Hydrophilic and hydrophobic copolymer systems based on acrylic derivatives of pyrrolidone and pyrrolidine

This article deals with the synthesis of hydrophilic methacrylic monomers derived from ethyl pyrrolidone [2‐ethyl‐(2‐pyrrolidone) methacrylate (EPM)] and ethyl pyrrolidine [2‐ethyl‐(2‐pyrrolidine) methacrylate (EPyM)] and their respective homopolymers. For the determination of their reactivity in radical copolymerization reactions, both monomers were copolymerized with methyl methacrylate (MMA), the reactivity ratios being calculated by the application of linear and nonlinear mathematical methods. EPM and MMA had ratios of r_EPM = 1.11 and r_MMA = 0.76, and this indicated that EPM with MMA had a higher reactivity in radical copolymerization processes than vinyl pyrrolidone (VP; r_VP = 0.005 and r_MMA = 4.7). EPyM and MMA had reactivity ratios of r_EPyM = 1.31 and r_MMA = 0.92, and this implied, as for the EPM–MMA copolymers, a tendency to form random or Bernoullian copolymers. The glass‐transition temperatures of the prepared copolymers were determined by differential scanning calorimetry (DSC) and were found to adjust to the Fox equation. Total‐conversion copolymers were prepared, and their behavior in aqueous media was found to be dependent on the copolymer composition. The swelling kinetics of the copolymers followed water transport mechanism case II, which is the most desirable kinetic behavior for a swelling controlled‐release material. Finally, the different states of water in the hydrogels—nonfreezing water, freezing bound water, and unbound freezing water—were determined by DSC and found to be dependent on the hydrophilic and hydrophobic units of the copolymers. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 395–407, 2003     

Influence of the loading path on the strength of fiber-reinforced composites subjected to transverse compression and shear

The influence of the loading path on the failure locus of a composite lamina subjected to transverse compression and out-of-plane shear is analyzed through computational micromechanics. This is carried out using the finite element simulation of a representative volume element of the microstructure, which takes into account explicitly fiber and matrix spatial distribution within the lamina. In addition, the actual failure mechanisms (plastic deformation of the matrix and interface decohesion) are included in the simulations through the corresponding constitutive models. Two different interface strength values were chosen to explore the limiting cases of composites with strong or weak interfaces. It was found that failure locus was independent of the loading path for the three cases analyzed (pseudo-radial, compression followed by shear and shear followed by compression) in the composites with strong and weak interfaces. This result was attributed to the fact that the dominant failure mechanism in each material was the same in transverse compression and in shear. Failure is also controlled by the same mechanisms under a combination of both stresses and the failure locus depended mainly on the magnitude of the stresses that trigger fracture rather than in the loading path to reach the critical condition.     

Determination of lithium in human serum by electrothermal atomic absorption spectrometry

An efficient method was developed for the determination of nanogram levels of lithium in biological samples. Serum samples from human subjects from southeastern Spain, treated or not treated with lithium carbonate, were analyzed by electrothermal atomic absorption spectrometry. The samples were previously treated with a matrix modifier consisting of 0.1% Triton X-100 and injected through a graphite tube with L'vov platform. The Li concentrations measured by the procedure described for the 3 certified reference samples used were not significantly different (p > 0.05) than certified levels. Sample recoveries and variability during several days, with coefficients of variation from 4.00 to 14.8%, demonstrated the reliability and accuracy of this technique. Mean Li concentration determined in the serum of individuals with psychiatric disorders treated with Li (n = 117, 5.077 +/- 1.795 microg Li/mL) was significantly higher (p < 0.001) than that in individuals not treated with Li (n = 24, 1.902 +/- 2.054 ng Li/mL).     

Enzyme catalysis in organic solvents: a promising field for optical biosensing

The ability of enzymes to work in non-aqueous media offers new and almost unexploited possibilities for the development of new optical biosensors. The advantages of performing biocatalytic reactions in non-aqueous media are discussed in relation to their possible application in optical biosensor design. Attention is focused on the factors that influence enzymatic catalysis in organic solvents, including the role of enzyme-associated water, criteria for solvent selection and the alteration of enzyme specificity. Recent examples of relevant applications and future prospects of organic-phase optical biosensing are discussed.     

Alkylation of β-diketones through their co(II), co(III) and zn(II) complexes. 1-Bromoadamantane as alkylating agent.

α-(1-adamantyl)-β-diketones are now accessible by the alkylation of Co(II) complexes of β-diketones with 1-bromoadamantane. The intermediacy of adamantyl cation is proposed. Co(II), Co(III) and Zn(II) complexes of pentane-2,4-dione react with alkyl halides precursors of stabilized carbenium ions, to give 3-alkylpentane-2,4-diones.     

Ferrocenyl and permethylferrocenyl cyclic and polyhedral siloxane polymers as mediators in amperometric biosensors

Cyclosiloxane and silsesquioxane-based ferrocenyl and permethylferrocenyl polymers have been used as mediators in amperometric enzyme electrodes for the detection of glucose. Biosensors have been prepared by electrostatically immobilizing the enzyme glucose oxidase (GOx) on electrodes modified with the polymers. The steady-state amperometric response of the sensors is investigated as a function of the applied potential and substrate concentration. The dependence of the sensors response on the structure of the siloxane-framework and on the presence or not of methyl groups on the ferrocenyl units is discussed.     

Selenium speciation by coupling vesicle mediated HPLC with off-line ETAAS and on-line focused microwave digestion HG-AAS detection

A novel High Performance Liquid Chromatography (HPLC) method for the separation of selenium species with specific detection by off-line Electrothermal Atomization Atomic Absorption Spectrometry (ETAAS) or on-line focused microwave digestion (MW) Hydride Generation Atomic Absorption Spectrometry (HG-AAS) is described. Vesicular mobile phases of the cationic surfactant didodecyldimethylammonium bromide (DDAB) have been evaluated for the liquid chromatographic separation of inorganic selenium (selenite and selenate) and different selenoaminoacids (selenocystine, selenomethionine and selenoethionine) on a C(18) reversed-phase column modified by DDAB molecules. The effects of different parameters (pH, buffer and vesicle concentrations) of the mobile phase on the retention times have been determined. The detection limit for selenium with the proposed off-line HPLC-ETAAS method has been found to be 5 microg/L of Se. The detection limit using HPLC-"on line" focused microwave digestion-HG-AAS has been found to be 1 microg/L of Se, with a precision (repeatability) better than +/- 5%. The latter proved to be an exceptional on-line real-time chromatographic detector for selenium speciation purposes.