially led to a better understanding and a systematic classification of solvent exchange and ligand substitution reactions of octahedral complexes of transition metal elements. The mechanistic picture for substution reactions on square planar complexes is well established and involves a concurrent bimolecular attack by solvent and the nucleophile on the substrate with a considerable discrimination among different entering groups. The search for factor promoting the conversion of the normal associative mode of activation into a dissociative process has then attracted much attention. Two attempts to induce dissociation, as studied by high-pressure NMR, are presented: one is to prevent the formation by means of sterically hindered ligands, the other one is to promote bond weakening at the leaving group.     

Engineering of a two-step purification strategy for a panel of monoclonal immunoglobulin M directed against undifferentiated human embryonic stem cells

A two-step purification strategy comprising of polyethylene glycol (PEG) precipitation and anion-exchange chromatography was developed for a panel of monoclonal immunoglobulin M (IgM) (pI 5.5–7.7) produced from hybridoma cultures. PEG precipitation was optimized with regards to concentration, pH and mixing. For anion-exchange chromatography, different resins were screened of which Fractogel EMD, a polymer grafted porous resin had the highest capacity. Despite its significantly slower mass transfer, the binding capacity was still higher compared to a convection driven resin (monolith). This purification strategy was successfully demonstrated for all 9 IgMs in the panel. In small scale most antibodies could be purified to >95% purity with the exception of two which gave a lower final purity (46% and 85%). The yield was dependent on the different antibodies ranging from 28% to 84%. Further improvement of recovery and purity was obtained by the digestion of DNA present in the hybridoma supernatant using an endonuclease, benzonase. So far this strategy has been applied for the purification of up to 2 l hybridoma supernatants.     

Optimization of capacity expansion planning for gas transportation networks

This paper presents techniques for solving the problem of minimizing investment costs on an existing gas transportation network. The goal of this program is to find, first, the optimal location of pipeline segments to be reinforced and, second, the optimal sizes (among a discrete commercial list of diameters) under the constraint of satisfaction of demands with high enough pressure for all users.     

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].     

Kinetics of partly diffusion-controlled reaction XXI: A simple algorithm for computing the apparent rate of reaction

Starting from Smoluchowski's hypothesis, a simple algorithm is developed in order to obtain the apparent rate constant at large values of time, t, with some physical and chemical processes, as in the case of diffusion controlled reactions. Some practical examples are illustrated, assuming nonuniform distribution function, space-dependent diffusion coefficient or short-range interaction leading to an asymptotic analytical expression of the form α + β/√t, where α and β are constants function of the system of interest.