Determination of oxygen permeability in soft contact lenses using a polarographic method : estimation of relevant physiological parameters

This work reports the apparent oxygen transmissibility Dk/t)app of four silicone hydrogel (Si-Hy) contact lenses (CLs). A method is described that allows the estimation of the oxygen tension at the lens-cornea interface for closed- and open-eyelids situations combining the instrument oxygen transmissibility (IOT) and corneal parameters such as corneal thickness, corneal permeability, and oxygen flux across the cornea. From these results, the biological oxygen apparent transmissibility (BOAT), equivalent oxygen percentage (EOP), partial pressure, (ptc), of oxygen at the cornea-CL interface and oxygen flux, (jc), were also obtained. This method allows the evaluation of the physiological environment under the lens using the formulations described in previous studies. The oxygen performance of four Si-Hy materials was evaluated using a polarographic cell coupled to a permeometer. Measurements of the apparent transmissibility, (Dk/t)app, and permeability, Dk, were performed in stacks containing from 1 to n repeated lenses and, from the values obtained, the error involved in the measurements in single samples was estimated. It was found that the values of (Dk/t)app and Dk obtained following the two different procedures (stack method and measurement of single sample) were significantly different from the nominal values given by the manufacturer, particularly for some samples. However, the impact of these differences on the values of the other physiologically relevant parameters (BOAT, EOP, ptc, and jc) was not significant. Furthermore, these parameters were similarfor the four lenses in spite of the different (Dk/t)app measured. The relationships of (Dk/t)app with theremaining physiological parameters were calculated and graphically represented for open and closed-eyelid conditions.Dirección General de Investigación Científica y Técnica (DGICYT) - bolsa MAT-2005-05648-C02-01Instituto de la Pequeña y Mediana Industria Valenciana (IMPIVA) - bolsa IMCOVA-2006/20.European Social Funding (ESF) - Contrato #8281/2002 para o bolseiro J.M.G.-M.Fundação para a Ciência e Tecnologia (FCT

Relaxation behavior of semiflexible polymers at very low frequencies

[EN] The dielectric activity of poly(monocyclohexylmethylene itaconate) (PMCI) and poly(dicyclohexylmethylene itaconate) (PDCI) in the glassy region and in the glass-rubber transition is studied by thermostimulated discharge current (TSDC) techniques. The spectra obtained by global TSDC experiments show a prominent alpha-glass-rubber relaxation peak with maxima located at 97 and 55 degrees C for PMCI and PDCI, respectively, following in decreasing order of temperature for a well developed beta absorption and a comparatively low intensity relaxation. Better resolution of the relaxation behavior of these polymers in the glassy region is obtained by calculating the components of the complex dielectric permittivity epsilon* at extremely low frequencies from partial TSDC experiments. The ac spectra thus obtained suggest that the beta absorption is composed by two relaxations, each of them presumably associated with the motions of a side group. The differences observed in these spectra with those reported for the beta mechanical relaxation reported for these polymers in the literature are interpreted in terms of the restrictions that the side groups produce in the conformational space of phase of the backbone. These restrictions also explain the small changes in enthalpy in the glass-rubber transition which preclude the possibility of obtaining the glass-rubber transition temperature of these polymers by differential scanning calorimetric techniques. (C) 1997 American Institute of Physics.Díaz Calleja, R.; Sanchis Sánchez, MJ.; Alvarez, C.; Riande, E. (1997). Relaxation behavior of semiflexible polymers at very low frequencies. Journal of Applied Physics. 81(8):3685-3691. doi:10.1063/1.364743S3685369181

Tales of a Jealous Demon of Zi bu yu 『子不語』: a Supplement

The biaxial stretching of sheets of liquid crystalline neo-Hookean elastomer has been studied in the isotropic case. The results suggest two types of laminate structures in the process of quasiconvexification of the free energy, a fact that implies the appearance of several shear terms in the deformation gradient matrix. More that one decomposition of the deformation gradient is possible, which is consistent with a bifurcation in the undeformed configuration ($\lambda$ = 1) . This situation is similar to the well-known Rivlin’s problem of the triaxial symmetric traction of a neo-Hookean cube. The problem can easily be generalized for an anisotropic material by introducing a semisoft term in the free-energy expression. In this case, the horizontal plateau corresponding to the minimal energy, characteristic of the soft elasticity, disappears, and only an equilibrium condition is obtained

Stress relaxation and creep experiments with the atomic force microscope: a unified method to calculate elastic moduli and viscosities of biomaterials (and cells)

We show that the atomic force microscope can perform stress relaxation and creep compliance measurements on living cells. We propose a method to obtain the mechanical properties of the studied biomaterial: the relaxation time, the elastic moduli and the viscosity.Comment: 17 pages, three figure

Effect of slight crosslinking on the mechanical relaxation behavior of poly(2-ethoxyethyl methacrylate) chains

The synthesis, thermal and mechanical characterizations of uncrosslinked and lightly crosslinked poly(2-ethoxyethyl methacrylate) are reported. The uncrosslinked poly(2-ethoxyethyl methacrylate) exhibits in the glassy state two relaxations called in increasing order of temperature, the gamma and beta processes respectively. These are followed by a prominent glass rubber or alpha relaxation. By decreasing the chains mobility by a small amount of crosslinking, the beta relaxation disappears and the peak maximum associated with the alpha relaxation is shifted from 268 K to 278 K, at 1 Hz. An investigation of the storage relaxation modulus of the crosslinked polymer indicates two inflexion points that presumably are related to segmental motions of dangling chains of the crosslinked networks and to cooperative motions of the chains between crosslinking points. Nanodomains formed by side-groups flanked by the backbone give rise to a Maxwell Wagner Sillars relaxation in the dielectric spectra that have no incidence in the mechanical relaxation spectra.We thank Dr. J. Guzman (Madrid) for providing us with the CEOEMA sample. This work was financially supported by the DGCYT and CAM through the Grant MAT2008-06725-C03 and MAT2012-33483. In memoriam of Professor Emeritus Evaristo Riande in recognition of his contribution to Polymer Science.Carsí Rosique, M.; Sanchis Sánchez, MJ.; Díaz Calleja, R.; Riande, E.; Nugent, MJD. (2013). Effect of slight crosslinking on the mechanical relaxation behavior of poly(2-ethoxyethyl methacrylate) chains. European Polymer Journal. 49(6):1495-1502. doi:10.1016/j.eurpolymj.2012.12.012S1495150249

Superdipole Liquid Scenario for the Dielectric Primary Relaxation in Supercooled Polar liquids

We propose a dynamic structure of coupled dynamic molecular strings for supercooled small polar molecule liquids and accordingly we obtain the Hamiltonian of the rotational degrees of freedom of the system. From the Hamiltonian, the strongly correlated supercooled polar liquid state is renormalized to a normal superdipole (SD) liquid state. This scenario describes the following main features of the primary or a-relaxation dynamics in supercooled polar liquids: (1) the average relaxation time evolves from a high temperature Arrhenius to a low temperature non-Arrhenius or super-Arrhenius behavior; (2) the relaxation function crosses over from the high temperature exponential to low temperature non-exponential form; and (3) the temperature dependence of the relaxation strength shows non-Curie features. According to the present model, the crossover phenomena of the first two characteristics arise from the transition between the superdipole gas and the superdipole liquid. The model predictions are quantitatively compared with the experimental results of glycerol, a typical glass-former.Comment: 40 pages, 3 figure

Relaxational study of poly(vinylpyrrolidone-co-butyl acrylate) membrane by dielectric and dynamic mechanical spectroscopy

[EN] A poly(vinylpyrrolidone-co-butyl acrylate) (60VP-40BA) membrane is synthesized as a tractable and hydrophilic material, obtaining a water-swelling percentage around 60%. An investigation of molecular mobility by means of differential scanning calorimetry, dynamic mechanical analysis and broadband dielectric relaxation spectroscopy (DRS) is fulfilled in the dry membrane. Dielectric and viscoelastic relaxation measurements are carried out on the 60VP-40BA sample at several frequencies between -150 and 150 degrees C. The dielectric spectrum shows several relaxation processes labelled gamma, beta and alpha in increasing order of temperature, whereas in the mechanical spectrum only the beta and alpha relaxation processes are completely defined. In the dielectric measurements, conductive contributions overlap the alpha-relaxation. The apparent activation energies have similar values for the beta-relaxation in both, the mechanical and the dielectric measurements. The beta process is a Johari-Golstein secondary relaxation and it is related to the local motions of the pyrrolidone group accompanied by the motion of the segments of the polymer backbone. The gamma process is connected with the butyl unit's motions, both located in the side chains of the polymer.BRF, MC, PO and MJS are grateful to CICYT for grant MAT2012-33483. FG and JMG thank the Spanish Ministerio de Economia y Competitividad-FEDER (MAT2011-22544) and the Consejeria de Educacion-Junta de Castilla y Leon (BU001A10-2).Redondo Foj, MB.; Carsí Rosique, M.; Ortiz Serna, MP.; Sanchis Sánchez, MJ.; García, FC.; García. José Miguel (2013). Relaxational study of poly(vinylpyrrolidone-co-butyl acrylate) membrane by dielectric and dynamic mechanical spectroscopy. JOURNAL OF PHYSICS D-APPLIED PHYSICS. 46(29):295304-1-295304-12. https://doi.org/10.1088/0022-3727/46/29/295304S295304-1295304-12462

Influence of the Water Content on the Diffusion Coefficients of Li⁺ and Water across Naphthalenic Based Copolyimide Cation-Exchange Membranes

The transport of lithium ions in cation-exchange membranes based on sulfonated copolyimide membranes is reported. Diffusion coefficients of lithium are estimated as a function of the water content in membranes by using pulsed field gradient (PFG) NMR and electrical conductivity techniques. It is found that the lithium transport slightly decreases with the diminution of water for membranes with water content lying in the range 14 < λ < 26.5, where λ is the number of molecules of water per fixed sulfonate group. For λ < 14, the value of the diffusion coefficient of lithium experiences a sharp decay with the reduction of water in the membranes. The dependence of the diffusion of lithium on the humidity of the membranes calculated from conductivity data using Nernst–Planck type equations follows a trend similar to that observed by NMR. The possible explanation of the fact that the Haven ratio is higher than the unit is discussed. The diffusion of water estimated by 1H PFG-NMR in membranes neutralized with lithium decreases as λ decreases, but the drop is sharper in the region where the decrease of the diffusion of protons of water also undergoes considerable reduction. The diffusion of lithium ions computed by full molecular dynamics is similar to that estimated by NMR. However, for membranes with medium and low concentration of water, steady state conditions are not reached in the computations and the diffusion coefficients obtained by MD simulation techniques are overestimated. The curves depicting the variation of the diffusion coefficient of water estimated by NMR and full dynamics follow parallel trends, though the values of the diffusion coefficient in the latter case are somewhat higher. The WAXS diffractograms of fully hydrated membranes exhibit the ionomer peak at q = 2.8 nm⁻1, the peak being shifted to higher q as the water content of the membranes decreases. The diffractograms present additional peaks at higher q, common to wet and dry membranes, but the peaks are better resolved in the wet membranes. The ionomer peak is not detected in the diffractograms of dry membranes.The authors acknowledge financial support provided by the DGICYT (Dirección General de Investigación Cientifíca y Tecnológica) through Grant MAT2011-29174-C02-02