Water‐soluble poly(ethylene oxide)‐block‐poly(p‐phenylene vinylene) copolymer: Synthesis and characterization

Water‐soluble and photoluminescent block copolymers [poly(ethylene oxide)‐block‐poly(p‐phenylene vinylene) (PEO‐b‐PPV)] were synthesized, in two steps, by the addition of α‐halo‐α′‐alkylsulfinyl‐p‐xylene from activated poly(ethylene oxide) (PEO) chains in tetrahydrofuran at 25 °C. This copolymerization, which was derived from the Vanderzande poly(p‐phenylene vinylene) (PPV) synthesis, led to partly converted PEO‐b‐PPV block copolymers mixed with unreacted PEO chains. The yield, length, and composition of these added sequences depended on the experimental conditions, namely, the order of reagent addition, the nature of the monomers, and the addition of an extra base. The addition of lithium tert‐butoxide increased the length of the PPV precursor sequence and reduced spontaneous conversion. The conversion into PPV could be achieved in a second step by a thermal treatment. A spectral analysis of the reactive medium and the composition of the resulting polymers revealed new evidence for an anionic mechanism of the copolymerization process under our experimental conditions. Moreover, the photoluminescence yields were strongly dependant on the conjugation length and on the solvent, with a maximum (70%) in tetrahydrofuran and a minimum (<1%) in water. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4337–4350, 2005     

Exploring the light-quark interaction

Two basic motivations for an upgraded JLab facility are the needs: to determine the essential nature of light-quark confinement and dynamical chiral symmetry breaking (DCSB); and to understand nucleon structure and spectroscopy in terms of QCD's elementary degrees of freedom. During the next ten years a programme of experiment and theory will be conducted that can address these questions. We present a Dyson-Schwinger equation perspective on this effort with numerous illustrations, amongst them: an interpretation of string-breaking; a symmetry-preserving truncation for mesons; the nucleon's strangeness σ-term; and the neutron's charge distribution.     

Controlled synthesis of carboxylic acid end‐capped poly(heptadecafluorodecyl acrylate) and copolymers with 2‐hydroxyethyl acrylate

1H,1H,2H,2H‐Heptadecafluorodecyl acrylate (AC8) was polymerized by reversible addition–fragmentation chain transfer and copolymerized with 2‐hydroxyethyl acrylate with the formation of random and block copolymers, respectively. The kinetics of the (co)polymerization was monitored with ¹H NMR spectroscopy and showed that the homopolymerization and random copolymerization of AC8 were under control. As a result of this control and the use of S‐1‐dodecyl‐S‐(α,α′‐dimethyl‐α″‐acetic acid)trithiocarbonate as a chain‐transfer agent, the copolymer chains were end‐capped by an α‐carboxylic acid group. Moreover, the controlled polymerization of AC8 was confirmed by the successful synthesis of poly(1H,1H,2H,2H‐heptadecafluorodecyl acrylate)‐b‐poly(2‐hydroxyethyl acrylate) diblock copolymers, which were typically amphiphilic compounds. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1499–1506, 2007     

Compact almost automorphic solutions to semilinear Cauchy problems with non-dense domain

In this work we study the existence and uniqueness of compact almost automorphic solutions to a first-order differential equation with a linear part dominated by a Hille-Yosida type operator with non dense domain.     

Effectiveness of isotopically labelled and non‐isotopically labelled internal standards in the gas chromatography/mass spectrometry analysis of sulfur compounds in wines: use of a statistically based matrix comprehensive approach

The effectiveness of isotopically and non‐isotopically labelled internal standards in reducing matrix‐induced effects is evaluated. The question is addressed in the quantitative analysis by gas chromatography/mass spectrometry (GC/MS) of dimethyl sulphide, chosen as a typical example of volatile sulphur compounds, in wine matrices. When matrix/run effects are not cancelled out the use of a variance component model (VCM) to handle the linear calibrations obtained by regression technique is successful. The method implies the estimation of an overall calibration straight line, which properly takes into account the uncertainty due to different matrices, the calibration run and the measurement error, making the use of an isotopically labelled internal standard not necessary. The obtained results show that the benefits of lowering times and costs for routine analyses compensate for the small increase in uncertainty in the concentration values obtained in the regression analysis and the slight increase in the detection limit. Copyright © 2009 John Wiley & Sons, Ltd.     

Fast measurement of heteronuclear relaxation: frequency-domain analysis of NMR accordion spectroscopy

NMR relaxation parameters are usually derived from series of 2D experiments. The whole procedure can be very time consuming, especially for the study of the relaxation of nuclei at natural abundance. Palmer and Mandel have proposed the use of accordion spectroscopy to determine one relaxation parameter using two experiments only. In this paper, we show that the experimental time can be further reduced, by recording only three experiments for the determination of both the longitudinal and transverse relaxation rates. The analysis of the experiments is performed in the frequency domain, the relaxation rates being deduced from the linewidth of the peaks of interest. A detailed statistical analysis of errors introduced by the line fitting procedure on derived relaxation parameters was used to derive guidelines for the choice of experimental parameters. This procedure was applied to the study of the Cα relaxation parameters of a six-residue unlabeled peptide. The results were compared with those obtained by classical accordion spectroscopy. Copyright © 2001 John Wiley & Sons, Ltd.     

Characterization of nanometric carbon materials by time-resolved fluorescence polarization anisotropy

In this work, time-resolved fluorescence polarization anisotropy (TRFPA) technique has been applied to the determination of the average size of asphaltenes and combustion-generated carbon nanoparticles. The characteristic depolarization time of fluorescence light following photon absorption is related to the typical particle size through the Stoke–Einstein rotational diffusion equation. The TRFPA technique employed in our experiment achieves sub-nanosecond time resolution, roughly corresponding to sub-nanometer accuracy in determining the particle size. The technique has been applied to both asphaltene and carbon nanoparticles, the former being a component of petroleum, whereas the latter result from combustion processes. Therefore, a complete and reliable characterization of such particles is of great importance in oil industry and atmospheric physics, respectively. Although the TRFPA technique has been developed and widely used on molecular and biological samples, it proves to be a very powerful tool for measuring the size of asphaltene and soot particles as small as few nanometers with a resolution of the order of 0.1 nm.     

Intermolecular Forces Driving Hexamethylenetetramine Co-Crystal Formation,a DFT and XRD Analysis

Interest in co-crystals formation has been constantly growing since their discovery, almost a century ago. Such success is due to the ability to tune the physical-chemical properties of the components in solid state by avoiding a change in their molecular structure. The properties influenced by the co-crystals formation range from an improvement of mechanical features and chemical stability to different solubility. In the scientific research area, the pharmacological field is undoubtedly one of those in which an expansion of the co-crystal knowledge can offer wide benefits. In this work, we described the crystalline structure of hexamethylenetetramine co-crystallized with the isophthalic acid, and we compared it with another co-crystal, showing the same components but different stoichiometry. To give a wider overview on the nature of the interactions behind the observed crystal packing and to rationalize the reasons of its formation, a computational analysis on such structures was carried out.