Wettability and topography of phospholipid DPPC multilayers deposited by spin-coating on glass, silicon, and mica slides

The surface free energy of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) layers deposited on glass, silicon, or mica by the spin-coating method was estimated. For this purpose, the advancing and receding contact angles of water, formamide, and diiodomethane were measured, and then two concepts of the interfacial interactions were applied. In the contact angle hysteresis approach, the apparent total surface free energy is calculated from the advancing and receding contact angles of the probe liquids, and in the Lifshitz-van der Waals/acid-base approach, the total surface free energy is calculated from previously determined components of the energy, that is, the apolar Lifshitz-van der Waals and the polar electron-donor and electron-acceptor, which are calculated from the advancing contact angles of the probe liquids alone. Comparison of the results obtained using these two approaches provided more information about changes in the hydrophobic/hydrophilic character of the DPPC layers and, simultaneously, a verification of the approaches. Moreover, the roughness and topography of the investigated layers were also examined by atomic force microscopy measurements. The hydrophilic character of the DPPC layers decreased if up to 0.5 mg of DPPC/mL was used to deposit on the substrates by the spin-coating method. Then it increased and leveled off if up to 2-2.5 mg of DPPC/mL was used. The changes in the energy were correlated with the changes in topography of the surfaces.     

Influence of surface-energy components of Ni-P-TiO2-PTFE nanocomposite coatings on bacterial adhesion

The influence of total surface energy on bacterial adhesion has been investigated intensively with the frequent conclusion that bacterial adhesion is less on low-energy surfaces. However, there are also a number of contrary findings that high-energy surfaces have a smaller biofouling tendency. Recently, it was found that the CQ ratio, which is defined as the ratio of Lifshitz-van der Waals (LW) apolar to electron donor surface-energy components of substrates, has a strong correlation to bacterial adhesion. However, the electron donor surface-energy components of substrates varied over only a very limited range. In this article, a series of Ni-P-TiO(2)-PTFE nanocomposite coatings with wide range of surface-energy components were prepared using an electroless plating technique. The bacterial adhesion and removal on the coatings were evaluated with different bacteria under both static and flow conditions. The experimental results demonstrated that there was a strong correlation between bacterial attachment (or removal) and the CQ ratio. The coatings with the lowest CQ ratio had the lowest bacterial adhesion or the highest bacterial removal, which was explained using the extented DLVO theory.     

Surface characterization of atomic oxygen beam-exposed polyimide films using contact angle measurements

Polyimide surfaces exposed to simulated low Earth orbit space environment, i.e., under hyperthermal atomic oxygen bombardment, were characterized by using atomic force microscopy, X-ray photoelectron spectroscopy, and contact angle measurements. The surface analytical results showed that the roughness and the O/C ratio at the atomic oxygen-exposed polyimide surface increased with increasing atomic oxygen fluence. The advancing and receding contact angles decreased with increasing O/C ratios at the polyimide surfaces. The Lifshitz-van der Waals component, the acid and base parameters of the surface free energy of polyimide films were calculated from the contact angles. The base parameter increased with increasing O/C ratio, whereas the acid parameter and the Lifshitz-van der Waals component did not show a remarkable change. These analytical results agree with the in situ XPS data showing the formation of surface functional groups due to atomic oxygen exposure. It was demonstrated in this study that the polyimide surface in a low Earth orbit space environment may become hydrophilic due to the bombardment by atomic oxygen. Received: 4 December 1999 Accepted: 31 August 2000     

Surface properties of polyethylene after low-temperature plasma treatment

The effect of oxygen and ammonia plasma treatments on changes of the surface properties of linear high-density polyethylene (HDPE) was studied. Surface energies of the polymer substrates were evaluated by contact angle measurements using Lifshitz-van der Waals acid-base approach. The surface energy of untreated HDPE is mainly contributed by Lifshitz-van der Waals interactions. After 5 min of plasma treatment, hydrogen bonds are formed on the surface, which is reflected in predominant acid-base interactions. The SEM results obtained demonstrate considerable changes of the surface roughness due to different types of the plasma gas used. Evolution of oxygen- or amino-containing moieties was detected by XPS and ATR FT IR. The prepared polyethylene surfaces were used as a basic support for further fabrication of novel hybrid biocomposite sandwich structures.     

On Neglecting the Polar Nature of Halogenated Hydrocarbons in the Surface Energy Determination of Polar Solids from Contact Angle Measurements

The generally accepted strategy of neglecting the polar nature of halogenated liquids in the surface energy determination using the Lifshitz-van der Waals/Lewis acid-base (LW/AB) approach may lead to erroneous and inconsistent results for polar solids. This was demonstrated in a simulation study carried out on monopolar basic surfaces using water, glycerol, and hypothetical liquids whose surface energy characteristics (gamma(L)(LW)=50 mJ/m(2), gamma(L)(-)=0, and gamma(L)(+)=0-1 mJ/m(2)) were chosen to approximate halogenated hydrocarbons. Neglect of the liquid polarity overestimates the LW component and underestimates the basic parameter of the solid surface energy. This effect increases rapidly with an increase in the actual (nonzero) gamma(L)(+) value of supposedly apolar liquid. Consequently, results with an appropriate level of precision can be obtained only with liquids having gamma(L)(+)<0.02 mJ/m(2). For liquids having gamma(L)(+) approximately 0.5 mJ/m(2) (diiodomethane, s-tetrabromoethane, and, probably, other halogenated hydrocarbons), neglect of the liquid polarity causes errors up to 15% in the LW component and up to 100% in the basic parameter of the solid surface energy. The quantitative trends established in the simulation study were indeed observed in an experimental study performed on the surfaces of poly(methyl methacrylate) and polystyrene using water, glycerol, and diiodomethane or s-tetrabromoethane as the test liquids. Copyright 2000 Academic Press.     

Surface modification of silicate glass using 3-(mercaptopropyl)trimethoxysilane for thiol-ene polymerization

A thiol-ene polymerization was accomplished on silicate glass slides to graft a series of homopolymers and copolymers using 3-(mercaptopropyl)trimethoxysilane (MTS) as both a silane coupling agent and initiator. MTS was initially covalently bonded to an acid cleaned glass surface via a classical sol-gel reaction. Poly(acrylic acid) (PAA), poly(acrylamide) (PAAm), poly(methyl acrylate) (PMA), poly(acrylamido-2-methyl-propanesulfonic acid) (PAMPS), and the copolymer poly(AA-co-AAm-co-MA-co-AMPS) were grafted from the thiol group of MTS. The surface chemistry of the MTS modified slides and polymer grafts was characterized with attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). Surface texture was evaluated with tapping mode atomic force microscopy (TM-AFM). The Owens-Wendt-Kaelble (OWK) and Lifshitz-van der Waals acid-base (LW-AB) methods were used to evaluate surface energies by sessile drop contact angle method. The synthetic approach demonstrated a facile, rapid method for grafting to glass surfaces.     

Spring constants and adhesive properties of native bacterial biofilm cells measured by atomic force microscopy

Bacterial biofilms were imaged by atomic force microscopy (AFM), and their elasticity and adhesion to the AFM tip were determined from a series of tip extension and retraction cycles. Though the five bacterial strains studied included both Gram-negative and -positive bacteria and both environmental and laboratory strains, all formed simple biofilms on glass surfaces. Cellular spring constants, determined from the extension portion of the force cycle, varied between 0.16+/-0.01 and 0.41+/-0.01 N/m, where larger spring constants were measured for Gram-positive cells than for Gram-negative cells. The nonlinear regime in the extension curve depended upon the biomolecules on the cell surface: the extension curves for the smooth Gram-negative bacterial strains with the longest lipopolysaccharides on their surface had a larger nonlinear region than the rough bacterial strain with shorter lipopolysaccharides on the surface. Adhesive forces between the retracting silicon nitride tip and the cells varied between cell types in terms of the force components, the distance components, and the number of adhesion events. The Gram-negative cells' adhesion to the tip showed the longest distance components, sometimes more than 1 microm, whereas the shortest distance adhesion events were measured between the two Gram-positive cell types and the tip. Fixation of free-swimming planktonic cells by NHS and EDC perturbed both the elasticity and the adhesive properties of the cells. Here we consider the biochemical meaning of the measured physical properties of simple biofilms and implications to the colonization of surfaces in the first stages of biofilm formation.     

Interaction forces between waterborne bacteria and activated carbon particles

Activated carbons remove waterborne bacteria from potable water systems through attractive Lifshitz-van der Waals forces despite electrostatic repulsion between negatively charged cells and carbon surfaces. In this paper we quantify the interaction forces between bacteria with negatively and positively charged, mesoporous wood-based carbons, as well as with a microporous coconut carbon. To this end, we glued carbon particles to the cantilever of an atomic force microscope and measured the interaction forces upon approach and retraction of thus made tips. Waterborne Raoultella terrigena and Escherichia coli adhered weakly (1-2 nN) to different activated carbon particles, and the main difference between the activated carbons was the percentage of curves with attractive sites revealed upon traversing of a carbon particle through the bacterial EPS layer. The percentage of curves showing adhesion forces upon retraction varied between 21% and 69%, and was highest for R. terrigena with positively charged carbon (66%) and a coconut carbon (69%). Macroscopic bacterial removal by the mesoporous carbon particles increased with increasing percentages of attractive sites revealed upon traversing a carbon particle through the outer bacterial surface layer.     

Surface thermodynamics and adhesion forces governing bacterial transmission in contact lens related microbial keratitis

Contact lens induced microbial keratitis results from bacterial transmission from one surface to another. We investigated the adhesion forces of Pseudomonas aeruginosa, Staphylococci and Serratia to different contact lenses, lens cases and corneal surfaces using AFM, and applied a Weibull analysis on these adhesion forces to calculate bacterial transmission probabilities from lens case to corneas with a contact lens as an intermediate. Also a new surface thermodynamic parameter was introduced, the interfacial free energy of transmission, which in essence compares the interfacial free energies of bacterial adhesion, calculated from measured contact angles with liquids on the donating and receiving surfaces in the transmission process. Bacterial adhesion forces were generally strongest among all eight strains for the lens case (-6.5 to -12.0 nN) and corneas (-3.5 to -11.5 nN), while contact lenses (-0.6 to -13.1 nN) exerted slightly smaller adhesion forces. Consequently, bacterial transmission from lens case to contact lens yielded a smaller contribution in the final transmission than from contact lens to cornea. Bacterial transmission probabilities as derived from force analyses were higher when the interfacial free energies of transmission were more negative, which is in line with surface thermodynamic principles. Therewith this parameter could provide useful in analyzing other bacterial transmission phenomena between donating and receiving surfaces as well.     

The measurement temperature: an important factor relating physicochemical and adhesive properties of yeast cells to biomaterials

Flow chambers applied to the study of the initial adhesion process of Candida parapsilosis are rarely found in the literature. The ability of these microorganisms to proliferate and form biofilms in environments at temperatures around 22 or 37 degrees C is reflected in the contamination of laboratory instruments and material or in human implant infections, respectively. The initial interaction between yeasts and substrata is mediated by physicochemical forces, which in turn originate from the physicochemical surface properties of both interacting phases. In this context, this work aims to relate the initial rates of adhesion rates to glass and silicone of Candida parapsilosis, strains 294 and 289, grown at 22 and 37 degrees C with the theoretical predictions of the adhesion process, expressed by the interaction free energies and calculated through the physicochemical parameters, which are also measured at 22 and 37 degrees C. The results indicate that physicochemical parameters of yeasts are changed not only by the culture temperature but also by the measurement temperature; only when the measurement temperature is equal to the growth temperature a coherent relation between in vitro adhesion data and interaction free energies can be established. In this sense, the adhesion to glass is mediated by long-range forces or, what amounts to the same thing, by Lifshitz-van der Waals interaction free energy. On the other hand, the adhesion to silicone rubber seems to be moderated by acid-base interaction free energy, which involves the presence of short-range forces. Based on these results, it can be assumed that the substratum surface properties are directly related to the kind of force acting on the initial microbial adhesion process, while cell surface properties dictate the changes in the strength of the force between different samples.     

A Simple Experimental Way of Measuring the Hamaker Constant A(11) of Divided Solids by Immersion Calorimetry in Apolar Liquids

Recent progress in interpretation of immersion calorimetry has shown the link between the immersion enthalpy (Delta(imm)H) value in apolar liquid and the Lifshitz-van der Waals contribution to surface energy (gamma(LW)(S)) of divided solids. In this work we show that a simple relationship can be established between the Hamaker constant (A(11)) of a solid and its immersion enthalpy in a pure apolar solvent. The results are satisfying compared to those already available in the scientific literature. The main interest of this method is the measurement of the Hamaker constants of solids for which contact angle measurements are impossible to carry out and for those for which the complexity of the solid structure hampers the ab initio calculation. Values are given for some clay minerals. Copyright 2000 Academic Press.     

Atomic force microscopy measurement of heterogeneity in bacterial surface hydrophobicity

The structure and physicochemical properties of microbial surfaces at the molecular level determine their adhesion to surfaces and interfaces. Here, we report the use of atomic force microscopy (AFM) to explore the morphology of soft, living cells in aqueous buffer, to map bacterial surface heterogeneities, and to directly correlate the results in the AFM force-distance curves to the macroscopic properties of the microbial surfaces. The surfaces of two bacterial species, Acinetobacter venetianus RAG-1 and Rhodococcus erythropolis 20S-E1-c, showing different macroscopic surface hydrophobicity were probed with chemically functionalized AFM tips, terminating in hydrophobic and hydrophilic groups. All force measurements were obtained in contact mode and made on a location of the bacterium selected from the alternating current mode image. AFM imaging revealed morphological details of the microbial-surface ultrastructures with about 20 nm resolution. The heterogeneous surface morphology was directly correlated with differences in adhesion forces as revealed by retraction force curves and also with the presence of external structures, either pili or capsules, as confirmed by transmission electron microscopy. The AFM force curves for both bacterial species showed differences in the interactions of extracellular structures with hydrophilic and hydrophobic tips. A. venetianus RAG-1 showed an irregular pattern with multiple adhesion peaks suggesting the presence of biopolymers with different lengths on its surface. R. erythropolis 20S-E1-c exhibited long-range attraction forces and single rupture events suggesting a more hydrophobic and smoother surface. The adhesion force measurements indicated a patchy surface distribution of interaction forces for both bacterial species, with the highest forces grouped at one pole of the cell for R. erythropolis 20S-E1-c and a random distribution of adhesion forces in the case of A. venetianus RAG-1. The magnitude of the adhesion forces was proportional to the three-phase contact angle between hexadecane and water on the bacterial surfaces.     

Effect of surface treatment on the Hamaker constant of intermediate modulus carbon fibers

The Hamaker constant of unsized intermediate modulus carbon fibers was evaluated by contact angle measurement following the Fowkes theory of interfacial energetics. The effects of a surface treatment (performed by the manufacturer) and an oxygen plasma treatment (performed by us), both of oxidizing nature, proved to slightly increase the value of the Hamaker constant to a level that enhanced by about 9% the Lifshitz-van der Waals contribution to the theoretical adhesion force between the fiber and an epoxy matrix. A possible explanation of the observed increase of the Hamaker constant is the higher contribution to the overall Lifshitz-van der Waals interaction of Keesom (orientation) and Debye (induction) forces.     

Force measurements of bacterial adhesion on metals using a cell probe atomic force microscope

The adhesion of microbial cells to metal surfaces in aqueous media is an important phenomenon in both the natural environment and engineering systems. The adhesion of two anaerobic sulfate-reducing bacteria (Desulfovibrio desulfuricans and a local marine isolate) and an aerobe (Pseudomonas sp.) to four polished metal surfaces (i.e., stainless steel 316, mild steel, aluminum, and copper) was examined using a force spectroscopy technique with an atomic force microscope (AFM). Using a modified bacterial tip, the attraction and repulsion forces (in the nano-Newton range) between the bacterial cell and the metal surface in aqueous media were quantified. Results show that the bacterial adhesion force to aluminum is the highest among the metals investigated, whereas the one to copper is the lowest. The bacterial adhesion forces to metals are influenced by both the electrostatic force and metal surface hydrophobicity. It is also found that the physiological properties of the bacterium, namely the bacterial surface charges and hydrophobicity, also have influence on the bacteria-metal interaction. The adhesion to the metals by Pseudomonas sp. and D. desulfuricans was greater than by the marine SRB isolate. The cell-cell interactions show that there are strong electrostatic repulsion forces between bacterial cells. Cell probe atomic force microscopy has provided some useful insight into the interactions of bacterial cells with the metal surfaces.     

Topography and surface free energy of DPPC layers deposited on a glass, mica, or PMMA support

An investigation of energetic properties of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) layers deposited on glass, mica, and PMMA (poly(methyl methacrylate)) surfaces was carried out by means of contact angles measurements (advancing and receding) for three probe liquids (diiodomethane, water, and formamide). DPPC was deposited on the surfaces from water (on glass and mica) or methanol (on PMMA) solutions. The topography of the tested surfaces was determined with a help of scanning electron microscopy (SEM) and atomic force microscopy (AFM). Using the measured contact angles, the total apparent surface free energy and its components of the studied layers were determined from van Oss et al.'s (Lifshitz-van der Waals and acid-base components, LWAB) and contact angle hysteresis (CAH) approaches. It allowed us to learn about changes in the surface free energy of the layers (hydrophobicity/hydrophilicity) depending on their number and kind of support. It was found that the changes in the energy greatly depended on the surface properties of the substrate as well as the statistical number of monolayers of DPPC. However, principal changes took place for first three monolayers.     

THE SURFACE,INTERFACIAL AND ELECTROKINETIC PROPERTIES OF BIOMINERALS

ABSTRACT

The apolar (Lifshitz van der Waals) component (γ ^LW _S) and the polar [electron-acceptor (γ ⁺ _S) and electron-donor (γ ^? _S)] parameters of the surface tension of biominerals and surfaces of dental hard tissues have been measured, as well as their ζpotentials. The interfacial tensions between their surfaces and aqueous solutions, determined using van Oss-Chaudhury-Good equations, are comparable with the interfacial free energy values obtained from the kinetics of crystallization and dissolution using a constant composition technique. The electron-donor (γ ^? _S) parameters indicate that most of these minerals have a moderate to high hydrophobicity. The interfacial tension values are consistent with the order of the solubilities of these minerals.     

Adhesion of Candida albicans and Candida dubliniensis to acrylic and hydroxyapatite

The aim of this work was to compare the ability of strains of Candida albicans and Candida dubliniensis to adhere to acrylic and hydroxyapatite (HAP). In order to interpret the adhesion results, the surface properties of cells and materials were determined. Surface tension components (polar and apolar) and hydrophobicity were calculated through contact angle measurement and the elemental composition was determined by X-ray photoelectron spectroscopy (XPS). The results showed no significant differences in the number of adhered cells of both species to acrylic and hydroxyapatite. This was corroborated by the similarities in their surface properties and elemental composition. For both species, the adhesion to acrylic increased in the presence of artificial saliva due to the increase in the electron-donor capacity of this material. In the absence of artificial saliva, the number of adhered cells to HAP was greater than to acrylic, on account of the higher number of electron-donor groups of HAP. Hydrophobicity played a minor role in the adhesion process of both candidal species. Conversely, Lewis acid–base interactions seamed to govern this phenomenon.     

Evolution of wood surface free energy after heat treatment

Surface free energies of pine and beech wood were investigated before and after heat treatment using the Lifshitz-van der Waals/acid-base approach from contact angles measured by the Wilhelmy method. The results obtained showed that the decrease of the electron-donating component of the acid-base component was the major parameter affecting the wetting of the modified wood's surface. The Lifshitz-van der Waals component was slightly modified after heat treatment indicating that the atomic and molecular interactions due to permanent or induced dipoles between wood macromolecules were weakly modified. Modification of the surface chemical composition was studied by X-ray photoelectron spectroscopy (XPS) and titration of acidity. XPS indicated an important decrease of the O/C ratio after heat treatment explaining the decrease of the electron-donating component (γ⁻) of the surface free energy. The decarboxylation and degradation of glucuronic acids present in hemicelluloses, demonstrated by titration of carboxylic acid functions of wood, had only limited effect on the electron-accepting component (γ⁺).     

Adhesion of Pseudomonas fluorescens on magnetic surfaces

The adhesion of Pseudomonas fluorescens (ATCC 700830) to perpendicularly polarized magnetic surfaces was recently discovered. The findings have found that the magnetic free surfaces from different magnetic polarities have different profound effects on the P. fluorescens bacterial adhesion to its surfaces. These phenomena can be explained by the surface magnetic effect, which was found to affect the surface free energy. An in situ experiment, by contrast microscopy and under static conditions, was conducted to determine the influence of magnetic surfaces, that are polarized under different external magnetizing field strengths, on bacterial adhesion. The effect of different magnetic polarities on the surface free energy has also been investigated.