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Surface modification of neural recording electrodes with conducting polymer/biomolecule blends.

The interface between micromachined neural microelectrodes and neural tissue plays an important role in chronic in vivo recording. Electrochemical polymerization was used to optimize the surface of the metal electrode sites. Electrically conductive polymers (polypyrrole) combined with biomolecules having cell adhesion functionality were deposited with great precision onto microelectrode sites of neural probes. The biomolecules used were a silk-like polymer having fibronectin fragments (SLPF) and nonapeptide CDPGYIGSR. The existence of protein polymers and peptides in the coatings was confirmed by reflective microfocusing Fourier transform infrared spectroscopy (FTIR). The morphology of the coating was rough and fuzzy, providing a high density of bioactive sites for interaction with neural cells. This high interfacial area also helped to lower the impedance of the electrode site and, consequently, to improve the signal transport. Impedance spectroscopy showed a lowered magnitude and phase of impedance around the biologically relevant frequency of 1 kHz. Cyclic voltammetry demonstrated the intrinsic redox reaction of the doped polypyrrole and the increased charge capacity of the coated electrodes. Rat glial cells and human neuroblastoma cells were seeded and cultured on neural probes with coated and uncoated electrodes. Glial cells appeared to attach better to polypyrrole/SLPF-coated electrodes than to uncoated gold electrodes. Neuroblastoma cells grew preferentially on and around the polypyrrole/CDPGYIGSR-coated electrode sites while the polypyrrole/CH(3)COO(-)-coated sites on the same probe did not show a preferential attraction to the cells. These results indicate that we can adjust the chemical composition, morphology, electronic transport, and bioactivity of polymer coatings on electrode surfaces on a multichannel micromachined neural probe by controlling electrochemical deposition conditions.

Animals↗

Plasma surface modification of poly vinyl chloride for improvement of antibacterial properties.

Plasma immersion ion implantation (PIII) was used to modify medical-grade PVC coated by triclosan and bronopol to enhance the antibacterial properties. The surface was first activated by O2 plasma to produce more hydrophilic groups so that triclosan and bronopol could be coated more effectively on the surface. Subsequently, an argon plasma treatment was conducted under optimal conditions to improve the antibacterial properties of the triclosan and bronopol-coated PVC samples. The modified surfaces were characterized by XPS, ATR-FTIR, SEM, and contact angle measurements. The antibacterial properties were evaluated utilizing the method of plate-counting of Staphylococcus aureus (gram positive) and Escherichia coli (gram negative). Our experimental results show that the plasma-modified PVC with bronopol exhibits good antibacterial properties while the favorable bulk properties of PVC are retained. The plasma-modified PVC with triclosan has better antibacterial performance against E. coli than bronopol. The change in the antibacterial effect on the modified PVC with time was also investigated and the antibacterial effect was observed to decrease with time.

Anti-Infective Agents↗

Surface modification of poly(oligoethylene oxide methacrylate) for resisting protein adsorption.

We prepare poly(2-methoxyethyl-, 2-(2-methoxyethoxy)ethyl-, 2-[2-(2-methoxyethoxy)ethoxy]ethyl methacrylate) (p(nEOMA), n=1, 2, and 3) brushed surfaces with varying the polymer density by surface initiated polymerization. The amount of bovine serum albumin (BSA) adsorbed on the surfaces is investigated. The mobility of the polymer chain in the polymer/water interfaces and the structure of adsorbed water on the surfaces are characterized by Electron Spin Resonance (ESR) and transmission-Fourier transform infrared (FT-IR) spectroscopy, respectively. This work reports the relationship between these surface properties and albumin adsorption. As a result, the surface having both a high molecular mobility and bulk-like water found to be very effective in preventing albumin adsorption.

Adsorption↗

Heterodimers of nanoparticles: formation at a liquid-liquid interface and particle-specific surface modification by functional molecules.

On the basis of a fundamental property of nanoparticles, the self-assembling at a liquid-liquid interface to form "colloidosomes", a heterogeneous reaction takes place on the exposed surface of the nanoparticles to produce the heterodimers of two distinct nanospheres, which can be modified by two different functional molecules in a particle-specific manner.

Dimerization↗

Surface modification based on Si-O and Si-C sublayers and a series of N-substituted acrylamide top-layers for capillary electrophoresis.

Two approaches were used to prepare a series of surface-modified capillaries. In the first, a sublayer was formed by coupling gamma-methacryloxypropyltrimethoxysilane to the surface silanol groups forming an SI-O bond; a top layer was then formed by polymerizing acrylamide in the capillary, which reacted with the sublayer. In the second approach, a sublayer was formed by silanol chlorination, followed by Grignard coupling of vinylmagnesium bromide to form an Si-C bond at the surface; a top layer was formed by polymerizing either acrylamide (AA), dimethylacrylamide (DMA), N-acryloylaminoethoxyethanol (AAEE), or N-acryloylaminopropanol (AAP) onto the sublayer. The Si-Cpoly(AA) capillaries were more stable and produced an approximately 10-fold lower electroosmotic flow compared to the Si-O-poly(AA) capillaries. The Si-C sublayer was used to compare the performance of all four top layers. Electroosmotic flow decreased in the order: Si-O-poly(AA), Si-C-poly(AA), Si-Cpoly(AAEE), Si-C-poly(DMA), and Si-C-poly(AAP). Si-C-poly(AA) showed evidence of irreversible degradation at pH 9 already after 40-50 runs. Si-C-polyAAP-coated capillaries demonstrated superior efficiency and migration time reproducibility for a number of alkaline proteins and for fluorescently labeled ovalbumin. Excellent performance was maintained, in the case of poly(AAP), for a least 300 runs (of 30 min duration) at pH 9.0.

Acrylamide↗

Influence of surface modification on catalytic activity of activated carbon toward decomposition of hydrogen peroxide and 2-chlorophenol.

The objective of this research was to investigate the influence of the activated carbons modified by chemical treatment on the surface catalyzed loss of H2O2 and 2-CP. The characteristics of the modified activated carbons were examined by several techniques including nitrogen adsorption, SEM, and EDS. The H2O2 decomposition rate would be suppressed significantly either by the change of surface properties modified with chemical treatment or the reduction of active sites occupied with the adsorption of 2-CP. In addition, the H2O2 decomposition rate with activated carbons within a specific time can be described by a second-order kinetic expression with respect to the concentration of GAC and H2O2 in the absence or presence of 2-CP. The catalytic activities of the three activated carbons toward 2-CP reduction followed the inverse sequence of those toward H2O2 loss, implying that acidic surface functional group could retard the H2O2 loss and reduce the effect of surface scavenging resulting in increasing the reduction efficiency of 2-CP. By the detection of chloride ions in reaction mixture, it can be demonstrated that the reduction of 2-CP was not only attributed to the advanced adsorption but also the oxidation of the 2-CP with effective radicals. The real oxidation efficiency of 2-CP for the activated carbon modified with hot nitric acid was observed between 0.04 and 0.01 (mol/mol), offering a comparable efficiency to that of the other oxidation system using metal oxide as catalyst.

Adsorption↗

Micrometrically controlled surface modification of Teflon by redox catalysis: electrochemical coupling between Teflon and a gold band ultramicroelectrode

Carbon-fluorine bonds of Teflon (polytetrafluoroethylene, PTFE) can be reduced electrochemically with the purpose of modifying its adhesive and wetting surface properties by micrometrically controlled surface carbonization of the material. This can be performed adequately by redox catalysis provided that the redox mediator couple has a sufficiently negative reduction potential. The process is investigated kinetically with benzonitrile as the mediator and a gold-band ultramicroelectrode mounted adjacent to a PTFE block, though separated from it by an insulating micrometric mylar gap. For moderate fluxes of reduced mediator, the whole device behaves as a generator-collector double-band assembly with a constant current amplification factor. This is maintained over long periods of time, during which the carbonized PTFE zones extends over distances that are much wider than the slowly expanding cylindrical diffusion layer generated at the gold-microband electrode. This establishes that the overall redox catalysis proceeds through electronic conduction in the n-doped carbonized material. Thus, carbonization progresses at the external edge of the freshly carbonized surface in a diffusion-like fashion (dependence on the square root of time), while the redox-mediator oxidized form is regenerated at the carbonized PTFE edge facing to the gold ultramicroelectrode, so that the overall rate of carbonization is controlled by solution diffusion only. For larger fluxes of mediator, the heterogeneous rate of reduction and doping of PTFE becomes limiting, and the situation is more complex. A conceptually simple model is developed which predicts and explains all the main dynamic features of the system under these circumstances and allows the determination of the heterogeneous rate constant of carbon-fluorine bonds at the interface between the carbonized zone and the fresh PTFE. This model can be further refined to account for the effect of ohmic drop inside the carbonized zone on the heterogeneous reduction rate constants and henceforth gives an extremely satisfactory quantitative agreement with the experimental data.

Journal Article↗

Effect of surface modification of rat erythrocytes of different ages on their partitioning behavior in charge-sensitive two-polymer aqueous phases.

Partitioning differences between cells in two-polymer aqueous phase systems originate from subtle differences between the surface properties of cells. Because of the exponential relation between the parameters affecting the partition ratio (P) and the P itself, differences in membrane components suspected of effecting the differential partitioning of closely related cell populations cannot be directly established by conventional chemical assay techniques. In order to study the chemical nature of the components responsible for the age-related changes in surface properties of rat red cells we have devised an approach which uses a combination of isotopic labeling of erythrocyte subpopulations of distinct cell age with different enzyme and/or chemical treatments followed by countercurrent distribution in charge-sensitive two-polymer aqueous phase systems. These studies show that: neuraminidase-susceptible sialic acid is not responsible for the cell age-related surface differences detected by partitioning; the component(s) responsible for the cell age-related surface differences can be extracted (from aldehyde-fixed red cells) with ethanol or cleaved with dilute sulfuric acid. Our data are consistent with the hypothesis that ganglioside-linked sialic acid is the chemical moiety responsible for the cell charge-associated surface differences among rat red blood cells of different ages.

Age Factors↗

Biomimetic surface modifications based on the cyanobacterial iron chelator anachelin.

Siderophores are natural iron chelators that have been evolutionarily selected to bind to Fe ions with very high binding constants. We utilize these unique properties to bind to metal oxide surfaces using a fragment of the cyanobacterial siderophore anachelin. The resulting poly(ethylene glycol) conjugate forms stable adlayers on TiO2 as has been shown by variable angle spectroscopic ellipsometry and X-ray photoelectron spectroscopy. Moreover, these coated surfaces are highly protein-resistant against the adsorption of full human serum.

Biomimetic Materials↗

Surface modification of H-ferrierite by reaction with triethoxysilane.

The interaction of triethoxysilane (TES) with H-ferrierite (H-FER) and its effects on acidity have been investigated by infrared spectroscopy. TES adsorbs only on the external surface of H-FER and allows the almost complete disappearance of the external silanol groups. New SiH groups are formed which appear to be inactive in acid-base interactions. The adsorption of propionitrile, which diffuses into the zeolitic channels, provides evidence for the lack of substantial perturbation of the strongly acidic internal bridging OH groups. On the contrary, the adsorption of the hindered basic probe molecule o-toluonitrile, which cannot penetrate the FER channels, shows that not only terminal silanols but also Al3+ Lewis acid sites present on the external surface of H-FER almost totally disappear after TES treatment. Treatment with TES seems to allow virtually the total deactivation of the H-FER external surface.

Journal Article↗

New methods for surface modification and covalent attachment of heparin.

Research is continually under way to improve biocompatibility performance in biomaterials. This article discusses a technique for the covalent attachment of heparin and other drugs onto a variety of polymer and metal surfaces. It offers the potential to improve haemocompatibility and lubricity in a number of medical device applications as well as new drug-delivery systems.

Adsorption↗

Microanalytical characterization and surface modification of TiNi orthodontic archwires.

Orthodontic archwires (equiatomic TiNi alloy) of both used (4 weeks) and unused conditions were microanalyzed by optical and scanning electron microscopes, energy dispersive X-ray spectroscopy, and electron diffraction to characterize the surface layers. They were also subjected to immersion and polarization corrosion tests in a 0.9% NaCl aqueous solution. Based on results obtained from these analytical and experimental studies, surfaces of TiNi archwires were further electrochemically treated to etch away nickel selectively and reform the surface morphology to uniform and porous surface layers. Main conclusions were: (a) surface layers of used archwires were covered contaminants causing the discoloration, and the contaminants were identified as mainly KCl crystals, (b) surfaces of both used and unused wires were observed to be irregular features characterized by lengthy island-like structures, where nickel was selectively dissolved, (c) corrosion tests in a 0.9% NaCl aqueous solution in immersion and polarization methods indicated that by increasing temperature from 3 degrees to 60 degrees C and acidity from pH 11 to pH 3, calculated corrosion rates increased, and (d) surface layers of TiNi archwires can be electrochemically modified to selectively etch nickel away, leaving a Ti-enriched surface layer and forming a uniformly distributed porous surface that may reduce the coefficient of friction against the orthodontic brackets.

Corrosion↗

Surface modification of EPDM rubber by plasma treatment.

The effect of argon, oxygen, and nitrogen plasma treatment of solvent cast EPDM rubber films has been investigated by means of atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and surface energy measurements. Plasma treatment leads to changes in the surface energy from 25 to 70 mN/m. Treatment conditions influenced both the changes in surface energy and the stability, and it became more difficult to obtain good contact angle measurements after longer (> ca. 4 min) treatment times, probably because of an increasingly uneven surface structure. XPS analyses revealed that up to 20 at. % oxygen can be easily incorporated and that variations of approximately 5% can be controlled by the plasma conditions. Oxygen was mainly found in hydroxyl groups, but also as carbonyl and carboxyl. XPS analyses showed more stable surfaces than expected from contact angles, probably because XPS analysis is less surface sensitive than contact angle measurements. AFM measurements revealed different surface structures with the three gases. The surface roughness increased generally with treatment time, and dramatic changes could be observed at longer times. At short times, surface energy changes were much faster than the changes in surface structure, showing that plasma treatment conditions can be utilized to tailor both surface energies and surface structure of EPDM rubber.

Journal Article↗

Tuning solid surfaces from hydrophobic to superhydrophilic by submonolayer surface modification.

Molecular-scale understanding and manipulation of the wetting behavior of water on solids remains a fundamental challenge. Using diamond as a model system, we show that the naturally hydrophobic behavior of a hydrogen-terminated C(111) surface can be manipulated by replacing the H termination with a monolayer of adsorbate. In particular, a mixed monolayer of 1/3 Na and 2/3 F atoms leads to superhydrophilic behavior, as shown by first-principles calculations. The physical origin of the superhydrophilic behavior is attributed to the ionic nature of the Na adatoms, which mediate the right degree of binding strength between water molecules and the substrate.

Journal Article↗

Electrochemical nitric oxide sensor preparation: a comparison of two electrochemical methods of electrode surface modification.

Platinum electrodes modified with Mn(II) 5-(N-(8-pyrrole-yl-3,6-dioxa-1-aminooctane)phenylamide-10,15,20-trimethoxyphenylporphyrin (Mn(II)triOMeTCPPyP) using multi-sweep cyclic voltammetry and differential pulse amperometry were evaluated as electrocatalytic surfaces for the oxidation of nitric oxide. The electrodes modified using the pulse amperometric approach were more sensitive towards the detection of nitric oxide. The increased sensitivity led to the attainment of a wider linear dynamic range for the quantification of nitric oxide.

Electrodes↗

How does surface modification aid in the dispersion of carbon nanofibers?

Small-angle light scattering is used to assess the dispersion behavior of vapor-grown carbon nanofibers suspended in water. These data provide the first insights into the mechanism by which surface treatment promotes dispersion. Both acid-treated and untreated nanofibers exhibit hierarchical morphology consisting of small-scale aggregates (small bundles) that agglomerate to form fractal clusters that eventually precipitate. Although the morphology of the aggregates and agglomerates is nearly independent of surface treatment, their time evolution is quite different. The time evolution of the small-scale bundles is studied by extracting the size distribution from the angle-dependence of the scattered intensity, using the maximum entropy method in conjunction with a simplified tube form factor. The bundles consist of multiple tubes possibly aggregated side-by-side. Acid oxidation has little effect on this bundle morphology. Rather acid treatment inhibits agglomeration of the bundles. The time evolution of agglomeration is followed by fitting the scattering data to a generalized fractal model. Agglomerates appear immediately after cessation of sonication for untreated fibers but only after hours for treated fibers. Eventually, however, both systems precipitate.

Journal Article↗