Comparison of three methods for fractionation and enrichment of low molecular weight proteins for SELDI-TOF-MS differential analysis

In most diseases, the clinical need for serum/plasma markers has never been so crucial, not only for diagnosis, but also for the selection of the most efficient therapies, as well as exclusion of ineffective or toxic treatment. Due to the high sample complexity, prefractionation is essential for exploring the deep proteome and finding specific markers.In this study, three different sample preparation methods (i.e., highly abundant protein precipitation, restricted access materials (RAM) combined with IMAC chromatography and peptide ligand affinity beads) were investigated in order to select the best fractionation step for further differential proteomic experiments focusing on the LMW proteome (MW inferior to 40,000 Da). Indeed, the aim was not to cover the entire plasma/serum proteome, but to enrich potentially interesting tissue leakage proteins. These three methods were evaluated on their reproducibility, on the SELDI-TOF-MS peptide/protein peaks generated after fractionation and on the information supplied.The studied methods appeared to give complementary information and presented good reproducibility (below 20%). Peptide ligand affinity beads were found to provide efficient depletion of HMW proteins and peak enrichment in protein/peptide profiles.     

Plasma brominated polymer particles as grafting substrate for thiol‐terminated telomers

A combined surface activation and “grafting to” strategy was developed to convert divinylbenzene particles into weak cation exchangers suitable for protein separation. The initial activation step was based on plasma modification with bromoform, which rendered the particles amenable to further reaction with nucleophiles by introducing Br to a surface content of 11.2 atom‐%, as determined by X‐ray photoelectron spectroscopy. Grafting of thiol‐terminated glydicyl methacrylate telomers to freshly plasma activated surfaces was accomplished without the use of added initiator, and the grafting was verified both by reduction in bromine content and the appearance of sulfur‐carbon linkages, showing that the surface grafts were covalently bonded. Following grafting the attached glydicyl methacrylate telomer tentacles were further modified by a two‐step procedure involving hydrolysis to 2,3‐hydroxypropyl groups and conversion of hydroxyl groups to carboxylate functionality by succinic anhydride. The final material was capable of baseline separating four model proteins in 3 min by gradient cation exchange chromatography in a fully aqueous eluent.     

Regiocontrolled fluorination of 2-hydroxyalkyl dihydropyrans and carbonyl derivatives

Reaction of polysubstituted 2-hydroxyalkyldihydropyrans with DAST led regiospecifically to fluorination at the exocyclic position, except for primary alcohols. Difluorination of carbonylated analogues with deoxo-fluor™ occurred also regioselectively. The unexpected stability and synthetic potential of these new allylic fluorides are discussed.     

Contingent derivatives of set-valued maps and applications to vector optimization

In this paper we investigate contingent derivatives of set-valued maps and their lower and upper semidifferentiability properties. We provide also some calculus rules for these derivatives in infinite dimensional spaces. The concept of contingent derivatives is then applied to produce several necessary and sufficient conditions for vector optimization problems with set-valued objectives.This paper was written when the author was at the University of Erlangen-Nurnberg under a grant of the Alexander von Humboldt Foundation.On leave from the Institute of Mathematics, Hanoi, Vietnam.     

Contrast enhancement on crystalline silicon in polarized reflection mode tip-enhanced Raman spectroscopy

Tip-enhanced Raman spectroscopy in reflection mode makes possible the nanoscale characterization of non-transparent samples, such as silicon, inaccessible in transmission mode. However, a particular feature of this technique is the superposition of the far-field Raman signal with the near-field one generated in the tip vicinity sometimes resulting in a low near-field-to-far-field contrast. By using a polarized configuration and orientation optimization of a (0 0 1) crystalline Si sample we were able to enhance significantly the contrast through reducing the far-field contribution, reaching a value of about 40. This contrast enhancement method can be applied in principle to any crystalline sample.     

Determination of k-factors by thermal neutron activation technique

The k_{o, Au}-factors of 10 elements have been determined by irradating the samples with thermal neutrons in the reactor thermal column. The proposed method has the advantage of eliminating the errors induced by the uncertainties of the neutron spectrum parameters and the nuclear data. The results obtained are in good agreement with the literature data.     

Liberating the Subgradient Optimality Conditions from Constraint Qualifications

In convex optimization the significance of constraint qualifications is evidenced by the simple duality theory, and the elegant subgradient optimality conditions which completely characterize a minimizer. However, the constraint qualifications do not always hold even for finite dimensional optimization problems and frequently fail for infinite dimensional problems. In the present work we take a broader view of the subgradient optimality conditions by allowing them to depend on a sequence of ε-subgradients at a minimizer and then by letting them to hold in the limit. Liberating the optimality conditions in this way permits us to obtain a complete characterization of optimality without a constraint qualification. As an easy consequence of these results we obtain optimality conditions for conic convex optimization problems without a constraint qualification. We derive these conditions by applying a powerful combination of conjugate analysis and ε-subdifferential calculus. Numerical examples are discussed to illustrate the significance of the sequential conditions.     

Microstructures réalisant toute compressibilité ou conductivité encadrée par les bornes de Hashin et Shtrikman

The conductivity or bulk modulus of an isotropic composite consisting of two well-ordered isotropic phases is situated between the lower and upper bounds of Hashin and Shtrikman. This work is concerned with the construction of two new microstructures capable of realizing every conductivity or bulk modulus comprised between these bounds. The two microstructures obtained, appearing to be simpler than those presented in the literature to achieve the same purpose, have the property that the variation of the corresponding conductivity or bulk modulus is strictly monotone with respect to the geometric parameter characterizing them. To cite this article: Q.-C. He, H.L. Quang, C. R. Mecanique 333 (2005).     

Uniform strain fields and exact results in an elastoplastic fibre-reinforced composite

This work is concerned with a two-phase material consisting of an elastoplastic matrix reinforced by linearly elastic fibres. It is first shown that uniform strain fields can be generated in this heterogeneous material. A return-mapping based algorithm is then proposed and used to find uniform strain loading paths. With the help of uniform strain fields, exact results, independent of the transverse geometry and arrangement of the fibres, are derived for the effective elastic properties and for the effective initial and current yield surfaces. To cite this article: Q.-C. He, H. Le Quang, C. R. Mecanique 332 (2004).