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Surface coating of hydrophilic-hydrophobic block co-polymers on a poly(acrylonitrile) haemodialyser reduces platelet adhesion and its transmembrane stimulation.

Surface design aimed at reduced adhesion and preserved functions of platelets is of great importance for extracorporeal devices. In this study, a coating technique using hydrophilic-hydrophobic block co-polymers on a hydrophobic poly(acrylonitrile) (PAN) haemodialyser was explored. The hydrophilic block of co-polymers was composed of either poly(methoxy polyethylene glycol methacrylate) or poly(dimethyl acrylamide), and the hydrophobic block was poly(methyl methacrylate). The co-polymers were coated on the dialyser membrane by means of a solution coating method. Upon coating, the hydrophobic block of the co-polymers was anchored on a PAN membrane and the hydrophilic block oriented towards the blood-material interface. This was deduced from water wettability measurements. Significantly reduced transmembrane stimulation of platelets was observed, which was evaluated by determining the intracellular calcium ion concentration of platelets eluted through treated hollow fibres. This suppression was enhanced as the relative fraction of the hydrophilic block of the co-polymers increased. Furthermore, the number of platelets adhering to the co-polymer-coated PAN membrane was drastically reduced. Thus, coating of the hydrophilic-hydrophobic block co-polymers provided better biocompatibility on a hydrophobic PAN dialyser.

Acrylamides↗

Adhesion and proliferation of cultured human aortic smooth muscle cells on polystyrene implanted with N+, F+ and Ar+ ions: correlation with polymer surface polarity and carbonization.

Physicochemical surface properties and biocompatibility were studied in polystyrene (PS) implanted with 150 keV N+, F+ and Ar+ at doses ranging from 1 x 10(12) to 1 x 10(15) cm-2. Adhesion and proliferation of cultured human aortic smooth muscle cells (SMCs) on ion implanted PS were thoroughly examined for dependence on implanted dose and ion species and in close relation to polymer surface oxidation, surface polarity, concentration of conjugated double bonds and sheet resistivity. The surface polarity of PS was a smooth, increasing function of the implanted dose. However, the dependence of SMC population density on the implanted dose was found to be more complicated. After 18 h cultivation time (i.e. when only cell attachment and spreading took place), the number of adhered SMCs and their degree of spreading first increased with increasing ion dose, and after reaching a maximum at the dose of 5 x 10(12) cm-2, they decreased to original values. For doses above 5 x 10(14) cm-2, an increase in SMC population density and spreading was again observed. The first maximum in cell adhesion can be explained by slight increases in the surface polarity and wettability, optimal for cell adhesion, and the second maximum by progressive carbonization of the PS surface. After 96 h cultivation time (i.e. when the cells proliferated intensively), the dramatic dependence of the SMC population density on implanted dose is mostly smeared out. This observed dependence of SMC attachment, spreading and subsequent proliferation on the implanted dose was similar in all three ion species, but highest cell densities were achieved on PS implanted with F+ ions.

Argon↗

Microbial adhesion to ionogenic PHEMA, PU and PP implants.

This study concentrates on adhesion of microorganisms to polymeric biomaterials implanted in the urinary tract. A number of extensively used polymeric biomaterials (i.e., poly(hydroxyethyl-methacrylate) and its copolymers with a series of acrylic monomers--acrylic acid and dimethylaminoethyl methacrylate--polyetherurethane and polypropylene (PP)) was prepared by using suitable polymerization methods. Their surface structures were characterized by wettability and surface free energy measurements, scanning electron microscopy, electron spectroscopy for chemical analysis, and attenuated total reflection Fourier transform infrared spectroscopy techniques. It was found that these surfaces have different surface free energies in the range of 26.9-63.0 erg cm-2 with different charge and charge densities. The adherence of two strains of Escherichia coli (non-pathogen and pathogen) isolated from indigenous flora of trachea and pathogen flora of urethral surfaces, and uropathogenic Candida albicans to the polymeric surfaces was studied in vitro by means of microscopic techniques. The hydrophobicity of cell surfaces was determined by using two methods including adhesion to hydrocarbons and contact angle measurements. The uropathogenic E. coli and C. albicans were found to be relatively hydrophobic with a similar surface free energy, approximately 40 erg cm-2, when compared with normal E. coli strain which has 61 erg cm-2 free energy. The uropathogenic strains were poorly adherent to hydrophilic polymer surfaces while showing excellent adherence on hydrophobic PP surfaces. However, a relatively hydrophilic, nonpathogenic E. coli strain showed the opposite adhesion behaviour to the same surfaces.

Bacterial Adhesion↗

A comparative study on pesticide formulations for application in running waters.

Release rates into water of monolinuron, desmetryne, and carbofuran from three different types of formulations have been studied to control aquatic weeds in running waters. The migration of active ingredients (AI) from conventional wettable powder formulations was complete within 1 day, while the migration from ethylene-vinyl acetate copolymeric matrix (EVA) lasted significantly longer due to low diffusion coefficients of monomeric pesticides in polymeric matrices Do = 10(-8)-10(-12) (cm2 X sec-1). The herbicidal action could be extrapolated up to several years. Release duration of AI from calcium alginate beads lasted 2 weeks. Herbicidal effectiveness of terbutryne-EVA formulation has been investigated in a laboratory-scale simulated flow system device with duckweed plants (Lemna minor) as test organism. Growth inhibition of duckweed could be achieved at approx 20 ppb terbutryne in steady state.

Absorption↗

The effect of ion implantation on cellular adhesion.

As there are only a finite number of materials suitable for orthopaedic reconstruction, considerable effort has been devoted recently to investigating ways of altering the surface chemistry of prosthetic materials without altering their bulk properties. Ion beam implantation is one such technique which is appropriate for orthopaedic reconstructive materials. This paper investigates the early effect of ion beam modification on cellular attachment of bone derived cells using a prototype device which measures the strength of attachment of individual cells to a silicon substratum. The results point to several conclusions. (1) There is no evidence that ion beam implantation with nitrogen, phosphorus, manganese or magnesium produces increased adhesion of human bone derived cells. (2) Surface etching with hydrofluoric acid, electron bombardment and thermal oxidation increases the strength of attachment between cells and substrata. (3) There is a correlation between wettability and rate of cellular attachment to oxygen implanted substrata during the first 2 h after cellular seeding. However, the increase in cellular attachment cannot be entirely explained by the change in critical surface tension or via increased fibronectin attachment to the substrata.

Bone Transplantation↗

Effects of SO2, NO2, and O3 on population development and morphological and physiological parameters of native herb layer species in a beech forest.

The native ground vegetation of a beech forest was fumigated with moderate doses of SO(2), NO(2), and O(3) in open-top chambers. The effects of fumigants on growth and above-ground development were dependent on species. The treatments caused early senescence in several of the species present. The epicuticular waxes were attacked by fumigation, which was shown by higher wettability of the leaf surfaces and by leaching of ions. Interspecific differences were observed in the responses of transpiration and photosynthesis to fumigation. Similar patterns of effects on transpiration and photosynthesis, however, were found in the same species. Carbohydrate metabolism was altered by fumigation, leading to starch accumulation in the leaves. Besides effects on higher plants, fumigations also resulted in alterations of the soil microflora. The bacteria/fungi ratio was depressed at the fumigation plots.

Journal Article↗

Effects of acid mist on needles from mature Sitka spruce grafts. Part II. Influence of developmental stage, age and needle morphology on visible damage.

Mature grafts of five Sitka spruce (Picea sitchensis (Bong.) Carr.) clones were exposed to simulated acid mist comprising an equimolar mixture of H(2)SO(4) and NH(4)NO(3) (1.6 and 0.01 mol m(-3)) at pH 2.5 and 5.0. Mist was applied to potted plants growing in open-top chambers on consecutive days, four times a week, at a precipitation equivalent of 1 mm per day. The total exposure to polluted mist was equivalent to three times that measured at an upland forest in SE Scotland. The aim of the experiment was to characterize the response of juvenile foliage produced by physiologically mature grafts (on seedling root stock) and compare it with the behaviour of juvenile foliage on seedlings. Development of visible foliar damage was followed through the growing season. Measurements of needle length, diameter, weight, surface area, surface was weight and wettability were made on current year needles to determine whether particular foliar characteristics increased susceptibility to injury. Significant amounts (> 10%) of visible needle damage was observed on only one of the five clones. Damage was most severe on the clone with the most horizontal branch and needle habit, but over the five clones there was no relationship between angle of branch display and damage. Likewise no combination of needle characteristics (length, width, area, amount of wax) was indicative of potential susceptibility. A comparison with previous acid misting experiments using seedlings suggests that juvenile foliage on physiologically mature trees is equally susceptible to visible injury as juvenile seedling foliage. Data of budburst differed among clones, and in this experiment exerted the over-riding influence on development of injury symptoms. Foliage exposed to a combination of strong acidity and high sulphate concentrations over the few weeks immediately following budburst suffered most visible injury. The absence of significant amounts of visible damage in UK forests probably reflects the general low susceptibility to visible injury of Sitka spruce exposed to acid mist.

Journal Article↗

Clinical application of collagen sheet, YCWM, as a burn wound dressing.

In the Linkou Burn Unit, a recently developed new wound dressing derived from porcine skin was evaluated. This newly designed porcine dressing, called young collagenous wettable membrane (YCWM), was developed by the staff of the Department of Cellular and Molecular Biology of Chang Gung Memorial Hospital. Many specific characteristics, such as negligible antigenicity, semitransparency, sterilizability, good pain relief and low costs, have been associated with it. The results of a clinical trial on 59 wounds on 50 burn patients proved encouraging. Some disadvantages such as maceration and delayed eschar separation were noted. We conclude that YCWM is suitable for the treatment of the clean, dry donor sites and superficial partial skin loss burn wounds of non-infected, non-immunocompromised patients.

Biological Dressings↗

Evaluation of acute toxicity of carbaryl and malathion to freshwater teleosts, Channa punctatus (Bloch) and Heteropneustes fossilis (Bloch).

Bioassay tests evaluated the acute toxicity of carbaryl (a carbamate) (50% wettable powder, W.P.), and malathion (50% E.C.) (an organophosphate) (50% emulsifiable concentrate; E.C.) by determining their LC50 and the acute toxic ranges for 24, 48 and 72, and 96-h exposure to Channa punctatus (Bl.) and Heteropneustes fossilis (Bl.). Regression equations and slope functions were determined for different time periods. The relative susceptibility of the fish, the relative toxicity, and the safe concentrations of these biocides were calculated on the basis of LC50 for 96 h. C. punctatus was found to be relatively more susceptible to both the compounds, while malathion was the more toxic of the two biocides.

Animals↗

Relationship between biomedical catheter surface properties and lubricity as determined using textural analysis and multiple regression analysis.

In this study, the surface properties of and work required to remove 12 commercially available and developmental catheters from a model biological medium (agar), a measure of catheter lubricity, were characterised and the relationships between these properties were examined using multiple regression and correlation analysis. The work required for removal of catheter sections (7 cm) from a model biological medium (1% w/w agar) were examined using tensile analysis. The water wettability of the catheters were characterised using dynamic contact angle analysis, whereas surface roughness was determined using atomic force microscopy. Significant differences in the ease of removal were observed between the various catheters, with the silicone-based materials generally exhibiting the greatest ease of removal. Similarly, the catheters exhibited a range of advancing and receding contact angles that were dependent on the chemical nature of each catheter. Finally, whilst the microrugosities of the various catheters differed, no specific relationship to the chemical nature of the biomaterial was apparent. Using multiple regression analysis, the relationship between ease of removal, receding contact angle and surface roughness was defined as: Work done (N mm)=17.18+0.055 Rugosity (nm)-0.52 Receding contact angle ( degrees ) (r=0.49). Interestingly, whilst the relationship between ease of removal and surface roughness was significant (r=0.48, p=0.0005), in which catheter lubricity increased as the surface roughness decreased, this was not the case with the relationship between ease of removal and receding contact angle (r=-0.18, p>0.05). This study has therefore uniquely defined the contributions of each of these surface properties to catheter lubricity. Accordingly, in the design of urethral catheters, it is recommended that due consideration should be directed towards biomaterial surface roughness to ensure maximal ease of catheter removal. Furthermore, using the method described in this study, differences in the lubricity of the various catheters were observed that may be apparent in their clinical use.

Biocompatible Materials↗

Inhibition of bacterial adhesion on PVC endotracheal tubes by RF-oxygen glow discharge, sodium hydroxide and silver nitrate treatments.

Medical-grade poly(vinyl chloride) (PVC) was chemically modified to study how the incorporation of monovalent silver influences Pseudomonas aeruginosa adhesion and colonization. The modification investigated consisted of a radio frequency-oxygen (RF-O(2)) glow discharge pre-functionalization, followed by a two-step wet-treatment in sodium hydroxide and silver nitrate solutions. X-ray photoelectron spectroscopy (XPS) analysis and contact angle measurements were used to investigate the chemical nature and surface wettability of the films following each step of the modification. XPS analysis proved that the RF-O(2) plasma pre-functionalization of native PVC reproducibly increased the amount of functional groups representative of PVC additives, including ether/alcohol, esters and carboxyl groups. More specifically, we demonstrated that the O-C=O groups representative of the phthalic ester and zinc carboxylate additives identified for native PVC increased by two-fold following the RF-O(2) plasma pre-functionalization step. Although RF-O(2) pre-functionalization did not have an effect on the silver content of the NaOH/AgNO(3) treated substrates, such a modification was necessary for biomaterial products that did not have reproducible surfaces amongst production lots. XPS analysis also demonstrated that saponification with sodium hydroxide (NaOH) of esters, like those of the phthalic ester additives of PVC is a simple, irreversible method of hydrolysis, which produced sodium carboxylate and sodium phthalate salts. Exposure of native PVC to NaOH resulted in an increased surface hydrophilicity (from ca 90 degrees to ca 60 degrees ) due to dechlorination. XPS analysis following further incubation in silver nitrate demonstrated that silver ions can be trapped when the sodium of sodium carboxylate is replaced by silver after performing a second treatment with a monovalent silver-containing solution. The creation of silver salt on native PVC resulted in an ultra-hydrophobic (>120 degrees ) surface. The chemical modifications using NaOH and AgNO(3) wet treatments completely inhibited bacterial adhesion of four strains of P. aeruginosa to both native and oxygen-pre-functionalized PVC, and efficiently prevented colonization over longer periods (72 h). Our results suggest that surface modifications that incorporate silver ions would be extremely effective at reducing bacterial colonization to medical devices.

Bacterial Adhesion↗

Synthesis and characterisation of cationically modified phospholipid polymers.

Phospholipid-like copolymers based on 2-(methacryloyloxyethyl) phosphorylcholine were synthesised using monomer-starved free radical polymerisation methods and incorporating cationic charge in the form of the choline methacrylate monomer in amounts varying from 0 to 30 wt%, together with a 5 wt% silyl cross-linking agent in order to render them water-insoluble once thermally cured. Characterisation using a variety of techniques including nuclear magnetic resonance spectroscopy, high-pressure liquid chromatography and gel permeation chromatography showed the cationic monomer did not interfere with the polymerisation and that the desired amount of charge had been incorporated. Gravimetric and differential scanning calorimetry methods were used to evaluate the water contents of polymer membranes cured at 70 degrees C, which was seen to increase with increasing cation content, producing materials with water contents ranging from 50% to 98%. Surface plasmon resonance indicated that the coatings swelled rapidly in water, the rate and extent of swelling increasing with increasing cation level. Dynamic contact angle showed that coatings of all the polymers possessed a hydrophobic surface when dry in air, characteristic of the alkyl chains expressed at the surface (>100 degrees advancing angle). Rearrangement of the hydrophilic groups to the surface occurred once wet, to produce highly wettable surfaces with a decrease in advancing angle with increasing cation content. Atomic force microscopy showed all polymer films to be smooth with no features in topographical or phase imaging. Mechanical properties of the dry films were also unaffected by the increase in cation content.

Biomimetic Materials↗

Influence of the concentrations of hyaluronic acid on the properties and biocompatibility of Cs-Gel-HA membranes.

The object of this study was to investigate the relationship between the concentrations of HA solutions and the physicochemical properties and the biocompatibility of Cs-Gel-HA membranes. The addition of different concentrations of HA not only improved the wettability significantly and extended the degradation time of Cs-Gel-HA membranes, but also changed their mechanical properties. The concentration of HA had a significant influence on the biocompatibility of Cs-Gel-HA membranes. Results demonstrated that it was only the concentrations of HA in a certain range (0.01-0.1%), that could promote the cell adhesion, migration and proliferation, while the concentration of HA was above 0.1% it would either reduce or even inhibit these behaviors.

Absorbable Implants↗

Response of MG63 osteoblast-like cells onto polycarbonate membrane surfaces with different micropore sizes.

Response of different types of cells on materials is important for the applications of tissue engineering and regenerative medicine. It is recognized that the behavior of the cell adhesion, proliferation, and differentiation on materials depends largely on surface characteristics such as wettability, chemistry, charge, rigidity, and roughness. In this study, we examined the behavior of MG63 osteoblast-like cells cultured on a polycarbonate (PC) membrane surfaces with different micropore sizes (0.2-8.0 microm in diameter). Cell adhesion and proliferation to the PC membrane surfaces were determined by cell counting and MTT assay. The effect of surface micropore on the MG63 cells was evaluated by cell morphology, protein content, and alkaline phosphatase (ALP) specific activity. It seems that the cell adhesion and proliferation were progressively inhibited as the PC membranes had micropores with increasing size, probably due to surface discontinuities produced by track-etched pores. Increasing micropore size of the PC membrane results in improved protein synthesis and ALP specific activity in isolated cells. There was a statistically significant difference (P<0.05) between different micropore sizes. The MG63 cells also maintained their phenotype under conditions that support a round cell shape. RT-PCR analysis further confirmed the osteogenic phenotype of the MG63 cells onto the PC membranes with different micropore sizes. In results, as micropore size is getting larger, cell number is reduced and cell differentiation and matrix production is increased. This study demonstrated that the surface topography plays an important role for phenotypic expression of the MG63 osteoblast-like cells.

Bone Substitutes↗

Immobilization of cell adhesive RGD peptide onto the surface of highly porous biodegradable polymer scaffolds fabricated by a gas foaming/salt leaching method.

A cell adhesive peptide moiety, Gly-Arg-Gly-Asp-Tyr (GRGDY), was immobilized onto the surface of highly porous biodegradable polymer scaffolds for enhancing cell adhesion and function. A carboxyl terminal end of poly(D,L-lactic-co-glycolic acid) (PLGA) was functionalized with a primary amine group by conjugating hexaethylene glycol-diamine. The PLGA-NH2 was blended with PLGA in varying ratios to prepare films by solvent casting or to fabricate porous scaffolds by a gas foaming/salt leaching method. Under hydrating conditions, the activated GRGDY could be directly immobilized to the surface exposed amine groups of the PLGA-NH2 blend films or scaffolds. For the PLGA blend films, the surface density of GRGDY, surface wettability change, and cell adhesion behaviors were characterized. The extent of cell adhesion was substantially enhanced by increasing the blend ratio of PLGA-NH2 to PLGA. The level of an alkaline phosphatase activity, measured as a degree of cell differentiation, was also enhanced as a result of the introduction of cell adhesive peptides.

Absorbable Implants↗

Modification of fibrous poly(L-lactic acid) scaffolds with self-assembling triblock molecules.

Molecular self-assembly offers an effective method to modify the surface properties of common biomaterials by presenting biologically relevant chemistry in a controlled, ordered fashion. This work reports on self-assembling triblock molecules containing rigid cholesteryl segments followed by flexible oligomers of L-(lactic acid) and second generation L-lysine dendrons. Second harmonic generation and small angle X-ray scattering indicate these molecules self-assemble into multilayer polar structures when cast from ethyl acetate solutions and segregate into polar polydomains when annealed. These self-assembled layers significantly improve water wettability when coated onto poly(L-lactic acid) fibers. Scaffolds formed from fibers modified by self-assembly enhance adhesion of 3T3 mouse calvaria cells and produce greater population growth rates. These results demonstrate the use of self-assembly to present biologically relevant chemistry on surfaces of biomaterials. Applications of this technology include the modification of substrates for cell culture, tissue engineering, and cell transplantation.

Acetates↗

Surface characteristics of holmium-loaded poly(L-lactic acid) microspheres.

Radioactive holmium-166-loaded poly(L-lactic acid) microspheres (Ho-PLLA-MS) are promising systems for the treatment of liver malignancies. The surface characteristics of Ho-PLLA-MS before and after both neutron and gamma irradiation were investigated in order to get insight into their suspending behaviour and to identify suitable surfactants for clinical application of these systems. X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were used for surface characterization. The residual amounts of poly(vinyl alcohol) (PVA) of the microspheres, which was used as an emulsifier during the solvent evaporation process, were determined using a colorimetric iodine-borate method and the wettability of microspheres and PLLA films with and without holmium (Ho) loading was tested using suspending experiments and contact angle measurements. XPS showed that the surface of Ho-PLLA-MS mainly consisted of PLLA, less than 10% of the surface was covered with PVA after several washing and sieving steps. A colorimetric assay showed that the microspheres contained 0.2-0.3% (w/w) PVA. Combined with XPS data, this assay demonstrates that the PVA is likely dissolved in the core of the microspheres. XPS analysis also showed that after neutron irradiation, some holmium appeared on the surface. Moreover, Ho-loaded PLLA films had a much higher contact angle (85 degrees) than non-loaded films (70 degrees). Therefore, the Ho on the surface of neutron-irradiated Ho-PLLA-MS is probably the reason for their poor suspending behaviour in saline. No surface changes were seen with XPS after gamma irradiation. Based on their surface characteristics, a pharmaceutically acceptable solvent (1% Pluronic F68 or F127 in 10% ethanol) was formulated with which a homogeneous suspension of radioactive Ho-PLLA-MS could be easily obtained, making these systems feasible for further clinical evaluation.

Holmium↗

Surface properties and cell response of low metal ion release Ti-6Al-7Nb alloy after multi-step chemical and thermal treatments.

Ti-6Al-7Nb samples treated by innovative multi-step chemical and thermal processes were characterized in order to evaluate their surface properties and cell interaction. The main object was to asses if the treatments were effective in order to obtain a surface presenting at the same time bone-like apatite induction ability, low metal ion release, good cell response and high protein binding. The morphology, crystallographic structure, porosity and wettability of the treated materials were investigated, as well as their interaction with simulated body fluid during soaking for different times. Cytotoxicity, protein adsorption tests and in vitro fibroblast and osteoblast-like cell cultures were also performed.

Animals↗