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Biomedical subjects

Thomas J McCarthy

Publications and source records attributed to Thomas J McCarthy.

12 recordsLinked to original sources
PubMed2006

A perfectly hydrophobic surface (thetaA/thetaR = 180 degrees /180 degrees).

A perfectly hydrophobic surface with both advancing and receding water contact angles of 180 degrees was prepared using a facile method on a silicon wafer. Phase separation of a toluene-swollen covalently attached methylsilicone results in a nanoscale network structure that is responsible for the superhydrophobicity. A method for testing extreme hydrophobicity was devised to distinguish between surfaces exhibiting contact angles of 180 and 179 degrees .

Journal Article↗
PubMed2006

Contact angle hysteresis explained.

A view of contact angle hysteresis from the perspectives of the three-phase contact line and of the kinetics of contact line motion is given. Arguments are made that advancing and receding are discrete events that have different activation energies. That hysteresis can be quantified as an activation energy by the changes in interfacial area is argued. That this is an appropriate way of viewing hysteresis is demonstrated with examples.

Journal Article↗
PubMed2006

"Artificial lotus leaf" prepared using a 1945 patent and a commercial textile.

Two polyester textiles, conventional polyester and microfiber polyester fabrics, were hydrophobized using a simple, patented water-repellent silicone coating procedure. Water contact angles on these two surfaces are theta(A)/theta(R) = 151 degrees/140 degrees and theta(A)/theta(R) = 170 degrees/165 degrees, respectively. A smooth surface of this of this coating exhibits theta(A)/theta(R) = 110 degrees/100 degrees. The binary length scale topography (approximately 2 microm/ approximately 50 microm) of the microfiber polyester is responsible for relieving receding contact line pinning and promoting water repellency that is superior to that of the lotus leaf. The recent literature on superhydrophobic surfaces is criticized for neglecting literature of the 1940s.

Journal Article↗
PubMed2006

Two-dimensional fluidics based on differential lyophobicity and gravity.

We have prepared planar fluidics devices using binary chemical patterns consisting of hydrophobic "roads" on which water droplets slide easily and more hydrophobic "curbs" that direct droplet motion. Contact angle and contact angle hysteresis both control the motion of liquid droplets on surfaces. The difference between the advancing contact angles of the two regions prevents the liquid from crossing the interface between them. The low hysteresis of the roads allows facile movement. Gravity (slight tilting of samples) forces droplets to move effortlessly in defined pathways even though the difference in contact angles is not large and both regions are hydrophobic.

Journal Article↗
PubMed2006

The "lotus effect" explained: two reasons why two length scales of topography are important.

Surfaces containing 4 x 8 x 40 microm staggered rhombus posts were hydrophobized using two methods. One, using a dimethyldichlorosilane reaction in the vapor phase, introduces a smooth modified layer, and the other, a solution reaction using methyltrichlorosilane, imparts a second (nanoscopic) length scale of topography. The smooth modified surface exhibits contact angles of thetaA/thetaR = 176 degrees /156 degrees . Arguments are made that the pinning of the receding contact line by the post tops (with thetaA/thetaR = 104 degrees /103 degrees ) is responsible for the hysteresis. The second level of topography raises the contact angles of the post tops and the macroscopic sample to theta(A)/theta(R) = >176 degrees />176 degrees and eliminates hysteresis. The increase in Laplace pressure due to the increase in the advancing contact angle of the post tops is a second reason that two length scales of topography are important.

Journal Article↗
PubMed2006

Condensation on ultrahydrophobic surfaces and its effect on droplet mobility: ultrahydrophobic surfaces are not always water repellant.

The condensation of water was studied on topography-based ultrahydrophobic surfaces containing hydrophobized silicon pillars. Optical microscopy showed that water nucleated and grew both on top of and between the pillars. As condensation progressed, water between the pillars became unstable and was forced upward to the surface. Macroscopic water droplets on top of the pillars coalesced with condensed water that remained between the pillars, pinning the droplets at their three-phase contact line. Dynamic contact angle measurements on ultrahydrophobic surfaces wet with condensation revealed a dramatic increase in hysteresis compared to that on dry surfaces, leading to a corresponding decrease in water drop mobility.

Journal Article↗
PubMed2006

Nylon surface modification: 2. Nylon-supported composite films.

We have developed techniques for the introduction of reactive functional groups to nylon surfaces via site-specific reactions targeting at the naturally abundant amide repeating units on the surface. In this report, we describe the fabrication of nylon-supported composite surfaces using the most efficient modification methods we have developed. N-Alkylation with (3-glycidoxypropyl)triethoxysilane (GPTES) in the presence of potassium tert-butoxide (t-BuOK) leads to surfaces with silica-like reactivity. Subsequent chemical vapor deposition using tetrachlorosilane (SiCl4) and water results in composite films with a thin layer of silica, which was made hydrophobic by reaction with a fluorinated silane reagent. Reduction of the amide groups with borane-THF (BH3-THF) complex leads to a 69% conversion of surface amides to the corresponding secondary amine groups. Alginate was chosen as the model polyelectrolyte for the introduction of a hydrated surface layer. Because of the strong electrostatic interaction between alginate and the amine-enriched nylon surfaces, the adsorption is fast and concentration-independent (within the concentration range studied). The polysaccharide coats the surface homogeneously, without the formation of large aggregates. The amine surfaces obtained by reduction with BH3-THF ((BH3-THF)nylon-NH) and by alkylation with 2-bromoethylamine hydrobromide (BEA-HBr, (EBA-HBr)nylon-NH2) were also used to study gold deposition through electroless plating. Immobilization of a negatively charged metal complex (AuCl4(-)) was achieved through electrostatic interaction. Gold particles disperse preferentially in the bulk of (EBA-HBr)nylon-NH2 films, while they remain confined to the outer surface layer of (BH3-THF)nylon-NH films.

Journal Article↗
PubMed2004

Chemical surface modification of poly(p-xylylene) thin films.

Electrophilic aromatic substitution reactions were studied at poly(p-xylylene) (PPX) film surface-reaction medium interfaces. The extent of the reactions (depth of penetration and degree of substitution) was determined by the interaction of the polymer with the reaction solution. Reaction with chlorosulfonic acid to produce sulfonyl chloride and sulfone functionalities occurred readily in the bulk of PPX, and yields were sensitive to time and temperature. Confinement of this reaction to the PPX surface was achieved by controlling the concentration of the acid. Functionalization of PPX with N-methylol-2-chloroacetamide in sulfuric acid to produce the chloroamidomethylated derivative occurred in high yield and was confined to the surface region of PPX. Hydrolysis of the amide to generate aminomethylated PPX was assessed by XPS and a derivatization reaction. Friedel-Crafts type chemistry (acylation and alkylation reactions) also produced functionalized surfaces, but with lower degrees of substitution than the other two reactions and was strictly surface-confined.

Membranes, Artificial↗
PubMed2004

Adsorption of poly(vinyl alcohol) from water to a hydrophobic surface: effects of molecular weight, degree of hydrolysis, salt, and temperature.

The adsorption of poly(vinyl alcohol) (PVOH) from aqueous solutions to a silicon-supported fluoroalkyl monolayer is described. Thickness, wettability, and roughness of adsorbed films are studied as a function of polymer molecular weight, degree of hydrolysis (from the precursor, poly(vinyl acetate)), polymer concentration, salt type and concentration, and temperature. The data suggest a two-stage process for adsorption of the polymer: physisorption due to a hydrophobic effect (decrease in interfacial free energy) and subsequent stabilization of the adsorbed layer due to crystallization of the polymer. Adsorption of lower-molecular-weight polymers results in thicker films than those prepared with a higher molecular weight; this is ascribed to better crystallization of more mobile short chains. Higher contents of unhydrolyzed acetate groups on the poly(vinyl alcohol) chain lead to thicker adsorbed films. Residual acetate groups partition to the outermost surface of the films and determine wettability. Salts, including sodium chloride and sodium sulfate, promote adsorption, which results in thicker films; at the same time, their presence over a wide concentration range leads to formation of rough coatings. Sodium thiocyanate has little effect on PVOH adsorption, only slightly reducing the thickness in a 2 M salt solution. Increased temperature promotes adsorption in the presence of salt, but has little effect on salt-free solutions. Evidently, higher temperatures favor adsorption but cause crystallization to be less thermodynamically favorable. These competing effects result in the smoothest coatings being formed in an intermediate temperature range.

Adsorption↗
PubMed2004

Curving and frustrating flatland.

Two polymer chains that occupy equal volumes when covalently linked together at one end self-assemble into an alternating lamellar morphology that has a characteristic period dictated by the molecular weight. When such copolymers are confined within alumina membranes that have cylindrical pores with diameters comparable to the repeat period, the interaction of the blocks with the confining walls and the imposed curvature induces a morphological transformation to relieve the constraints. Here, we show a lamella-to-toroid transition, captured through the dissolution of the surrounding membrane.

Journal Article↗
PubMed2004

Simultaneous tailoring of surface topography and chemical structure for controlled wettability.

Wettability was controlled in a rational manner by individually and simultaneously manipulating surface topography and surface chemical structure. The first stage of this research involved the adsorption of charged submicrometer polystyrene latex particles to oppositely charged poly(ethylene terephthalate) (PET) film samples to form surfaces with different topographies/roughness; adsorption time, solution pH, solution ionic strength, latex particle size, and substrate charge density are external variables that were controlled. The introduction of discrete functional groups to smooth and rough surfaces through organic transformations was carried out in the second stage. Amine groups (-NH(2)) and alcohol groups (-OH) were introduced onto smooth PET surfaces by amidation with poly(allylamine) and adsorption with poly(vinyl alcohol) (PVOH), respectively. On latex particle adsorbed surfaces, a thin layer of gold was evaporated first to prevent particle redistribution before chemical transformation. Reactions with functionalized thiols and adsorption with PVOH on patterned gold surfaces successfully enhanced surface hydrophobicity and hydrophilicity. Particle size and biomodal particle size distribution affect both hydrophobicity and hydrophilicity. A very hydrophobic surface exhibiting water contact angles of 150 degrees /126 degrees (theta(A)/theta(R)) prepared by adsorption of 1-octadecanethiol and a hydrophilic surface with water contact angles of 18 degrees /8 degrees (theta(A)/theta(R)) prepared by adsorption of PVOH were prepared on gold-coated surfaces containing both 0.35 and 0.1 microm latex particles. The combination of surface topography and surface-chemical functionality permits wettability control over a wide range.

Adsorption↗