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PubMed2004

Cr(VI) removal from synthetic wastewater using coconut shell charcoal and commercial activated carbon modified with oxidizing agents and/or chitosan.

In this study, the technical feasibility of coconut shell charcoal (CSC) and commercial activated carbon (CAC) for Cr(VI) removal is investigated in batch studies using synthetic electroplating wastewater. Both granular adsorbents are made up of coconut shell (Cocos nucifera L.), an agricultural waste from local coconut industries. Surface modifications of CSC and CAC with chitosan and/or oxidizing agents, such as sulfuric acid and nitric acid, respectively, are also conducted to improve removal performance. The results of their Cr removal performances are statistically compared. It is evident that adsorbents chemically modified with an oxidizing agent demonstrate better Cr(VI) removal capabilities than as-received adsorbents in terms of adsorption rate. Both CSC and CAC, which have been oxidized with nitric acid, have higher Cr adsorption capacities (CSC: 10.88, CAC: 15.47 mg g(-1)) than those oxidized with sulfuric acid (CSC: 4.05, CAC: 8.94 mg g(-1)) and non-treated CSC coated with chitosan (CSCCC: 3.65 mg g(-1)), respectively, suggesting that surface modification of a carbon adsorbent with a strong oxidizing agent generates more adsorption sites on their solid surface for metal adsorption.

Adsorption↗

PubMed2003

Porous polymer scaffolds surface-modified with arginine-glycine-aspartic acid enhance bone cell attachment and differentiation in vitro.

This study was designed to determine if the surface modification of porous poly(lactic acid) (PLA) scaffolds would enhance osteogenic precursor cell (OPC) attachment, growth, and differentiation. A covalently grafted amino group (-NH(2)), poly(L-lysine) (PLL), and the peptide arginine-glycine-aspartic acid (RGD) were selected for the evaluation. The hypothesis was that surface modification would have a positive impact on cell-substratum interactions. The experiment was performed by OPC cells being placed on PLA films and scaffolds modified with NH(2), PLL, or RGD in tissue culture media. OPC attachment to PLA films was assessed after 24 h of incubation. The growth and differentiation of the adherent OPCs on porous PLA scaffolds were assessed after 14 and 28 days for alkaline phosphatase (APase) activity and calcium levels, both of which increase as OPCs differentiate into mature bone cells. All assays were accomplished in triplicate, and data were tested with post hoc orthogonal contrasts (i.e., Fisher's least significant difference) at p < or = 0.05. The PLA film surface-modified with RGD showed better OPC cell attachment than the other films. The cells on the PLA scaffolds surface-modified with RGD also exhibited an increase in APase activity and calcium levels in comparison with those on other scaffolds. This difference was apparent at both time intervals and was especially evident in the tissue culture media containing an osteogenic supplement. The results of this study indicate that modifying the surface of PLA polymer scaffolds with RGD enhances bone cell attachment and differentiation and may improve their ability to regenerate bone tissue more efficiently in wound models.

Absorbable Implants↗

PubMed2006

Surface modified amorphous ribbon based magnetoimpedance biosensor.

Magnetoimpedance (MI) changes due to surface modification of the sensitive element caused by human urine, were studied with the aim of creating a robust biosensor working on a principle of electrochemical magnetoimpedance spectroscopy. A biosensor prototype with an as-quenched amorphous ribbon sensitive element was designed and calibrated for a frequency range of 0.5-10 MHz at a current intensity of 60 mA. Measurements as a function of the exposure time were made both in a regime where chemical surface modification and MI measurements were separated as well as in a regime where they were done simultaneously. The MI variation was explained by the change of the surface magnetic anisotropy. It was shown that the magnetoimpedance effect can be successfully employed as a new option to probe the electric features of the Fe(5)Co(70)Si(15)B(10) amorphous ribbon magnetic electrode surface modified by human urine.

Biosensing Techniques↗

PubMedDate not supplied

Modification of surface histidine residues abolishes the cytotoxic activity of Clostridium difficile toxin A.

Clostridium difficile toxin A displays both cytotoxic and enterotoxic activities. It has recently been demonstrated that toxin A exerts its cytotoxic effect by the glucosylation of the small GTP-binding proteins of the Rho family. Diethyl pyrocarbonate, at pH 7.0, was used to chemically modify exposed histidine residues on toxin A. Modification of toxin A with diethyl pyrocarbonate abolished both its cytotoxic activity and the ability of the toxin to bind Zn-Sepharose gel. Treatment of toxin A with [(14)C]-diethyl pyrocarbonate revealed concentration dependent labelling of histidine residues on the toxin molecules. The effects of diethyl pyrocarbonate could be reversed by hydroxylamine treatment. These data suggest the modified histidine residues on toxin A are critical to its cytotoxic activity. Histidine modification had no effect on the glucosyl transferase enzyme activity of toxin A. However, modification abolished the 'cold' binding of toxin to bovine thyroglobulin in an ELISA and reduced ligand binding activity in a rabbit erythrocyte haemagglutination assay. The data suggest that the histidine residues may be crucial to the receptor-binding activity of toxin A. Exposed histidines on toxin A are available for zinc chelation, and these have been exploited in the development of a novel purification protocol for toxin A using zinc-chelating chromatography.

Animals↗

PubMed2000

Three-dimensional appearance of bovine epidermal keratinocytes in different stages of differentiation revealed by cell maceration and scanning electron microscopic investigation.

The epidermis of the modified skin of the bovine hoof is a highly mechanical loaded tissue. Consequently, all cell connections have to withstand high mechanical forces. As an adaptation to this stress, the epidermal keratinocytes show characteristic surface modifications. Furthermore, the tissue displays a complex three-dimensional architecture which is difficult to appreciate from histological sections. SEM-observation of macerated tissue samples is a fast, easy to use and reliable tool to receive three-dimensional information about the appearance and spatial relationship of cells within a tissue. Using cell maceration, the aim of this study was to separate individual as well as smaller groups of keratinocytes in order to reveal the formations of the cell surface, the appearance of individual cells and the spatial relationship of cells within the tissue. A NaOH maceration method described in literature was modified and applied to tissue samples from the wall and bulbar segment of the hooves of six cows. The method facilitated separation between the epidermal cells. Single cells as well as cell groups were available for SEM observation which revealed a three dimensional appearance characteristic for different stages of differentiation of the keratinocytes. The observed findings suggest that throughout the process of differentiation the surface modifications provide the basis for a stable cell to cell adhesion which is established by desmosomes and the intercellular cementing substance. Additionally, the broadened cellular surface area is related to the supply of the highly metabolic active living epidermal cells with nutrients and oxygen. Longer cell processes typically found in the central surface area of the keratinocytes may carry gap junctions and may be involved in cell communication. This, however, has to be clarified by further electron microscopic studies. The demonstrated appearance of individual cells and the complex architecture enable the hoof epidermis to fulfill its unique biomechanical functions.

Animals↗

PubMed2004

Robust polymer microfluidic device fabrication via contact liquid photolithographic polymerization (CLiPP).

Microfluidic devices are commonly fabricated in silicon or glass using micromachining technology or elastomers using soft lithography methods; however, invariable bulk material properties, limited surface modification methods and difficulty in fabricating high aspect ratio devices prevent these materials from being utilized in numerous applications and/or lead to high fabrication costs. Contact Liquid Photolithographic Polymerization (CLiPP) was developed as an alternative microfabrication approach that uniquely exploits living radical photopolymerization chemistry to facilitate surface modification of device components, fabrication of high aspect ratio structures from many different materials with numerous covalently-adhered layers and facile construction of three-dimensional devices. This contribution describes CLiPP and demonstrates unique advantages of this new technology for microfabrication of polymeric microdevices. Specifically, the procedure for fabricating devices with CLiPP is presented, the living radical photopolymerization chemistry which enables this technology is described, and examples of devices made using CLiPP are shown.

Equipment Design↗

PubMed2005

Gentamicin supplementation of polyvinylidenfluoride mesh materials for infection prophylaxis.

Hernia repair evolved from pure tissue repair to mesh repair due to decreased recurrence rates. However, concern exists about mesh-related infections occurring even several years after initial operation. Therefore, a polyvinylidenfluoride (PVDF) mesh material was constructed and surface modified by plasma-induced graft polymerization of acrylic acid (PVDF+PAAc). Antimicrobial treatment was sought by binding of gentamicin (PVDF+PAAc+Gentamicin). In vitro efficacy and cytotoxicity was measured by agar diffusion test, L929 cytotoxicity testing and by analyzing the amount of gentamicin release from the mesh surface. In vivo biocompatibility was evaluated in 45 Sprague-Dawley rats. 7, 21 and 90 days after mesh implantation the amount of inflammatory and connective tissue as well as the percentage of proliferating (Ki67) and apoptotic cells (TUNEL) were analyzed at the perifilamentary region. Agar diffusion tests showed sufficient local antimicrobiotic effects against the bacteria tested after 24h of incubation. No signs of cytotoxicity could be identified by L929 testing. Furthermore, surface modification did not affect the in vivo biocompatibility. At the end of the observation period, no significant differences were found for the perifilamentary amount of inflammatory cells and connective tissue and the percentage of Ki67 and TUNEL positive stained cells. The presented data confirm that an antibiotic surface modification of PVDF mesh samples is feasible. By analyzing cytotoxicity in vitro as well as biocompatibility in vivo no side effects were observed.

Animals↗

PubMed2001

Sorption of nonpolar aromatic contaminants by chlorosilane surface modified natural minerals.

The efficacy of the surface modification of natural diatomite and zeolite material by chlorosilanes is demonstrated. Chlorosilanes used were trimethylchlorosilane (TMSCI), tert-butyldimethylchlorosilane (TBDMSCI), dimethyloctadecylchlorosilane (DMODSCI), and diphenyldichlorosilane (DPDSCI) possessing different headgroups and chemical properties. Silanol groups of the diatomite and zeolite were modified by chemical reaction with the chlorosilanes resulting in a stable covalent attachment of the organosilanes to the mineral surface. The alteration of surface properties of the modified material was proved by measurements of water adsorption capacity, total organic carbon (TOC) content, and thermoanalytical data. The surface modified material showed great stability even when exposed to extremes in ionic strength, pH, and to pure organic solvents. Sorption of toluene, o-xylene, and naphthalene from water was greatly enhanced by the surface modification compared to the untreated materials which showed no measurable sorption of these compounds. The enhanced sorption was dependent on the organic carbon content as well as on chemical characteristics of the chlorosilanes used. Batch sorption experiments showed that the phenyl headgroups of DPDSCI have the best affinity for aromatic compounds. Removal from an aqueous solution of 10 mg/L of naphthalene, o-xylene, and toluene was 71%, 60%, and 30% for surface modified diatomite and 51%, 30%, and 16% for modified clinoptilolite, respectively. Sorption data were well described by the Freundlich isotherm equation, which indicated physical adsorption onto the lipophilic surface rather than partitioning into the surface organic phase. The chlorosilane modified materials have an apparent potential for application in environmental technologies such as permeable reactive barriers (PRB) or wastewater treatment.

Adsorption↗

PubMed2004

Plasma protein adsorption and thrombus formation on surface functionalized polypyrrole with and without electrical stimulation.

A surface modification technique was developed in which heparin was covalently immobilized onto electrically conductive polypyrrole (PPY) film through poly(ethylene glycol) methacrylate (PEGMA) graft copolymerization and subsequent cyanuric chloride activation. In vitro plasma protein adsorption and thrombus formation experiments were carried out on the various films. The PEGMA-graft-copolymerized PPY surfaces with immobilized heparin have good bioactivity indicated by low level of protein adsorption, high ratio of albumin to fibrinogen adsorption, and low thrombus formation, making them potentially good candidates for biomedical applications. Since the PPY film retained significant electrical conductivity after surface modification, the effect of electrical stimulation on protein adsorption and thrombus formation was also evaluated. The covalently immobilized heparin on the PPY film was able to retain its bioactivity after 4 days of immersion in PBS. The film after long-term immersion in PBS also retained sufficient electrical conductivity for electrical stimulation still to be effective for reducing protein adsorption.

Journal Article↗

PubMed2004

Biodegradable poly(ether ester urethane)urea elastomers based on poly(ether ester) triblock copolymers and putrescine: synthesis, characterization and cytocompatibility.

Polymers with elastomeric mechanical properties, tunable biodegradation properties and cytocompatibility would be desirable for numerous biomedical applications. Toward this end a series of biodegradable poly(ether ester urethane)urea elastomers (PEEUUs) based on poly(ether ester) triblock copolymers were synthesized and characterized. Poly(ether ester) triblock copolymers were synthesized by ring-opening polymerization of epsilon-caprolactone with polyethylene glycol (PEG). PEEUUs were synthesized from these triblock copolymers and butyl diisocyanate, with putrescine as a chain extender. PEEUUs exhibited low glass transition temperatures and possessed tensile strengths ranging from 8 to 20MPa and breaking strains from 325% to 560%. Increasing PEG length or decreasing poly(caprolactone) length in the triblock segment increased PEEUU water absorption and biodegradation rate. Human umbilical vein endothelial cells cultured in a medium supplemented with PEEUU biodegradation solution suggested a lack of degradation product cytotoxicity. Endothelial cell adhesion to PEEUUs was less than 60% of tissue culture polystyrene and was inversely related to PEEUU hydrophilicity. Surface modification of PEEUUs with ammonia gas radio-frequency glow discharge and subsequent immobilization of the cell adhesion peptide Arg-Gly-Asp-Ser increased endothelial adhesion to a level equivalent to tissue culture polystyrene. These biodegradable PEEUUs thus possessed properties that would be amenable to applications where high strength and flexibility would be desirable and exhibited the potential for tuning with appropriate triblock segment selection and surface modification.

Absorbable Implants↗

PubMed2003

Physicochemical and blood compatibility characterization of polypyrrole surface functionalized with heparin.

A surface modification technique was developed for the covalent immobilization of heparin onto electrically conductive polypyrrole (PPY) film. The PPY film was first graft copolymerized with poly(ethylene glycol) methacrylate (PEGMA) and then activated with cyanuric chloride (CC). Heparin was then immobilized onto the film through the reaction between the chloride groups of CC and the amine and/or hydroxyl groups of heparin. X-ray photoelectron spectroscopy (XPS) was used to characterize the surface-modified film after each stage. The biocompatibility of the surface-modified PPY was evaluated using plasma recalcification time (PRT) and platelet adhesion. After surface modification, the film had improved wettability while retaining significant electrical conductivity. With immobilized heparin, platelet adhesion and platelet activation on PPY film was significantly suppressed, and the PRT was significantly prolonged. Electrical stimulation also plays a positive role in decreasing platelet adhesion and increasing PRT on pristine and surface-modified PPY films.

Adsorption↗

PubMed2006

Direct grafting of RGD-motif-containing peptide on the surface of polycaprolactone films.

Direct surface modification of biodegradable polycaprolactone (PCL) was performed without the necessity of synthesis of functionisable co-polymers. An easy-to-perform three-step procedure consisting of amination, reaction with hetero-bifunctional cross-linkers and conjugation of an RGD-motif-containing peptide was used to modify polymer films and improve the attachment of endothelial cells. The biological activity of modified surfaces was assessed by estimating microvascular endothelial cell attachment. Covalent coating with RGD resulted in an approximately 11-fold increase of endothelial cell attachment on modified PCL surfaces compared with untreated polymer. The specificity of the attachment enhancement was confirmed by using a control peptide. It is concluded that chemical surface modification is an appropriate method of rendering degradable polymers, such as PCL, cell-adhesive.

Animals↗

PubMed2001

Pullout strengths of self-reinforced poly-L-lactide (SR-PLLA) rods versus Kirschner wires in bovine femur.

OBJECTIVE: To determine the relative amount of fixation of self-reinforced poly-L-lactide (SR-PLLA) rods and Kirschner wires in bovine cancellous bone by comparing their pullout strength DESIGN: An in vitro laboratory study was performed using bovine femurs. Ten two-millimeter-diameter pins of each type were inserted into cancellous bone and then pulled out, using a material testing machine. The maximum force (pullout strength) was selected over other measurements to compare the amount of fixation of the two types of pins. All of the pins were retrieved for microscopic analysis. A paired t test was performed to analyze the differences between the pullout strength of the two types of pins. SETTING: Orthopaedic Bioengineering Laboratory, University of Louisville School of Medicine, Louisville, Kentucky, U.S.A. SPECIMENS: Two young fresh bovine distal femurs, ten two-millimeter-diameter Kirschner wires, ten two-millimeter-diameter bioabsorbable SR-PLLA rods MAIN OUTCOME MEASUREMENTS: Pullout strength in Newtons, and microscopic pin surface aspect after insertion. RESULTS: Significant differences were noted between the maximum force required to remove the two types of pins (p < 0.01) The K-wire mean pullout force was 37.7 N (SD 13.6), and the SR-PLLA rod mean pullout force was 53.6 N (SD 19.3). Microscopic analysis indicated surface modification only on the SR PLLA rods. DISCUSSION: SR-PLLA composites have shown comparable clinical results to their metallic counterparts. In this study, the pullout strength of SR-PLLA rods was compared with that of conventional K-wires. A significant difference (p < 0.01) favoring bioabsorbable pullout strength was noted. The bioabsorbable pin surface modification during insertion is an interesting finding that warrants further investigation as a potential source of improved fixation. CONCLUSION: SR-PLLA rods retain their hold in bovine cancellous bone better than K-wires. This finding offers to the orthopaedic surgeon more information about new pin fixation methods.

Animals↗

PubMed1995

Synthesis of phospholipid polymers having a urethane bond in the side chain as coating material on segmented polyurethane and their platelet adhesion-resistant properties.

Surface modification of segmented polyurethanes (SPUs) was carried out using new blood compatible polymers having both phospholipid polar groups and urethane bonds in the side chains. The polymers were composed of 2-methacryloyloxyethyl phosphorylcholine (MPC), n-butyl methacrylate (BMA) and methacrylate with a urethane bond (MU). The MPC copolymers were soluble in ethanol. The SPU membranes were immersed in an ethanol solution of MPC copolymers and dried in vacuo for coating. The surface formed was completely covered with the MPC copolymer which was confirmed by X-ray photoelectron spectroscopic analysis. The polymer coatings were hardly detached in water, ethanol and 40% aqueous solution of ethanol compared with poly(MPC-co-BMA) which did not have the MU moieties. Therefore, the MU moieties had affinity for the SPU. The surface modification of the SPUs suppressed platelet adhesion effectively after contact with platelet-rich plasma for 180 min.

Biocompatible Materials↗

PubMed2006

Silica-based monolithic columns with mixed-mode reversed-phase/weak anion-exchange selectivity principle for high-performance liquid chromatography.

This article describes the synthesis, chromatographic characterization, and performance evaluation of analytical (100 x 4.6 mm id) and semipreparative (100 x 10 mm id) monolithic silica columns with mixed-mode RP/weak anion-exchange (RP/WAX) surface modification. The monolithic RP/WAX columns were obtained by immobilization of N-(10-undecenoyl)-3-aminoquinuclidine onto thiol-modified monolithic silica columns (Chromolith) by a radical addition reaction. Their chromatographic characterization by Engelhardt and Tanaka tests revealed slightly lower hydrophobic selectivities than C-8 phases, as well as higher polarity and also improved shape selectivity than RP-18e silica rods. The surface modification enabled separation by both RP and anion-exchange chromatography principles, and thus showed complementary selectivities to the RP-18e monoliths. The mixed-mode monoliths have been tested for the separation of peptides and turned out to be particularly useful for hydrophilic acidic peptides, which are usually insufficiently retained on RP-18e monolithic columns. Compared to a corresponding particulate RP/WAX column (5 microm, 10 nm pore diameter), the analytical RP/WAX monolith caused lower system pressure drops and showed, as expected, higher efficiency (e.g. by a factor of about 2.5 lower C-term for a tetrapeptide). The upscaling from the analytical to semipreparative column dimension was also successful.

Anions↗

PubMed2001

Immobilization of poly(ethylene glycol) or its sulfonate onto polymer surfaces by ozone oxidation.

A novel surface modification method has been developed to improve biocompatibility of polymeric biomaterials. This approach involves ozonation and then followed by graft polymerization with acrylates containing PEG, sulfonated PEG or by coupling of PEG derivatives. All the reactions were confirmed by ATR FT-IR and ESCA. The degree of ozonation measured by the iodide method was dependent on the ozone permeability of the polymers used. Surface hydrophilicity was investigated by measuring the contact angles. Ozonation itself yielded a slight increase in hydrophilicity and a decrease in platelet adhesion, but PEG immobilization showed a significant effect on surface hydrophilicity and platelet adhesion to confirm well-known PEG's passivity which minimize the adhesion of blood components on polymer surfaces. Both graft polymerization and coupling were effective for PU. In contrast, only grafting gave enough yields for PMMA and silicone. Platelet adhesion results demonstrated that all PEG modified surfaces adsorbed lower platelet adhesion than untreated or ozonated ones. Polymers coupled with sulfonated PEG exhibited the lowest platelet adhesion when compared with control and PEG coupled ones by virtue of the synergistic effect of non-adhesive PEG and negatively charged SO3 groups. This PEG or sulfonated PEG immobilization technology using ozonation is relatively simple for introducing uniform surface modification and therefore very useful for practical application of blood contacting medical devices.

Biocompatible Materials↗

PubMed2004

Characterization and protein-adsorption behavior of deposited organic thin film onto titanium by plasma polymerization with hexamethyldisiloxane.

Plasma polymerized hexamethyldisiloxane (HMDSO) thin film was deposited onto titanium using a radio-frequency apparatus for the surface modification of titanium. A titanium disk was first polished using colloidal silica at pH=9.8. Plasma-polymerized HMDSO films were firmly attached to the titanium by heating the titanium to a temperature of approximately 250 degrees C. The thickness of the deposited film was 0.07-0.35mum after 10-60min of plasma polymerization. The contact angle with respect to double distilled water significantly increased after HMDSO coating. X-ray photoelectron spectroscopy revealed that the deposited thin film consisted of Si, C, and O atoms. No Ti peaks were observed on the deposited surface. The deposited HMDSO film was stable during 2-weeks immersion in phosphate buffer saline solution. Fourier transform reflection-absorption spectroscopy showed the formation of Si-H, Si-C, C-H, and Cz.dbnd6;O bonds in addition to Si-O-Si bonds. Quartz crystal microbalance-dissipation measurement demonstrated that the deposition of HMDSO thin films on titanium has a benefit for fibronectin adsorption at the early stage. In conclusion, plasma polymerization is a promising technique for the surface modification of titanium. HMDSO-coated titanium has potential application as a dental implant material.

Adsorption↗

PubMed2006

Corrosion evaluation of Ti-48Al-2Cr-2Nb (at.%) in Ringer's solution.

The corrosion behavior of Ti-48Al-2Cr-2Nb (at.%) in Ringer's solution was studied to evaluate its potential as a biocompatible material. Corrosion properties of Ti-6Al-4V were determined under the same conditions for comparison. Two electrochemical techniques, potentiodynamic anodic polarization and electrochemical impedance spectroscopy, were employed to test Ti-48Al-2Cr-2Nb and Ti-6Al-4V. Surface modifications to the samples were made by autoclaving and by oxidation in air at 500 degrees C and 800 degrees C. The results show excellent corrosion resistance for unmodified Ti-48Al-2Cr-2Nb, corroborated by the high values of polarization resistance and corrosion potential and low values of corrosion current and corrosion rate. Ti-48Al-2Cr-2Nb appears to possess corrosion characteristics similar to Ti-6Al-4V. Surface modification rendered the Ti-48Al-2Cr-2Nb material extremely corrosion resistant.

Alloys↗