Peculiar scaling of self-avoiding walk contacts

The nearest neighbor contacts between the two halves of an N-site lattice self-avoiding walk offer an unusual example of scaling random geometry: for N-->infinity they are strictly finite in number but their radius of gyration R(c) is power law distributed proportional to R(-tau)(c), where tau>1 is a novel exponent characterizing universal behavior. A continuum of diverging length scales is associated with the R(c) distribution. A possibly superuniversal tau = 2 is also expected for the contacts of a self-avoiding or random walk with a confining wall.     

Efficient synthesis of (Z)- and (E)-methyl 2-(methoxyimino)-2-phenylacetate

Direct oximation of 2-oxo-2-phenylacetate (3) gave the (Z)-methyl 2-(methoxyimino)-2-phenylacetate (1) in 71% yield, while the E oxime 2 was prepared from 3 in 65% yield via oxime isomerization of 2-(methoxyimino)-2-phenylacetic acid (5). Computational studies suggest that the isomerization of 5 is thermodynamically driven, while the direct oximation of ketoester 3 is kinetically controlled.     

Evaluation of comprehensive on-line liquid chromatography thermally assisted hydrolysis and methylation-gas chromatography-mass spectrometry for characterization of sulfonated lignins

Sulfonated lignins, used as dispersants in agrochemical formulations, have been characterized by hyphenation of ion-pair RPLC and thermally assisted hydrolysis and methylation-GC-MC (THM-GC-MS). The chemical structure of a series of selected lignins was evaluated, both in terms of overall composition and in terms of composition as a function of molecular size. Some sulfonated lignins give rise to unstable formulations. In the compositional analysis, these samples were found to yield additional fragments. A newly developed comprehensive method made it possible to monitor the occurrence of these fragments as a function of molecular size. In addition to differences in the molecular size between "good" and "bad" batches, clear differences in chemical composition were established.     

Determination of the carboxylic acids in acidic and basic process samples by capillary zone electrophoresis

Capillary zone electrophoresis (CZE) with indirect UV detection was used in developing a method for the simultaneous determination of inorganic anions, aliphatic and heterocyclic organic acids in various processed samples. The analytes were determined simultaneously in 10 min using an electrolyte containing 20 mM 2,3-pyrazine dicarboxylic acid, 65 mM tricine, 2 mM BaCl₂, 0.5 mM cetyltrimethylammonium bromide, and 2 M urea at pH 8.06. Linear plots for the analytes were obtained in the concentration range of 2–150 mg L⁻¹. Relative standard deviations (RSDs) of peak areas during a 3-day analysis period varied from 5.5% for glycolate to 9.5% for oxalate. RSDs of migration times varied between 0.4% and 1.1%. The detection limit (at S/N 3) was 1 mg L⁻¹ for all the analytes studied. The proposed method was successfully demonstrated for the determination of carboxylic acids in eight oxygen treated samples of commercial softwood and hardwood kraft lignin and two red wine samples of Pinot Noir grapes. In the kraft lignin samples the concentrations of carboxylic acids correspond to the oxidation time. The acid concentrations of wine varied considerable.     

Central limit theorems for empirical product densities of stationary point processes

We prove the asymptotic normality of kernel estimators of second- and higher-order product densities (and of the pair correlation function) for spatially homogeneous (and isotropic) point processes observed on a sampling window \(W_n\) , which is assumed to expand unboundedly in all directions as \(n \rightarrow \infty \,\) . We first study the asymptotic behavior of the covariances of the empirical product densities under minimal moment and weak dependence assumptions. The proof of the main results is based on the Brillinger-mixing property of the underlying point process and certain smoothness conditions on the higher-order reduced cumulant measures. Finally, the obtained limit theorems enable us to construct \(\chi ^2\) -goodness-of-fit tests for hypothetical product densities.     

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.