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1.
J Colloid Interface Sci ; 637: 317-325, 2023 May.
Artigo em Inglês | MEDLINE | ID: mdl-36706727

RESUMO

HYPOTHESIS: Improving the processing efficiency of aerosol-coating technologies during mass production requires optimal nozzle spacing to allow complete surface coverage while at the same time not over-using the coating fluid. The difficult challenge is to estimate quantitatively the substrate coverage of fine droplets. Bouncing, splashing, and imbibition of droplets on solid surfaces have been widely explored, but little attention has been paid to liquid imbibition into woven textiles. EXPERIMENTS: Here, we experimentally and theoretically study the imbibition dynamics of aqueous droplets on woven cloths. The experimental process was observed using magnified visual observation. A proposed continuum mathematical model well predicts the aqueous imbibition fronts as a function of time. FINDINGS: A captivating four-petal imbibition spreading pattern is observed at enhanced magnification. The imbibition occurs separately in the megapores of the cloth between yarns, and in smaller minipores within individual yarn bundles. Surprisingly, weave intersections do not allow cross imbibition accentuating an anisotropic imbibition pattern. The proposed model achieves quantitative agreement with experiment. This is the first time that the mechanisms of four-petal droplet deposition, spreading, and imbibition into woven cloth have been outlined and successfully simulated. The mathematical model predicts advancement of liquids in anisotropic woven cloth, and permits evaluation of the coverages of droplet spreading.

2.
Adv Colloid Interface Sci ; 288: 102335, 2021 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-33360298

RESUMO

A triple-layer model of the mica/water electrical double layer (EDL) unifies prediction of zeta potential, ion-exchange, and surface-force isotherms. The theory treats cations as partially dehydrated and complexed specifically to the anionic exchange sites of mica. A diffuse layer commencing at the outer Helmholtz plane (OHP) balances the surface charge not neutralized by adsorbed cations in the inner Helmholtz plane (IHP). Ion-binding equilibrium constants are assessed from zeta-potential measurements and used thereafter to predict ion-exchange isotherms and surface forces. Basal-plane mica surface charge is almost completely neutralized by specific binding of cations, including hydronium ions. The charge in the diffuse layer is only a few percent of the mica crystallographic charge density but leads to long-range electrostatic interactions between charged surfaces. The Grahame triple-layer model of the aqueous EDL provides a robust, quantitative, and unified description of the mica/water interface.

3.
Langmuir ; 35(2): 428-434, 2019 01 15.
Artigo em Inglês | MEDLINE | ID: mdl-30540194

RESUMO

Asphaltenes in crude oil play a pivotal role in reservoir oil production because they control rock-surface wettability. Upon crude oil invasion into a brine-filled reservoir trap, rock adherence of sticky asphaltene agglomerates formed at the crude oil/brine interface can change the initially water-wet porous medium into mixed-oil wetting. If thick, stable water films coat the rock surfaces, however, asphaltenic-oil adhesion is thought to be prevented. We investigate whether water films influence the uptake of asphaltenes in crude oil onto silica surfaces. Water films of known thickness are formed at a silica surface in a quartz crystal microbalance with dissipation and contacted by toluene-solubilized asphaltene. We confirm that thick water films prevent asphaltene molecular contact with the silica surface blocking asphaltene adhesion. The thicker the water film, the smaller is the amount of asphaltene deposited. Film thickness necessary for complete blockage onto silica is greater than about 500 nm, well beyond the range of molecular-chain contact. Water films of thickness less than 500 nm, sandwiched between toluene and solid silica, apparently rupture into thick water pockets and interposed molecularly thin water layers that permit asphaltene adherence.

5.
J Control Release ; 239: 242-8, 2016 10 10.
Artigo em Inglês | MEDLINE | ID: mdl-27565214

RESUMO

We measure and, for the first time, theoretically predict four prototypical aqueous-drug diffusion coefficients in five soft-contact-lens material hydrogels where solute-specific adsorption is pronounced. Two-photon fluorescence confocal microscopy and UV/Vis-absorption spectrophotometry assess transient solute concentration profiles and concentration histories, respectively. Diffusion coefficients are obtained for acetazolamide, riboflavin, sodium fluorescein, and theophylline in 2-hydroxyethyl methacrylate/methacrylic acid (HEMA/MAA) copolymer hydrogels as functions of composition, equilibrium water content (30-90%), and aqueous pH (2 and 7.4). At pH2, MAA chains are nonionic, whereas at pH7.4, MAA chains are anionic (pKa≈5.2). All studied prototypical drugs specifically interact with HEMA and nonionic MAA (at pH2) moieties. Conversely, none of the prototypical drugs adsorb specifically to anionic MAA (at pH7.4) chains. As expected, diffusivities of adsorbing solutes are significantly diminished by specific interactions with hydrogel strands. Despite similar solute size, relative diffusion coefficients in the hydrogels span several orders of magnitude because of varying degrees of solute interactions with hydrogel-polymer chains. To provide a theoretical framework for the new diffusion data, we apply an effective-medium model extended for solute-specific interactions with hydrogel copolymer strands. Sorptive-diffusion kinetics is successfully described by local equilibrium and Henry's law. All necessary parameters are determined independently. Predicted diffusivities are in good agreement with experiment.


Assuntos
Hidrogéis/metabolismo , Metacrilatos/metabolismo , Água/metabolismo , Difusão , Hidrogéis/química , Metacrilatos/química , Preparações Farmacêuticas/química , Preparações Farmacêuticas/metabolismo , Solubilidade , Água/química
6.
Acta Biomater ; 18: 112-7, 2015 May.
Artigo em Inglês | MEDLINE | ID: mdl-25725471

RESUMO

Equilibrium water content of and solute partitioning in silicone hydrogels (SiHys) are investigated using gravimetric analysis, fluorescence confocal laser-scanning microscopy (FCLSM), and back extraction with UV/Vis-absorption spectrophotometry. Synthesized silicone hydrogels consist of silicone monomer, hydrophilic monomer, cross-linking agent, and triblock-copolymer macromer used as an amphiphilic compatibilizer to prevent macrophase separation. In all cases, immiscibility of the silicone and hydrophilic polymers results in microphase-separated morphologies. To investigate solute uptake in each of the SiHy microphases, equilibrium partition coefficients are obtained for two hydrophilic solutes (i.e., theophylline and caffeine dissolved in aqueous phosphate-buffered saline) and two oleophilic solutes (i.e., Nile Red and Bodipy Green dissolved in silicone oil), respectively. Measured water contents and aqueous-solute partition coefficients increase linearly with increasing solvent-free hydrophilic-polymer volume fraction. Conversely, oleophilic-solute partition coefficients decrease linearly with rising solvent-free hydrophilic-polymer volume fraction (i.e., decreasing hydrophobic silicone-polymer fraction). We quantitatively predict equilibrium SiHy water and solute uptake assuming that water and aqueous solutes reside only in hydrophilic microdomains, whereas oleophilic solutes partition predominately into silicone microdomains. Predicted water contents and solute partition coefficients are in excellent agreement with experiment. Our new procedure permits a priori estimation of SiHy water contents and solute partition coefficients based solely on properties of silicone and hydrophilic homopolymer hydrogels, eliminating the need for further mixed-polymer-hydrogel experiments.


Assuntos
Hidrogéis/química , Silicones/química , Água/química , Cafeína/química , Interações Hidrofóbicas e Hidrofílicas , Solventes/química , Teofilina/química
7.
J Colloid Interface Sci ; 449: 462-79, 2015 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-25648681

RESUMO

In spite of over 7 decades of effort, the thermodynamics of thin free liquid films (as in emulsions and foams) lacks clarity. Following a brief review of the meaning and measurement of thin-film forces (i.e., conjoining/disjoining pressures), we offer a consistent analysis of thin-film thermodynamics. By carefully defining film reversible work, two distinct thermodynamic formalisms emerge: a film model with two zero-volume membranes each of film tension γ(f) and a membrane model with a single zero-volume membrane of membrane tension 2γ(m). In both models, detailed thermodynamic analysis gives rise to thin-film Gibbs adsorption equations that allow calculation of film and membrane tensions from measurements of disjoining-pressure isotherms. A modified Young-Laplace equation arises in the film model to calculate film-thickness profiles from the film center to the surrounding bulk meniscus. No corresponding relation exists in the membrane model. Illustrative calculations of disjoining-pressure isotherms for water are presented using square-gradient theory. We report considerable deviations from Hamaker theory for films less than about 3 nm in thickness. Such thin films are considerably more attractive than in classical Hamaker theory. Available molecular simulations reinforce this finding.

8.
Acta Biomater ; 15: 48-54, 2015 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-25484335

RESUMO

Partitioning of aqueous packaging, wetting, and care-solution agents into and out of soft contact lenses (SCLs) is important for improving wear comfort and also for characterizing lens physico-chemical properties. We illustrate both features of partitioning by application of fluorescent-solute partitioning into DAILIES TOTAL1® (delefilcon A) water-gradient SCLs, which exhibit a layered structure of a silicone-hydrogel (SiHy) core sandwiched between thin surface-gel layers. Two-photon fluorescence confocal laser-scanning microscopy and attenuated total-reflectance Fourier-transform infrared spectroscopy (ATR-FTIR) characterize the lens and assess uptake profiles of six prototypical fluorescent solutes. Comparison of solute uptake in a SiHy-core prototype lens (i.e., O2OPTIX(TM)) validates the core SiHy structure of DAILIESTOTAL1®. To establish surface-layer charge, partition coefficients and water contents are obtained for aqueous pH values of 4 and 7.4. Solute fluorescence-intensity profiles clearly confirm a layered structure for the DAILIES TOTAL1® lenses. In all cases, aqueous solute partition coefficients are greater in the surface layers than in the SiHy core, signifying higher water in the surface gels. ATR-FTIR confirms surface-layer mass water contents of 82±3%. Water uptake and hydrophilic-solute uptake at pH 4 compared with that at pH 7.4 reveal that the surface-gel layers are anionic at physiologic pH 7.4, whereas both the SiHy core and O2OPTIX™ (lotrafilcon B) are nonionic. We successfully confirm the layered structure of DAILIES TOTAL1®, consisting of an 80-µm-thick SiHy core surrounded by 10-µm-thick polyelectrolyte surface-gel layers of significantly greater water content and aqueous solute uptake compared with the core. Accordingly, fluorescent-solute partitioning in SCLs provides information on gel structure and composition, in addition to quantifying uptake and release amounts and rates.


Assuntos
Lentes de Contato Hidrofílicas , Avidina/química , Dextranos/química , Fluoresceína-5-Isotiocianato/análogos & derivados , Fluoresceína-5-Isotiocianato/química , Fluorescência , Hidrodinâmica , Concentração de Íons de Hidrogênio , Interações Hidrofóbicas e Hidrofílicas , Microscopia de Fluorescência , Espectroscopia de Infravermelho com Transformada de Fourier , Água/química
9.
Adv Colloid Interface Sci ; 222: 600-14, 2015 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-24472562

RESUMO

The fundamental underpinnings of the Gibbs adsorption equation (GAE) are enunciated including sundry choices for the location of the zero-volume dividing surface. Comparison is made to the finite-volume thermodynamic analyses of Guggenheim and Hansen. Provided that Gibbs phase rule is properly invoked, only invariant surface properties appear in the GAE. In the framework of invariant surface properties, both the zero-volume (Gibbs) and the finite-volume (Guggenheim) treatments of the surface phase give identical results for the GAE, confirming the thermodynamic generality and rigor of the expression. Application of the GAE is made to strong and weak electrolytes, to electrified interfaces (Lippmann equation), and to surface complexation. Usefulness of the GAE in molecular simulation of interfaces is outlined. Special attention is paid to the seminal contributions of Fainerman and Miller in applying molecular-thermodynamic interfacial-layer models toward predicting adsorption behavior at fluid/fluid interfaces. Conversion of adsorption isotherms into two-dimensional interfacial-tension equations of state via the GAE is highlighted. Confusion over interpretation of the Gibbs adsorption equation arises primarily because of imprecise meaning for adsorbed amounts. Once invariant adsorptions are recognized and utilized, the Gibbs adsorption equation yields identical results for Gibbs zero-volume surface thermodynamics and for Guggenheim finite-volume surface thermodynamics.

10.
Curr Eye Res ; 39(6): 580-95, 2014 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-24502301

RESUMO

PURPOSE: Dry-eye disease, an increasingly prevalent ocular-surface disorder, significantly alters tear physiology. Understanding the basic physics of tear dynamics in healthy and dry eyes benefits both diagnosis and treatment of dry eye. We present a physiological-based model to describe tear dynamics during blinking. MATERIALS AND METHODS: Tears are compartmentalized over the ocular surface; the blink cycle is divided into three repeating phases. Conservation laws quantify the tear volume and tear osmolarity of each compartment during each blink phase. Lacrimal-supply and tear-evaporation rates are varied to reveal the dependence of tear dynamics on dry-eye conditions, specifically tear osmolarity, tear volume, tear-turnover rate (TTR), and osmotic water flow. RESULTS: Predicted periodic-steady tear-meniscus osmolarity is 309 and 321 mOsM in normal and dry eyes, respectively. Tear osmolarity, volume, and TTR all match available clinical measurements. Osmotic water flow through the cornea and conjunctiva contribute 10 and 50% to the total tear supply in healthy and dry-eye conditions, respectively. TTR in aqueous-deficient dry eye (ADDE) is only half that in evaporative dry eye (EDE). CONCLUSIONS: The compartmental periodic-steady tear-dynamics model accurately predicts tear behavior in normal and dry eyes. Inclusion of osmotic water flow is crucial to match measured tear osmolarity. Tear-dynamics predictions corroborate the use of TTR as a clinical discriminator between ADDE and EDE. The proposed model is readily extended to predict the dynamics of aqueous solutes such as drugs or fluorescent tags.


Assuntos
Síndromes do Olho Seco/metabolismo , Voluntários Saudáveis , Lágrimas/química , Lágrimas/fisiologia , Piscadela/fisiologia , Dessecação , Humanos , Hidrodinâmica , Aparelho Lacrimal/fisiologia , Concentração Osmolar , Volatilização , Água/química , Equilíbrio Hidroeletrolítico
11.
Adv Colloid Interface Sci ; 206: 250-64, 2014 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-23842140

RESUMO

Tear-film instability is widely believed to be a signature of eye health. When an interblink is prolonged, randomly distributed ruptures occur in the tear film. "Black spots" and/or "black streaks" appear in 15 to 40 s for normal individuals. For people who suffer from dry eye, tear-film breakup time (BUT) is typically less than a few seconds. To date, however, there is no satisfactory quantitative explanation for the origin of tear rupture. Recently, it was proposed that tear-film breakup is related to locally high evaporative thinning. A spatial variation in the thickness of the tear-film lipid layer (TFLL) may lead to locally elevated evaporation and subsequent tear-film breakup. We examine the local-evaporation-driven tear-film-rupture hypothesis in a one-dimensional (1-D) model for the evolution of a thin aqueous tear film overriding the cornea subject to locally elevated evaporation at its anterior surface and osmotic water influx at its posterior surface. Evaporation rate depends on mass transfer both through the coating lipid layer and through ambient air. We establish that evaporation-driven tear-film breakup can occur under normal conditions but only for higher aqueous evaporation rates. Predicted roles of environmental conditions, such as wind speed and relative humidity, on tear-film stability agree with clinical observations. More importantly, locally elevated evaporation leads to hyperosmolar spots in the tear film and, hence, vulnerability to epithelial irritation. In addition to evaporation rate, tear-film instability depends on the strength of healing flow from the neighboring region outside the breakup region, which is determined by the surface tension at the tear-film surface and by the repulsive thin-film disjoining pressure. This study provides a physically consistent and quantitative explanation for the formation of black streaks and spots in the human tear film during an interblink.


Assuntos
Córnea , Lágrimas/química , Fenômenos Biofísicos , Humanos , Volatilização
12.
Adv Colloid Interface Sci ; 197-198: 33-57, 2013 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-23694847

RESUMO

Water-evaporation reduction by duplex-oil films is especially important to understand the physiology of the human tear film. Secreted lipids, called meibum, form a duplex film that coats the aqueous tear film and purportedly reduces tear evaporation. Lipid-layer deficiency is correlated with the occurrence of dry-eye disease; however, in-vitro experiments fail to show water-evaporation reduction by tear-lipid duplex films. We review the available literature on water-evaporation reduction by duplex-oil films and outline the theoretical underpinnings of spreading and evaporation kinetics that govern behavior of these systems. A dissolution-diffusion model unifies the data reported in the literature and identifies dewetting of duplex films into lenses as a key challenge to obtaining significant evaporation reduction. We develop an improved apparatus for measuring evaporation reduction by duplex-oil films including simultaneous assessment of film coverage, stability, and temperature, all under controlled external mass transfer. New data reported in this study fit into the larger body of work conducted on water-evaporation reduction by duplex-oil films. Duplex-oil films of oxidized mineral oil/mucin (MOx/BSM), human meibum (HM), and bovine meibum (BM) reduce water evaporation by a dissolution-diffusion mechanism, as confirmed by agreement between measurement and theory. The water permeability of oxidized-mineral-oil duplex films agrees with those reported in the literature, after correction for the presence of mucin. We find that duplex-oil films of bovine and human meibum at physiologic temperature reduce water evaporation only 6-8% for a 100-nm film thickness pertinent to the human tear film. Comparison to in-vivo human tear-evaporation measurements is inconclusive because evaporation from a clean-water surface is not measured and because the mass-transfer resistance is not characterized.


Assuntos
Lágrimas/química , Água/química , Humanos , Óleos/química , Oxirredução , Propriedades de Superfície , Temperatura , Volatilização
13.
J Colloid Interface Sci ; 394: 498-508, 2013 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-23347999

RESUMO

The kinetic behavior of aqueous cellulase on insoluble cellulose is best quantified through surface-based assays on a well-defined cellulose substrate of known area. We use a quartz crystal microbalance (QCM) to measure the activity of binary mixtures of Trichoderma longibrachiatum cellobiohydrolase I (Cel7A) and endoglucanase I (Cel7B) on spin-coated cellulose films. By extending a previous surface kinetic model for cellulase activity, we obtain rate constants for competitive adsorption of Cel7A and Cel7B, their irreversible binding, their complexation with the cellulose surface, and their cooperative cellulolytic activity. The activity of the two cellulases is linked through the formation of cellulose chain ends by Cel7B that provide complexation sites from which Cel7A effects cellulose chain scission. Although the rate-limiting step in Cel7A activity is complexation, Cel7B activity is limited by adsorption to the cellulose surface. A 2:1 bulk mass ratio of aqueous Cel7A:Cel7B, corresponding to a 4:1 surface mass ratio, effects the greatest rate of cellulose degradation across a range of cellulase concentrations at 25 °C. We find that surface chain-end concentration is a major predictor of Cel7A activity. Disruption of the hydrogen-bonding structure of cellulose by Cel7B enhances the activity of Cel7A on the cellulose surface.


Assuntos
Celulose 1,4-beta-Celobiosidase/metabolismo , Celulose/metabolismo , Trichoderma/enzimologia , Cinética , Técnicas de Microbalança de Cristal de Quartzo
14.
Cont Lens Anterior Eye ; 35(6): 260-5, 2012 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-22840754

RESUMO

In addition to improving oxygen permeability, modern silicone-hydrogel (SiHy) soft contact lenses (SCLs) exceed a limiting diffusive ion permeability to aqueous sodium chloride. Below the ion-permeability threshold, siloxane-based SCLs are prone to bind against the corneal epithelium. Salt permeability is argued to reflect indirectly water hydraulic permeability. However, no quantitative explanation is available to date for a threshold salt permeability. We hypothesize that molecular salt diffusion through a SCL supports the postlens tear film (PoLTF) by enhancing water flow into the PoLTF from the cornea. Higher salt concentrations in the PoLTF raise the osmotic pressure there relative to that in the cornea increasing osmotic water withdrawal from the cornea. The proposed osmotic-withdrawal mechanism successfully predicts a self-consistent threshold lens salt permeability when thin-film attractive binding forces are introduced. For the first time, we present a quantitative picture for the possible origin of a threshold salt permeability in SCL manufacture.


Assuntos
Lentes de Contato Hidrofílicas , Membranas Artificiais , Modelos Químicos , Osmose , Géis de Silicone/química , Cloreto de Sódio/química , Adesividade , Simulação por Computador , Difusão , Desenho de Equipamento
15.
Cont Lens Anterior Eye ; 35(4): 155-62, 2012 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-22456099

RESUMO

Prevention of Pseudomonas aeruginosa binding to soft-contact lenses (SCLs) may curtail sight-threatening microbial keratitis. Substrate surface wettability is known to modulate adhesion of P. aeruginosa. This study investigates the use of aqueous alkoxylate block co-polymer surfactants for enhanced wettability and antibacterial adhesion of SCLs under leaching conditions. Specifically, Pluronic(®) F127 (PF) and three ethylene oxide-butylene oxide (EOBO) surfactants were studied with four commercially available silicone-hydrogel contact lenses: Pure Vision™, Acuvue Advance™, Acuvue Oasys™ and O(2)Optix™. Dilute aqueous PF and EOBO surfactants impregnated all four soft-contact lenses, as demonstrated by surface-tension decline for leached surfactant. For PF surfactant, significant surface-wettability improvement upon rinsing occurred only after overnight leaching. EOBO surfactant showed a similar pattern with O(2)Optix™ lenses. EOBO-pretreated Pure Vision™ lenses, however, showed fast leaching and a significant change in surface energy towards improved wettability. Adhesion assays of P. aeruginosa displayed a small decrease in the binding rate of PAK bacteria for EOBO-pretreated Pure Vision™ lenses, but not for EOBO-pretreated O(2)Optix™ lenses. P. aeruginosa strain-PAO1 bacteria adhesion to all lenses was independent of surface wettability. Despite the ability of polymeric surfactants to lower advancing contact angles under leaching conditions, increased lens wettability is not a universal panacea for antifouling of soft-contact lenses.


Assuntos
Aderência Bacteriana/fisiologia , Lentes de Contato Hidrofílicas/microbiologia , Compostos de Epóxi/farmacologia , Óxido de Etileno/farmacologia , Hidrogéis , Poloxâmero/farmacologia , Pseudomonas aeruginosa/fisiologia , Silicones , Tensoativos/farmacologia , Molhabilidade/efeitos dos fármacos , Tensão Superficial
16.
Langmuir ; 28(2): 1222-34, 2012 Jan 17.
Artigo em Inglês | MEDLINE | ID: mdl-22133053

RESUMO

Nucleation and growth of ice in the fibrous gas-diffusion layer (GDL) of a proton-exchange membrane fuel cell (PEMFC) are investigated using isothermal differential scanning calorimetry (DSC). Isothermal crystallization rates and pseudo-steady-state nucleation rates are obtained as a function of subcooling from heat-flow and induction-time measurements. Kinetics of ice nucleation and growth are studied at two polytetrafluoroethylene (PTFE) loadings (0 and 10 wt %) in a commercial GDL for temperatures between 240 and 273 K. A nonlinear ice-crystallization rate expression is developed using Johnson-Mehl-Avrami-Kolmogorov (JMAK) theory, in which the heat-transfer-limited growth rate is determined from the moving-boundary Stefan problem. Induction times follow a Poisson distribution and increase upon addition of PTFE, indicating that nucleation occurs more slowly on a hydrophobic fiber than on a hydrophilic fiber. The determined nucleation rates and induction times follow expected trends from classical nucleation theory. A validated rate expression is now available for predicting ice-crystallization kinetics in GDLs.

17.
Prog Retin Eye Res ; 30(6): 471-92, 2011 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-21820076

RESUMO

Wear of low-oxygen-transmissible soft contact lenses swells the cornea significantly, even during open eye. Although oxygen-deficient corneal edema is well-documented, a self-consistent quantitative prediction based on the underlying metabolic reactions is not available. We present a biochemical description of the human cornea that quantifies hypoxic swelling through the coupled transport of water, salt, and respiratory metabolites. Aerobic and anaerobic consumption of glucose, as well as acidosis and pH buffering, are incorporated in a seven-layer corneal model (anterior chamber, endothelium, stroma, epithelium, postlens tear film, contact lens, and prelens tear film). Corneal swelling is predicted from coupled transport of water, dissolved salts, and especially metabolites, along with membrane-transport resistances at the endothelium and epithelium. At the endothelium, the Na+/K+ - ATPase electrogenic channel actively transports bicarbonate ion from the stroma into the anterior chamber. As captured by the Kedem-Katchalsky membrane-transport formalism, the active bicarbonate-ion flux provides the driving force for corneal fluid pump-out needed to match the leak-in tendency of the stroma. Increased lactate-ion production during hypoxia osmotically lowers the pump-out rate requiring the stroma to swell to higher water content. Concentration profiles are predicted for glucose, water, oxygen, carbon dioxide, and hydronium, lactate, bicarbonate, sodium, and chloride ions, along with electrostatic potential and pressure profiles. Although the active bicarbonate-ion pump at the endothelium drives bicarbonate into the aqueous humor, we find a net flux of bicarbonate ion into the cornea that safeguards against acidosis. For the first time, we predict corneal swelling upon soft-contact-lens wear from fundamental biophysico-chemical principles. We also successfully predict that hypertonic tear alleviates contact-lens-induced edema.


Assuntos
Edema da Córnea/metabolismo , Epitélio Corneano/metabolismo , Oxigênio/metabolismo , Lentes de Contato Hidrofílicas/efeitos adversos , Edema da Córnea/etiologia , Humanos , Hipóxia/etiologia , Hipóxia/metabolismo , Bombas de Íon/metabolismo , Modelos Teóricos
18.
J Colloid Interface Sci ; 362(1): 58-66, 2011 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-21723562

RESUMO

Binding of bacteria to solid surfaces is complex with many aspects incompletely understood. We investigate Pseudomonas aeruginosa uptake kinetics onto hydrogel surfaces representative of soft-contact lenses made of nonionic poly(2-hydroxyethylmethacrylate) (p-HEMA), anionic poly(methacrylic acid) (p-MAA), and anionic poly(acrylic acid) (p-AA). Using a parallel-plate flow cell under phase-contrast microscopy, we document a kinetic "burst" at the anionic hydrogel surface: dilute aqueous P. aeruginosa first rapidly accumulates and then rapidly depletes. Upon continuing flow, divalent cations in the suspending solution sorb into the hydrogel network causing the previously surface-accumulated bacteria to desorb. The number of bacteria eventually bound to the surface is low compared to the nonionic p-HEMA hydrogel. We propose that the kinetic burst is due to reversible divalent-cation bridging between the anionic bacteria and the negatively charged hydrogel surface. The number of surface bridging sites diminishes as divalent cations impregnate into and collapse the gel. P. aeruginosa association with the surface then falls. Low eventual binding of P. aeruginosa to the anionic hydrogel is ascribed to increased surface hydrophilicity compared to the counterpart nonionic p-HEMA hydrogel.


Assuntos
Lentes de Contato/microbiologia , Hidrogel de Polietilenoglicol-Dimetacrilato/química , Pseudomonas aeruginosa/isolamento & purificação , Resinas Acrílicas/química , Sítios de Ligação , Cloreto de Cálcio/química , Cátions Bivalentes/química , Interações Hidrofóbicas e Hidrofílicas , Metacrilatos/química , Ácidos Polimetacrílicos/química , Cloreto de Sódio/química , Molhabilidade
19.
Water Environ Res ; 82(6): 483-91, 2010 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-20572454

RESUMO

Activated sludge foaming caused by filamentous microorganisms is a major wastewater treatment plant operating problem. This paper presents the results of an investigation of the role of dispersed nocardioforms in activated sludge foaming. Dispersed nocardioforms had a greater propensity for foaming than floc-bound nocardioforms. The mode of effluent withdrawal from an aeration basin plays a major role in determining the relative proportion of dispersed and floc-bound nocardioforms in the activated sludge. Reactors with "trapping" features (sub-surface mixed liquor withdrawal) had significantly higher dispersed nocardioform populations than reactors with "non-trapping" features (surface mixed liquor withdrawal). High dispersed nocardioform filament concentrations were correlated with a high propensity for foaming. Cationic polymer and polyaluminum chloride reduced foaming by flocculating dispersed nocardioforms, thereby converting them to floc-bound nocardioforms. Low non-ionic surfactant concentrations changed the relative proportions of dispersed and floc-bound nocardioforms by deflocculating floc-bound filaments and converting them to the dispersed growth form. This could act as a trigger for initiating the rapid-onset nocardioform foaming events observed at activated sludge plants.


Assuntos
Bactérias Aeróbias/fisiologia , Esgotos/química , Esgotos/microbiologia , Eliminação de Resíduos Líquidos , Cloreto de Alumínio , Compostos de Alumínio/farmacologia , Bactérias Aeróbias/efeitos dos fármacos , Reatores Biológicos , Cátions/química , Cátions/farmacologia , Cloretos/farmacologia , Polímeros/química , Polímeros/farmacologia , Fatores de Tempo , Microbiologia da Água
20.
J Phys Chem B ; 113(20): 7128-37, 2009 May 21.
Artigo em Inglês | MEDLINE | ID: mdl-19438276

RESUMO

Multilayers of sodium salt of poly(4-styrene sulfonate) (PSS) and poly(diallyl dimethyl ammonium) chloride (PDADMAC) have been built layer by layer (LbL) both at the solid/aqueous interface (solid supported) and the air/aqueous interface (liquid supported). For the solid-supported multilayers, the adsorption kinetics and the complex shear modulus were measured using a dissipative quartz crystal microbalance and a null ellipsometer. A bubble tensiometer was used to measure the adsorption kinetics and the elasticity modulus of the liquid-supported multilayers. At the solid/aqueous interface, adsorption kinetics changes with the number of adsorbed layers. However, at the air/aqueous interface, PSS dynamics were the same for all adsorbed layers except the first. Conversely, the adsorption kinetics of PDADMAC at the air/water surface differed between those layers close to the interface and those far from it. Multilayers grow at the air/water interface by an intrinsic-charge-compensation process, whereas, for the same ionic strengths, solid-supported layers deposit by the extrinsic-charge-compensation process. No significant differences were found between the recoverable dilational storage modulus of the liquid-supported multilayers and the real part of the shear modulus of the solid-supported ones built at the same ionic strength. The values of the modulus are in the MPa range, which corresponds to gel-like films. This result is in agreement with the strong hydration degree of the LbL films calculated from ellipsometry measurements.

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