Grafting polysiloxane onto ultrafiltration membranes to optimize surface energy and mitigate fouling.

Conventional approaches to mitigate fouling of membrane surfaces impart hydrophilicity to the membrane surface, which increases the water of hydration and fluidity near the surface. By contrast, we demonstrate here that tuning the membrane surface energy close to that of the dispersive component of water surface tension (21.8 mN m-1) can also improve the antifouling properties of the membrane. Specifically, ultrafiltration (UF) membranes were first modified using polydopamine (PDA) followed by grafting of amine-terminated polysiloxane (PSi-NH2). For example, with 2 g L-1 PSi-NH2 coating solution, the obtained coating layer contains 53% by mass fraction PSi-NH2 and exhibits a total surface energy of 21 mN m-1, decreasing the adsorption of bovine serum albumin by 44% compared to the unmodified membrane. When challenged with 1 g L-1 sodium alginate in a constant-flux crossflow system, the PSi-NH2-grafted membrane exhibits a 70% lower fouling rate than the pristine membrane at a water flux of 110 L (m2 h)-1 and good stability when cleaned with NaOH solutions.

Geometric control of rippling in supported polymer nanolines.

We study the swelling behavior of finlike polymer line gratings supported on a rigid substrate and show that the edge-supported polymer laminae undergo a rippling instability with a well-defined ripple wavelength λ transverse to the plane of the solid supporting substrate and a ripple amplitude that monotonically decreases from its maximum at the free-edge. These ripple patterns develop due to inhomogeneous compressive strains that arise from the geometric constraints that progressively suppress swelling near the supporting substrate where the laminae are clamped. By experimentally examining the influence of swelling strain and pattern geometry on the observed rippling instability, we find that the ripple wavelength λ scales with line width w for sufficiently long gratings, which is consistent with a simple theory. These trends were validated for polymer nanoline test patterns having w between (50 to 250) nm and a height-to-width aspect-ratio in the range 0.5 to 5. Our results suggest that line geometry, rather than material properties, governs the onset of rippling and suggest simple rules for their control.

Effects of sample preparation on bacterial colonization of polymers.

Characterization of materials developed for medical usage frequently includes studies in which the materials are inoculated with bacteria in order to assess bacterial colonization and biofilm formation. Observed differences in bacterial growth are typically considered to be due to the material or the incubation conditions. To our knowledge, the method used to prepare the materials has generally not been considered with regard to its influence on bacterial colonization. The objective of this study was to determine the effects that various preparation methods exert on bacterial colonization of polymer disks. Polymer disks of the same dimethacrylate composition were photopolymerized: (1) between untreated glass slides, (2) between polyester release film, (3) between glass slides treated with an alkyl silane, (4) between glass slides treated with a perfluorinated silane, or (5) with one free surface in an argon-purged chamber. Surface chemistry was quantified using X-ray photoelectron spectroscopy, hydrophobicity was assessed by water contact angle, and topography was characterized using atomic force microscopy. The disks were inoculated with Streptococcus mutans for 4 h, fixed, and visualized using confocal laser scanning microscopy. Differences among all groups were found with regard to surface chemistry, hydrophobicity, topography, and bacteria morphology, density, and coverage, indicating that the method of sample preparation strongly affects both the surface properties and the initial bacterial colonization. Polymerization on untreated slides was selected as the preferred method of preparation due to minimal material transfer to the polymer and consistent, reproducible bacterial colonization.

Exercise-induced asthma may be associated with diminished sweat secretion rates in humans.

BACKGROUND: Muscarinic receptor agonists increase water secretion from the acinar cells of respiratory, sweat, salivary, and lacrimal glands. Mice lacking the gene for aqueous water channel aquaporin (Aqp) 5 exhibit methacholine-induced bronchiolar hyperreactivity when compared to normal mice. Individuals with asthma also have enhanced airway responsiveness to methacholine and diminished airway hydration. Because Aqp5 in humans is also expressed in respiratory, sweat, salivary, and lacrimal glands, we hypothesized that those individuals with exercise-induced asthma and excessive bronchiolar reactivity should also have decreased muscarinic receptor-dependent sweat, salivary, and tear gland secretions. METHODS: Healthy, athletic subjects who are suspected of having exercise-induced bronchospasm were recruited, and FEV(1) values were determined following provocative airway challenges with methacholine. Measurements of pilocarpine-induced sweat secretion were taken in 56 volunteers, and some additional subjects also had timed collections of saliva and tear production. RESULTS: Subjects manifesting excessive airway reactivity demonstrated by exaggerated methacholine-induced reductions in FEV(1) also had diminished values for pilocarpine-induced sweat secretion (n = 56; r = - 0.59; p < 0.0001). The rate of pilocarpine-stimulated sweat secretion in our subjects correlated highly with salivary flow rate (r = 0.69; p < 0.0001) and tearing rate (r = 0.86; p < 0.001). CONCLUSION: Hyperhidrosis, sialorrhea, and excessive tearing are traits that may indicate a phenotype that predicts resistance to hyperactive airway diseases such as exercise-induced asthma in humans.

Short-time dental resin biostability and kinetics of enzymatic degradation.

Resin biostability is of critical importance to the durability of methacrylate-based dental resin restorations. Current methods for evaluating biostability take considerable time, from weeks to months, and provide no short-time kinetics of resin degradation. The objective of this study is to develop a more sensitive method to assess resin biostability over short-time spans (hours to days) that will enhance our understanding of biostability and its resin chemistry. Ultra-flat resin films of equimolar urethane dimethacrylate (UDMA) and triethylene glycol dimethacrylate (TEGDMA) are produced through photo-curing between two flat surfaces. Next, metal-covered enclaves and bare-resin channels are generated using stencil lithography to create both degradable and protected (internal reference) regions simultaneously in a single specimen. Resins having three different degrees of vinyl conversion (DC) are compared, and changes of surface roughness and step height in the two regions are monitored by atomic force microscopy (AFM) before and after incubated in enzyme solutions and saline controls. Specimen biostability is ranked based on the topological profile changes when viewed in cross-section before and after enzymatic challenges. In addition, a model is proposed to quantify specimen enzymatic degradation. Based on this model, enzymatic degradation is detected as early as 4 h, and a surge of enzymatic degradation is detected between 4 h and 8 h. The correlation between the DC of resin network and the surge in degradation is discussed. In summary, this new method is effective in ranking biostability and quantifying enzymatic degradation while also reducing labor, time and cost, which lends itself well to materials development and evaluation of dental resins. STATEMENT OF SIGNIFICANCE: We report, for the first time, the short-time kinetics of enzymatic degradation of methacrylate dental resins. A nanotechnology based method is developed to accelerate the evaluation of resin biostability. This new method reduces experimental time from weeks to one or two days, which will significantly reduce the costs of labor and enzymes. It also introduces a corresponding parameter (ΔH) and a three-cause model for ranking biostability, which confirms the correlation of chemical structure (DC) and material performance and opens new opportunities for studying the resin biostability and its impact on dental applications. Overall, this is a new tool for evaluating resin biostability and developing new materials.

Using Indentation to Quantify Transport Properties of Nanophase-Segregated Polymer Thin Films.

Indentation of hydrated Nafion thin films reveals that both the in-plane diffusivity of water and the intrinsic permeability of the phase-segregated network decrease dramatically with decreasing film thickness. Using pore-network theory, this decrease in diffusivity is attributed to both an increase in ionic-domain heterogeneity and a reduction in ionic-domain connectivity upon confinement.

Surface wrinkling: a versatile platform for measuring thin-film properties.

Surface instabilities in soft matter have been the subject of increasingly innovative research aimed at better understanding the physics of their formation and their utility in patterning, organizing, and measuring materials properties on the micro and nanoscale. The focus of this Review is on a type of instability pattern known as surface wrinkling, covering the general concepts of this phenomenon and several recent applications involving the measurement of thin-film properties. The ability of surface wrinkling to yield new insights into particularly challenging materials systems such as ultrathin films, polymer brushes, polyelectrolyte multilayer assemblies, ultrasoft materials, and nanoscale structured materials is highlighted. A perspective on the future directions of this maturing field, including the prospects for advanced thin-film metrology methods, facile surface patterning, and the control of topology-sensitive phenomena, such as wetting and adhesion, is also presented.

Quantification of the binding affinity of a specific hydroxyapatite binding peptide.

The genesis of bone and teeth involves highly coordinated processes, which involve multiple cell types and proteins that direct the nucleation and crystallization of inorganic hydroxyapatite (HA). Recent studies have shown that peptides mediate the nucleation process, control HA microstructure or even inhibit HA mineralization. Using phage display technology, a short peptide was identified that binds to crystalline HA and to HA-containing domains of human teeth with chemical and morphological specificity. However, the binding affinity and specific amino acids that significantly contribute to this interaction require further investigation. In this study, we employ a microfluidic chip based surface plasmon resonance imaging (SPRi) technique to quantitatively measure peptide affinity by fabricating a novel 4 layer HA SPR sensor. We find the peptide (SVSVGMKPSPRPGGGK) binds with relatively high affinity (K(D) = 14.1 microM +/- 3.8 microM) to HA. The independently measured amino acid fragment SVSV seems to impart a significant contribution to this interaction while the MKPSP fragment may provide a conformational dependent component that enhances the peptides affinity but by itself shows little specificity in the current context. These data show that together, the two moieties promote a stronger synergistic binding interaction to HA than the simple combination of the individual components.

Generation of monolayer gradients in surface energy and surface chemistry for block copolymer thin film studies.

We utilize a vapor deposition setup and cross-diffusion of functionalized chlorosilanes under dynamic vacuum to generate a nearly linear gradient in surface energy and composition on a silicon substrate. The gradient can be tuned by manipulating chlorosilane reservoir sizes and positions, and the gradient profile is independent of time as long as maximum coverage of the substrate is achieved. Our method is readily amenable to the creation of gradients on other substrate surfaces, due to the use of vapor deposition, and with other functionalities, due to our use of functionalized chlorosilanes. Our gradients were characterized using contact angle measurements and X-ray photoelectron spectroscopy. From these measurements, we were able to correlate composition, contact angle, and surface energy. We generated a nearly linear gradient with a range in mole fraction of one component from 0.15 to 0.85 (34 to 40 mJ/m(2) in surface energy) to demonstrate its utility in a block copolymer thin film morphology study. Examination of the copolymer thin film surface morphology with optical and atomic force microscopy revealed the expected morphological transitions across the gradient.

A buckling-based metrology for measuring the elastic moduli of polymeric thin films.

As technology continues towards smaller, thinner and lighter devices, more stringent demands are placed on thin polymer films as diffusion barriers, dielectric coatings, electronic packaging and so on. Therefore, there is a growing need for testing platforms to rapidly determine the mechanical properties of thin polymer films and coatings. We introduce here an elegant, efficient measurement method that yields the elastic moduli of nanoscale polymer films in a rapid and quantitative manner without the need for expensive equipment or material-specific modelling. The technique exploits a buckling instability that occurs in bilayers consisting of a stiff, thin film coated onto a relatively soft, thick substrate. Using the spacing of these highly periodic wrinkles, we calculate the film's elastic modulus by applying well-established buckling mechanics. We successfully apply this new measurement platform to several systems displaying a wide range of thicknessess (nanometre to micrometre) and moduli (MPa to GPa).