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Apatite deposition on titanium surfaces--the role of albumin adsorption.

Titanium implant surfaces are known to spontaneously nucleate apatite layers when in contact with simulated body fluids. However, adsorption of proteins may influence the process of apatite layer formation. In this study the role of bovine serum albumin (BSA) adsorption in the process of apatite deposition on titanium substrates is investigated. Deposition of calcium phosphate was induced by immersing titanium substrates in a Hank's balanced salt solution (HBSS) for times ranging from 1 to 23 days. The resulting substrates were studied by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), wettability measurements and electrochemical impedance determinations. All these methods indicate the presence of a calcium phosphate layer. The same procedure was repeated substituting HBSS with a solution of BSA in HBSS. Although SEM, EDS and electrochemical impedance spectra do not reveal the presence of an apatite layer, XPS analysis strongly indicates that the inhibition of apatite formation by BSA is only partial. The competition between BSA adsorption and apatite deposition seems to lead to a mixed film where the protein co-exists with calcium phosphate. Wettability studies suggest that this surface film is heterogeneous and porous, similar to the thicker films formed in albumin-free HBSS.

Adsorption↗

Preparation of poly(ethylene glycol)-polystyrene block copolymers using photochemistry of dithiocarbamate as a reduced cell-adhesive coating material.

This article reports a novel preparation method of poly(ethylene glycol) (PEG)-polystyrene (PST) amphiphilic block copolymers with well-defined block lengths by using photopolymerization of an iniferter, benzyl N,N-diethyldithiocarbamate. PEG macroiniferters, which were prepared by end-capping of PEG monomethyl ethers with benzyl N,N-diethyldithiocarbamate group at one end, were irradiated with UV light in the presence of styrene (ST). NMR analyses showed that the PST block was chain-extended from the PEG block, resulting in the preparation of PEG-PST block copolymers. The number-average molecular weights of the copolymers increased almost linearly with irradiation time, light intensity, and concentration of ST. The polydispersities of the copolymers remained relatively small throughout the reaction (Mw/Mn approximately 1.3). The composition of two PEG-PST block copolymers thus obtained was as follows: PEG (Mn; 1.9 x 10(3) gmol(-1))-PST (3.0 x 10(3) gmol(-1)) and PEG (4.9 x 10(3) gmol(-1))-PST (2.6 x 10(3) gmol(-1)). These copolymers were coated onto a poly(ethylene terephthalate) film surface. X-ray photoelectron spectroscopy analyses and water wettability measurements showed that the PST block was enriched at the outermost layer as cast in air, whereas upon immersion into water, the PEG block was oriented toward water. Enhanced wettability was observed for the diblock copolymer with a higher PEG content. Significantly reduced cell adhesion was observed on both the coated surfaces. Thus, the PEG-PST block copolymer may function as a cell adhesion-resistant coating which reduced cell-substrate interaction.

Animals↗

Pulsed plasma deposition of allylamine on polysiloxane: a stable surface for neuronal cell adhesion.

Allylamine was pulse-plasma polymerized onto a hydrophobic polysiloxane substrate to create cell adhesion surfaces for cell culture that would not require pretreatment with polylysine, could be sterilized via autoclaving, and could be re-used for several culture cycles. We investigated two different plasma deposition protocols at 200 W RF power: (1) a duty cycle of 3 ms on and 5 ms off; and (2) a cycle of 3 ms on and 45 ms off. Control surfaces were unmodified polysiloxane, activated polysiloxane via flaming, and flamed polysiloxane further modified with poly-D-lysine (PDL). The different surfaces were characterized with XPS analysis, water contact angle, and cell adhesion and growth using dissociated murine embryonic spinal tissue. We found that both the amine content of the 3/45 duty cycle surface and the wettability was higher than that of the 3/5 surface. Also, spinal cord cells were better dispersed 24 h after seeding on the 3/45 surface, suggesting a difference in early adhesion dynamics. However, the networks on the two types of modified surfaces revealed no obvious morphological differences after 2 weeks in vitro. The stability of allylamine-decorated surfaces after autoclaving was high with only minor changes in wettability and nitrogen content. Cell growth on such surfaces after autoclaving was comparable to that found on flamed polysiloxane, freshly modified with PDL. Allylamine surfaces were still usable as cell growth substrates after three autoclaving cycles, 4 weeks under warm culture medium, and simple cleaning procedures, indicating the achievement of a long-lasting modification that did not require the repeated use of PDL before each seeding.

Allylamine↗

The use of solution calorimetry with micellar solvent systems for the detection of polymorphism.

The presence of multiple polymorphic forms in seven batches of raw material of a model compound having poor wettability properties (cimetidine) was studied by solution calorimetry. Due to the large number of polymorphic forms described in the literature ('Gazz. Chim. Ital., 109 (1979) 535'; 'J. Pharm. Sci., 73 (1983) 1436'; 'J. Pharm. Biomed. Anal., 3 (1985) 303') and its poor wettability characteristics, cimetidine was chosen as a model compound to illustrate the possible use of solution calorimetry in the detection of polymorphism using surfactant systems as solvents for dissolution. Due to the closeness of the melting points of the different polymorphic forms of cimetidine, DSC was not the best investigational tool. As initially suspected, the measurement of enthalpy of solution values in water of the cimetidine batches was not possible. However, the use of sodium dodecyl sulfate (SDS) and polysorbate 20 (Tween 20(R)) at concentrations above their respective cmc values permitted the detection of significant differences in enthalpy of solution among several batches. The presence of different polymorphic forms was confirmed by microscopy, X-ray powder diffractometry, and Fourier transform infrared spectroscopy.

Calorimetry↗

Surface composition of spray-dried milk protein-stabilised emulsions in relation to pre-heat treatment of proteins.

Several important technical properties of spray-dried food powders depend on particle-liquid interactions (e.g. wettability, dispersability) and particle-particle interactions (e.g. flowability). It can be assumed that the chemical composition of the surface layer of the particles to a large extent determine these properties. The present study has been aimed to investigate the relation between the surface composition of spray-dried milk protein-stabilised emulsions and pre-heat treatment of the proteins. Solutions of WPC were heat-treated at low (60-90 degrees C) and high (140 degrees C) temperature and the degree of denaturation was determined, prior to the preparation of emulsions with rapeseed oil. The surface composition of the dry powders were established by using ESCA (electron spectroscopy of chemical analysis). The emulsions were characterised by droplet size distribution before spray drying and after dissolution of the powders. Also free fat extractions and estimations of wettability (dissolution rates) were performed. The powder surface coverage of protein decreased with increasing degree of protein denaturation before the emulsification, whereas the emulsion droplet size increased both before spray drying and after reconstitution of powders. The free fat extraction as well as the dissolution rate, whereof the latter decreased with increasing surface fat coverage, correlated well with the fat coverage of the powder surface.

Journal Article↗

Modulation of adhesion, spreading and cytoskeleton organization of 3T3 fibroblasts by sulfonic groups present on polymer surfaces.

The early phase of 3T3 fibroblast interaction with sulfonated styrene copolymer surfaces, of two sulfonic group densities and thus of differing wettability, was studied. The sulfonic groups present on copolymer surfaces affected the behaviour of cells, i.e. they stimulated cell adhesion, activated cell spreading and influenced cytoskeleton reorganization. The relative number of adhering cells correlated, while the number of spreading cells inversely correlated, with the surface density of sulfonic groups. Cell shape and the pattern of distribution of F-actin, alpha-actinin and vinculin in the interacting cells also depend on the surface density of sulfonic groups. On surfaces of high sulfonic group density, highly polarized cells were observed with F-actin bundles. On surfaces of low sulfonic group density, the cells spread with a square-like morphology with F-actin organized in stress fibres. In contrast, the cells spread poorly on nonsulfonated surfaces and cell adhesion was unaffected by surface wettability. The contribution of alpha(5)beta(1), alpha(4), and beta(5)integrins to the cell interaction with fibronectin (FN) and vitronectin (VN) adsorbed from serum-containing medium on polymer surfaces was examined. Our results suggest that surface sulfonic groups influence the conformation of FN and VN adsorbed on polymer surfaces and, in turn, determine the integrins that are involved in cell adhesion.

3T3 Cells↗

Powder dynamic contact angle data in the pharmaceutical industry.

Formulation scientists generate physicochemical data that are used in process modelling and in the prediction of end-product quality. In this respect, contact angles are of particular importance as the surface energy of substances influences their processability and bioavailability. Dynamic contact angle (DCA) analysis represents a straightforward wettability assay. Now fully adapted to powders, DCA analysis also proves to be more efficient than other methods for wettability determination.

Journal Article↗

An instrument for measuring bacterial penetration through fabrics used for barrier clothing.

A new instrument has been designed to measure the penetration by rubbing of bacteria from cloth contaminated in the nursing of burn patients through fabrics designed for barrier garments. Most fabrics tested dry reduced the transfer of bacteria from the source cloth to about 10%, irrespective of the results of air filter tests, which agrees with mock nursing results. When the fabrics were tested against a wet surface, the transfer of bacteria rapidly reached 100% if the fabrics had a high wettability, but was slower for fabrics with a low wettability. Through closely woven waterproofed cotton, transfer was 5--25%, but increased three- to four-fold after ten launderings, in line with the water absorption. Transfer through plastic-laminated material was less than 1%. The results suggest that barrier garments should be made either of plastic or of recently waterproofed closely woven cotton at points of contact between nurse and patient where the clothes may be wetted by bacteria-containing wound secretions.

Asepsis↗

Composition and structure of agents responsible for development of water repellency in soils following oil contamination.

Soil from the Ellerslie site of experimental oil contamination in Alberta developed water repellency some years after initial remediation. The water-repellent soils were compared to clean soils and contaminated but wettable soils by solid-state nuclear magnetic resonance (NMR). The effects of extraction with CH2Cl2 (for petroleum hydrocarbons), NaOH (for natural organic matter), and 2-propanol/ammonia (IPA/NH3) on wettability were evaluated by the molarity of the ethanol droplet (MED) test. Soil extracts and whole soils, after extraction, were examined using NMR and Fourier transform infrared spectroscopy (FTIR). On the basis of the structure--MED correlations, a model of a thin-layer natural organic matter--petroleum products complex formed under strong drying conditions is proposed to account for the development of water repellency. Studies of two similar soils from accidental oil spills are supportive.

Environmental Pollution↗

Reversible super-hydrophobicity to super-hydrophilicity transition of aligned ZnO nanorod films.

Remarkable surface wettability transition occurs with an inducement of ultraviolet (UV) for aligned ZnO nanorod films. The inorganic oxide films, which show super-hydrophobicity (left), become super-hydrophilic (right) when exposed to UV illumination. After the films are placed in the dark, the wettability evolves back to super-hydrophobicity. This reversible effect is ascribed to the cooperation of the surface photosensitivity and the aligned nanostructure. Such special property will greatly extend the applications of ZnO films.

Journal Article↗

Non-covalent assembly of a photoswitchable surface.

A noncovalently bound multilayered thin film in which individual layers are linked by metal ligand interactions undergoes a photochemically initiated permanent change in surface wettability. The film consists of three separate layers: a SAM on gold of 4-[(10-mercaptodecyl)oxy]pyridine-2,6-dicarboxylic acid, a layer of Cu(II) ions that are deposited onto the SAM and bind symmetrically in the site provided by the two carboxylate groups and the pyridyl nitrogen atom, and a layer of cis-2,2'-dipyridylethylene, which caps the Cu(II) layer by complexation through both pyridyl nitrogen atoms (Film I). Photoexcitation of the film in chloroform at 300 nm leads to substantial cis-trans isomerization as indicated by conductivity, impedance, grazing incidence IR, and contact angle measurements. The latter show a decrease in contact angle (increase in wettability) of 17 degrees , which is attributed to exposure of both the underlying Cu(II) layer and one of the pyridyl ring nitrogen atoms following isomerization to the trans isomer.

Journal Article↗

Reversible control of free energy and topography of nanostructured surfaces.

We describe a facile method for the formation of dynamic nanostructured surfaces based on the modification of porous anodic aluminum oxide with poly(N-isopropyl acrylamide) (PNIPAAm) via surface-initiated atom transfer radical polymerization. The dynamic structure of these surfaces was investigated by atomic force microscopy (AFM), which showed dramatic changes in the surface nanostructure above and below the aqueous lower critical solution temperature of PNIPAAm. These changes in surface structure are correlated with changes in the macroscopic wettability of the surfaces, which was probed by water contact angle measurements. Principal component analysis was used to develop a quantitative correlation between AFM image intensity histograms and macroscopic wettability. Such correlations and dynamic nanostructured surfaces may have a variety of uses.

Acrylic Resins↗

Adsorption of microstructured particles at liquid-liquid interfaces.

The solid particles are adsorbed at interfaces and form self-assembled structures when the particles have suitable wettability to both liquids. Here, we show theoretically how the microstructure on the particle surface affects their adsorption properties. The physical properties of the interface adsorbing a particle will be described by taking into account the surface roughness due to the microstructure. The microstructure on the surface changes drastically the wettability and the equilibrium position of the adsorbed particle. Therefore, the contact angle of the particle at the three-phase contact line shifts with the particle surface area, because the surface roughness enhances the interfacial properties of the particle surface. Moreover, the range of the interfacial tensions at which the particle is adsorbed becomes narrower with the increase of the surface roughness. The effect of the particle shape on the adsorption properties is also studied. In the case of disk-shaped particles, the energy changes discontinuously when the plane surface of the particle contacts the liquid-liquid interface. The adsorbing position does not change with the surface roughness. The orientation of a parallelepiped particle at the liquid-liquid interface is governed by the aspect ratio and the surface area of the particle. On the other hand, the particle which is partially covered with the microstructured surface is adsorbed firmly at the interface in an oriented state. We should consider not only the interfacial tensions but also the surface structure and the particle shape to control the adsorption behavior of the particle.

Journal Article↗

Inversion of silica-stabilized emulsions induced by particle concentration.

Emulsions of equal volumes of a cyclic silicone oil and water stabilized by fumed silica nanoparticles alone can be inverted from oil-in-water (o/w) to water-in-oil (w/o) by simply increasing the concentration of particles. The phenomenon is found to be crucially dependent both on the inherent hydrophobicity of the particles and on their initial location. Inversion only occurs in systems with particles of intermediate hydrophobicity when dispersed in oil; emulsions prepared from the same particles but initially dispersed in water remain o/w at all particle concentrations. The stability and drop size distributions in the different emulsions are compared. Various hypotheses are put forward and argued to explain this novel inversion route including adsorption of oil onto particle surfaces, hysteresis of contact angle affecting particle wettability in situ, and the structure of particle dispersions in oil or water prior to emulsification inferred from rheology and light scattering measurements. We propose that the tendency for particles to behave more hydrophobically at higher concentrations in oil is due to the reduction in the effective silanol content at their surfaces as a result of gel formation via silanol-silanol hydrogen bonds. In water, solvation of particle surfaces prevents this from occurring and particles behave as hydrophilic ones at all concentrations. A concentration-induced change in particle wettability is thus advanced.

Journal Article↗

Fabrication gradient surfaces by changing polystyrene microsphere topography.

A rather simple yet effective way to fabricate gradient surfaces by changing polystyrene (PS) microsphere topography in a temperature gradient field is proposed. The wettability of the film has an obvious gradient change from 88.7 to 148.1 degrees . The changes of the PS microsphere topography are believed to be responsible for the changing of the wettability.

Journal Article↗

Particle zips: vertical emulsion films with particle monolayers at their surfaces.

Vertical emulsion films with particle monolayers at their surfaces have been studied by direct microscope observations. The effects of particle wettability and surface coverage on the structure and stability of water films in octane and octane films in water have been investigated. Monodisperse silica particles (3 microm in diameter) hydrophobized to different extents have been used. It is found that the structure and stability of emulsion films strongly depend on the film type (water-in-oil or oil-in-water), the particle contact angle, the interactions between particles from the same and the opposite monolayer, and the monolayer density. Stable films are observed only when the particle wettability fulfills the condition for stable particle bridges--in agreement with the concept that hydrophilic particles can give stable oil-in-water emulsions, whereas hydrophobic ones give water-in-oil emulsions. In the case of water films with dilute disordered monolayers at their surfaces, the hydrophilic particles are expelled from the film center toward its periphery, giving a dimple surrounded by a ring of particles bridging the film surfaces. In contrast, the thinning of octane films with dilute ordered monolayers at their surfaces finally leads to the spontaneous formation of a dense crystalline monolayer of hydrophobic particles bridging both surfaces at the center of the film. The behaviors of water and octane films with dense close-packed particle monolayers at their surfaces are very similar. In both cases, a transition from bilayer to bridging monolayer is observed at rather low capillary pressures. The implications of the above finding for particle stabilized emulsions are discussed.

Journal Article↗

Benzoic and aliphatic carboxylic acid monomolecular layers on oxidized GaAs surface as a tool for two-dimensional photonic crystal infiltration.

The possibility of using surface-adsorbed monolayers on oxidized GaAs single crystals is investigated to explore liquid crystal (LC) wettability and alignment. A technological process is developed to chemically activate the GaAs surface with a view to perform the infiltration of tunable two-dimensional (2-D) photonic crystals with LC materials. We demonstrate a vapor growth method to fabricate self-organized monolayers of carboxylated derivatives on plasma-activated surfaces. Our monolayers strongly increase the wettability of liquid crystal surfaces and may be helpful in achieving the infiltration of 2-D GaAs photonic crystals. Two types of molecular families were studied in this work: benzoic acids and fatty acids. Para-substituted benzoic acids with a wide range of electrical dipoles allow adsorption to be followed by measuring the surface potential of the grafted substrates using the Kelvin probe technique. These model compounds yield important information on the grafting conditions and the stability of the layers. Surface-adsorbed fatty acids are well-known to produce hydrophobic surfaces. The water contact angles measured on modified GaAs surfaces are equivalent to the ones measured on classical alkanethiol layers on gold.

Journal Article↗

Pattern formation and dewetting in thin films of liquids showing complete macroscale wetting: from "pancakes"to "swiss cheese".

Based on the complete 3D numerical solutions of the nonlinear thin film equation, we address the problems of surface instability, dynamics, morphological diversity and evolution in unstable thin films of the liquids that display complete macroscale wetting. The twin constraints of complete macroscale wettability and nanoscale instability produce a variety of microscopic morphological phases approximating sharp crystal surfaces with flat tops resembling a mesa or a micro "pancake" or a slice of Swiss cheese. While the maximum thickness of flat regions is found to be independent of the initial film thickness, the precise lateral morphology of microdomains formed depends on the film thickness. As the film thickness is increased, the initial pathway of evolution changes from the formation of small spherical droplets, to long mesas (parapets) and islands, to circular holes, all of which eventually resolve by ripening into a collection of round pancakes at equilibrium. However, beyond a certain transition thickness, a novel metastable honeycombed morphology, resembling a membrane or a slice of Swiss cheese, is uncovered, which is produced by an abrupt "freezing" of the evolution during hole growth. In contrast, the spinodal dewetting in thin films of partially wettable systems always engenders spherical droplets at equilibrium. The equilibrium dewetted area from simulations, as well as from simple mass balance, is shown to decline linearly with the initial film thickness.

Journal Article↗