Thermodynamic evidence for Ca2+-mediated self-aggregation of Lewis X gold glyconanoparticles. A model for cell adhesion via carbohydrate-carbohydrate interaction

Thermodynamic evidence for the selective Ca(2+)-mediated self-aggregation via carbohydrate-carbohydrate interactions of gold glyconanoparticles functionalized with the disaccharides lactose (lacto-Au) and maltose (malto-Au), or the biologically relevant trisaccharide Lewis X (Le(X)-Au), was obtained by isothermal titration calorimetry. The aggregation process was also directly visualized by atomic force microscopy. It was shown in the case of the trisaccharide Lewis X that the Ca(2+)-mediated aggregation is a slow process that takes place with a decrease in enthalpy of 160 +/- 30 kcal mol(-)(1), while the heat evolved in the case of lactose and maltose glyconanoparticles was very low and thermal equilibrium was quickly achieved. Measurements in the presence of Mg(2+) and Na(+) cations confirm the selectivity for Ca(2+) of Le(X)-Au glyconanoparticles. The relevance of this result to cell-cell adhesion process mediated by carbohydrate-carbohydrate interactions is discussed.     

Unexpected formation of 1-diethylaminobutadiene in photosensitized oxidation of triethylamine induced by 2,3-dihydro-oxoisoaporphine dyes. A 1H NMR and isotopic exchange study

[reaction: see text] Photoreduction of oxoisoaporphine dyes occurs via a stepwise mechanism of electron-proton-electron transfer that leads to the N-hydrogen oxoisoaporphine anion. When triethylamine, TEA, was used as the electron donor in anaerobic conditions, 1-diethylaminobutadiene, DEAB, was one of the oxidation products of TEA, among diethylamine and acetaldehyde. DEAB was identified by (1)H NMR and GC-MS experiments by comparison with the authentic 1-diethylaminobutadiene. This is the first report of a butadienyl derivative formed in the dye-sensitized photooxidation of TEA. In addition, isotopic exchange experiments with TEA-d(15) and D(2)O show that the hydrogens at carbon-2 and carbon-4 of the butadienyl moiety are exchangeable. The observed isotopic exchange pattern could be explained by the head-to-tail coupling of an N,N-diethylvinylamine intermediate that exchanges hydrogens at the C-beta via the enammonium ion.     

Effects of Adsorbed Polyaniline on Redox Process on MoO3 Surface

The effects exhibited by adsorbed conducting polyaniline on the redox process on a molybdenum oxide surface were studied. Thermogravimetric results indicate a 4% polyaniline deposition. Cyclic voltammograms of the adsorbed polymer on MoO3 show that polyaniline exerts remarkable effects on the molybdenum blue oxidation-reduction process, with oxidation and reduction potentials of 0.33 and 0.18 V, respectively. This effect strongly enhances the electrode response, and can be used as an important tool in qualitative and/or quantitative determinations of molybdenum in solution as well as in any substrate. Copyright 1999 Academic Press.     

Electrochemical study of antioxidants at a polypyrrole electrode modified by a nickel phthalocyanine complex. Application to their HPLC separation and to their FIA system detections

A polypyrrole electrode modified with a tetrasulfonated nickel(II) phthalocyanine complex (GCE/PPy/NiPcTs) was used as amperometric electrochemical detector in a flow injection system, in order to determine some antioxidants in foods. The lather were separated by HPLC and detected at the modified electrode. Previous investigations carried out in our laboratory employed this electrode and cyclic voltammetry (CV), obtaining excellent results, due to an electrocatalytic effect on the oxidation of certain alimentary antioxidants, such tert-butylhydroquinone (TBHQ), 3-tert-butyl-4-hydroxyanisole (BHA) and propylgallate (PG). In order to obtain good separation, the chromatographic conditions were optimised. The geometry of the flow injection analysis (FIA) circuit and the reproducibility of the results were also optimised and, finally, the linear relationship between the signal and the concentration was verified. The proposed procedure is more precise and accurate than the conventional voltammetry methods. These results offer new analytical possibilities to this type of modified electrodes. The developed methods were applied to the determination of these antioxidants in commercial food.     

Interactions between cellulose nanofibers and retention systems in flocculation of recycled fibers

Although the positive effect that cellulose nanofibers (CNF) can have on paper strength is known, their effect on flocculation during papermaking is not well understood, and most relevant studies have been carried out in presence of only cationic starch. Flocculation is the key to ensuring retention of fibers, fines, and fillers, and furthermore floc properties have a great influence on paper quality. The aim of this research is to study the interactions between CNF and flocculants by assessing the effect of two types of CNF, from eucalyptus and corn, on the flocculation process induced by three different retention systems [a dual system, polyvinylamine (PVA), and cationic starch as reference]. The results showed that CNF interacted with the flocculants in different ways, affecting flocculation efficiency and floc properties. In general, addition of CNF increased floc stability and minimized overdosing effects. Moreover, presence of CNF increased floc size for given PVA dose; therefore, CNF addition could contribute to improve the wet end in the paper machine if combined with the optimal flocculant and dose.     

奥尔堡PBL模式对提升有机波谱分析教学效果的启示

概述了有机波谱分析课程教学中存在的主要问题，介绍了奥尔堡PBL模式的主要特点和优势，分析了将奥尔堡PBL模式用于有机波谱分析课程教学的必要性和可行性，并从课时分配、教学内容、教学方式和考核方式等4方面提出了教学改革方案，旨在提高教学效果。     

Pyrolysis study of hydrophobic tholins By TG-MS, TG, DTA and DSC methods

This study presents the thermogravimetry (TG) of hydrophobic tholins, obtained from different simulation experiments of prebiotic synthesis carried out in a CH₄/N₂/H₂ atmosphere with spark discharge activation of aqueous aerosols and liquid water. Differential thermal analysis and differential scanning calorimetry were also used to evaluate the thermal behaviour of these complex organic compounds that could play an important role in prebiotic chemistry. A coupled thermogravimetry-mass spectrometry system allowed us to analyse the principal volatile thermal decomposition and fragmentation products of the hydrophobic tholins under dynamic conditions and an inert atmosphere. During their thermal degradation, which occurs in two stages, a wide variety of hydrocarbon products including methane, vinyl monomers (such as ethylene and propylene), acetylene, oligomers, and some other unknown compounds are found. Besides, a thermally stable structure is present (graphitic structure) in these particular organic substances. Finally, data collected from TG experiments in an oxidative atmosphere showed significant differences at temperatures above 240 °C. According to these results, the different techniques of thermal analysis here applied have proved to be an adequate methodology for the study and characterization of these complex systems, structures of which remain controversial even in these days.     

Achiral diacrylate with an anticlinic smectic phase

We present an achiral diacrylate that shows a phase transition from the synclinic smectic C phase (SmC) to the anticlinic smectic C (SmCalt). This last phase has been previously reported only for swallow-tailed or dimeric compounds. Our studies using differential scanning calorimetry, X-ray diffraction, polarizing optical microscopy and broad band dielectric spectroscopy suggest the existence of this mesophase in this bifunctional smectogen.     

Conformational Analysis of the Anti‐obesity Drug Lorcaserin in Water: How To Take Advantage of Long‐Range Residual Dipolar Couplings

The conformational state of 8‐chloro‐1‐methyl‐2,3,4,5‐tetrahydro‐1H‐3‐benzazepine hydrochloride (lorcaserin) in water has been determined on the basis of one‐bond and long‐range C? H residual dipolar coupling (RDC) data along with DFT computations and ³J_HH coupling‐constant analysis. According to this analysis, lorcaserin exists as a conformational equilibrium of two crown‐chair forms, of which the preferred conformation has the methyl group in an equatorial orientation.