31 research outputs found

    Thermal transitions and dynamics in nanocomposite hydrogels

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    Hydrogels based on nanocomposites of statistical poly(hydroxyethyl acrylate-co-ethyl acrylate) and silica, prepared by simultaneous copolymerization and generation of silica nanoparticles by sol-gel process at various copolymer compositions and silica contents, characterized by a fine dispersion of filler, were investigated with respect to glass transition and polymer dynamics by dielectric techniques. These include thermally stimulated depolarization currents and dielectric relaxation spectroscopy, covering together broad ranges of frequency and temperature. In addition, equilibrium water sorption isotherms were recorded at room temperature (25 A degrees C). Special attention was paid to the investigation of effects of silica on glass transition, polymer dynamics (secondary gamma and beta (sw) relaxations and segmental alpha relaxation), and electrical conductivity in the dry systems (xerogels) and in the hydrogels at various levels of relative humidity/water content. An overall reduction of molecular mobility is observed in the nanocomposite xerogels, in particular at high silica contents. Analysis of the results and comparison with previous work on similar systems enable to discuss this reduction of molecular mobility in terms of constraints to polymeric motion imposed by interfacial polymer-filler interactions and by the formation of a continuous silica network interpenetrated with the polymer network at filler contents higher than about 15 wt%.The research leading to these results has received support from the program for basic research PEBE 2010 funded by the National Technical University of Athens.Kyritsis, A.; Spanoudaki, A.; Pandis, C.; Hartmann, L.; Pelster, R.; Shinyashiki, N.; Rodríguez Hernández, JC.... (2012). Thermal transitions and dynamics in nanocomposite hydrogels. Journal of Thermal Analysis and Calorimetry. 108(3):1067-1078. doi:10.1007/s10973-011-2093-5S106710781083Peppas NA, editor. Hydrogels in medicine and pharmacy, vol. I. Boca Raton, FL: CRC Press; 1986.Stoy V, Kliment C. Hydrogels: speciality plastics for biomedical and pharmaceutical applications. Basel: Technomic; 1996.Kyritsis A, Pissis P, Gomez Ribelles JL, Monleon Pradas M. Depolarization thermocurrent studies in poly(hydroxyethyl acrylate)/water hydrogels. J Polym Sci Part B Polym Phys. 1994;32:1001–8.Kyritsis A, Pissis P, Grammatikakis J. Dielectric relaxation spectroscopy in poly(hydroxyethyl acrylate)/water hydrogels. J Polym Sci Part B Polym Phys. 1995;33:1737–50.Kyritsis A, Pissis P, Gomez Ribelles JL, Monleon Pradas M. Polymer-water interactions in poly(hydroxyethyl acrylate) hydrogels studied by dielectric, calorimetric and sorption isotherm measurements. Polym Gels Netw. 1995;3:445–69.Gallego Ferrer G, Monleon Pradas M, Gomez Ribelles JL, Pissis P. Swelling and thermally stimulated depolarization currents in hydrogels formed by interpenetrating polymer networks. J Non-Cryst Solids. 1998;235–237:692–6.Gomez Ribelles JL, Monleon Pradas M, Gallego Ferrer G, Peidro Torres N, Perez Gimenez V, Pissis P, Kyritsis A. Poly(methyl acrylate)/poly(hydroxyethyl acrylate) sequential interpenetrating polymer networks. Miscibility and wáter sorption behavior. J Polym Sci Part B Polym Phys. 1999;37:1587–99.Campillo-Fernandez AJ, Salmeron Sanchez M, Sabater i Serra R, Meseguer Duenas JM, Monleon Pradas M, Gomez Ribelles JL. Water-induced (nano) organization in poly(ethyl acrylate-co-hydroxyethyl acrylate) networks. Eur Polym J. 2008;44:1996–2004.Kyritsis A, Spanoudaki A, Pandis C, Hartmann L, Pelster R, Shinyashiki N, Rodríguez Hernández JC, Gómez Ribelles JL, Monleón Pradas M, Pissis P. Water and polymer dynamics in poly(hydroxyl ethyl acrylate-co-ethyl acrylate) copolymer hydrogels. Eur Polym J. 2011;47:2391–2402.Haraguchi K. Nanocomposite hydrogels. Curr Opin Solid State Mater Sci. 2007;11:47–54.Janovák L, Varga J, Kemény L, Dékány I. Swelling properties of copolymer hydrogels in the presence of montmorillonite and alkylammonium montmorillonite. Appl Clay Sci. 2009;43:260–70.Janovák L, Varga J, Kemény L, Dékány I. The effect of surface modification of layer silicates on the thermoanalytical properties of poly(NIPAAm-co-AAm) based composite hydrogels. J Therm Anal Calorim. 2009;98:485–93.Rodriguez Hernandez JC, Salmeron Sanchez M, Gomez Ribelles JL, Monleon Pradas M. Polymer-silica nanocomposites prepared by sol–gel technique: nanoindentation and tapping mode AFM studies. Eur Polym J. 2007;43:2775–83.Rodriguez Hernandez JC, Monleon Pradas M, Gomez Ribelles JL. Properties of poly(2-hydroxyethyl acrylate)-silica nanocomposites obtained by the sol–gel process. J Non-Cryst Solids. 2008;354:1900–8.Pandis C, Spanoudaki A, Kyritsis A, Pissis P, Rodriguez Hernandez JC, Gomez Ribelles JL, Monleon Pradas M. Water sorption characteristics of poly(2-hydroxyethyl acrylate)/silica nanocomposite hydrogels. J Polym Sci Part B Polym Phys. 2011;49:657–68.Stathopoulos A, Klonos P, Kyritsis A, Pissis P, Christodoulides C, Rodriguez Hernandez JC, Monleon Pradas M, Gomez Ribelles JL. Water sorption and polymer dynamics in hybrid poly(hydroxyethyl-co-ethyl acrylate)/silica hydrogels. Eur Polym J. 2010;46:101–11.Kremer F, Schoenhals A, editors. Broadband dielectric spectroscopy. Berlin: Springer; 2002.Donth E. The glass transition: relaxation dynamics in liquids and disordered materials. Berlin: Springer; 2001.Havriliak S Jr, Havriliak SJ. Dielectric and mechanical relaxation in materials. Munich: Hanser; 1997.Kripotou S, Pissis P, Savelyev YV, Robota LP, Travinskaya TV. Polymer dynamics in polyurethane/clay nanocomposites studied by dielectric and thermal techniques. J Macromol Sci Phys. 2010;49:86–110.Pelster R, Spanoudaki A, Kruse T. Microstructure and effective properties of nanocomposites: ferrofluids as tunable model systems. J Phys D Appl Phys. 2004;37:307–17.Pissis P, Kyritsis A. Electrical conductivity studies in hydrogels. Solid State Ionics. 1997;97:105–13.Angell CA. Relaxation in liquids, polymers and plastic crystals—strong/fragile patterns and problems. J Non-Cryst Solids. 1991;131–133:13–31.Fragiadakis D, Pissis P. Glass transition and segmental dynamics in poly(dimethylsiloxane)/silica nanocomposites studied by various techniques. J Non-Cryst Solids. 2007;353:4344–52.Kourkoutsaki Th, Logakis E, Kroutilova I, Matejka L, Nedbal J, Pissis P. Polymer dynamics in rubbery epoxy networks/polyhedral oligomeric silsequioxanes nanocomposites. J Appl Polym Sci. 2009;113:2569–82.Fragiadakis D, Bokobza L, Pissis P. Dynamics near the particle surface in natural rubber–silica nanocomposites. Polymer. 2011;52:3175–3182.Klonos P, Panagopoulou A, Bokobza L, Kyritsis A, Peoglos V, Pissis P. Comparative studies on effects of silica and titania nanoparticles on crystallization and complex segmental dynamics in poly(dimethylsiloxane). Polymer. 2010;51:5490–9.Napolitano S, Wuebbenhorst M. The lifetime of the deviations from bulk behavior in polymers confined at the nanoscale. Nat Commun. 2011;2:260. doi: 10.1038/incomms1259

    Occupational and consumer risk estimates for nanoparticles emitted by laser printers

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    Several studies have reported laser printers as significant sources of nanosized particles (<0.1 μm). Laser printers are used occupationally in office environments and by consumers in their homes. The current work combines existing epidemiological and toxicological evidence on particle-related health effects, measuring doses as mass, particle number and surface area, to estimate and compare the potential risks in occupational and consumer exposure scenarios related to the use of laser printers. The daily uptake of laser printer particles was estimated based on measured particle size distributions and lung deposition modelling. The obtained daily uptakes (particle mass 0.15–0.44 μg d−1; particle number 1.1–3.1 × 109 d−1) were estimated to correspond to 4–13 (mass) or 12–34 (number) deaths per million persons exposed on the basis of epidemiological risk estimates for ambient particles. These risks are higher than the generally used definition of acceptable risk of 1 × 10−6, but substantially lower than the estimated risks due to ambient particles. Toxicological studies on ambient particles revealed consistent values for lowest observed effect levels (LOELs) which were converted into equivalent daily uptakes using allometric scaling. These LOEL uptakes were by a factor of about 330–1,000 (mass) and 1,000–2,500 (particle surface area) higher than estimated uptakes from printers. This toxicological assessment would indicate no significant health risks due to printer particles. Finally, our study suggests that particle number (not mass) and mass (not surface area) are the most conservative risk metrics for the epidemiological and toxicological risks presented here, respectively

    The role of cervical Electrical Impedance Spectroscopy in the prediction of the course and outcome of induced labour

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    BACKGROUND: Previous work by us and others had suggested that cervical electrical impedance spectroscopy (EIS) may be predictive of the outcome of induced labour. We sought to determine which probe configuration of the EIS device is predictive of the outcome of induced labour and compare this to digital assessment by the Bishop score. METHODS: In a prospective cohort of 205 women admitted for induction of labour, we used four probes of diameter 3, 6, 9 and 12 mm connected to an impedance meter to measure cervical resistivity (CR) in Ohm.meters at 14 electrical frequencies and compared their values to digital assessment of the cervix by the Bishop score for the prediction of the outcome of induced labour. We tested the association of labour characteristics and outcomes with CR and Bishop score by stepwise multilinear regression analyses, and the accuracy of prediction of categorical clinical outcomes by analysis of the area under the curves (AUC) of derived Receiver Operator Characteristic (ROC) curves.RESULTS:Of the four CR probe dimensions studied, only the 12 mm probe was predictive of any labour indices. In the frequency range 19 - 156 kHz, CR obtained with this probe was higher in women who delivered by caesarean section (CS) than those who delivered vaginally, and in labours lasting > 24 hrs. Cervical resistivity at 78.1 kHz best predicted vaginal delivery [optimal cut-off 24 hrs [optimal cut-off 2.27 O.m, AUC 0.65 (95% CI 0.58, 0.72), sensitivity 71%, specificity 59%, LR+ 1.72, LR- 0.50, P 12 hours and induction-delivery interval < 24 hrs [optimal cut-off = 4, AUC 0.8 (95% CI 0.75, 0.86), sensitivity 77%, specificity 76%, LR+ 3.3, LR- 0.3, P < 0.05] whilst CR did not. CONCLUSION: Cervical resistivity appears predictive of labour duration and delivery mode following induced labour. However the low predictive values obtained suggest that its current design proffers no immediate clinical utility
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