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Control of the electrical conductivity of composites of antimony doped tin oxide (ATO) nanoparticles and acrylate by grafting of 3-methacryloxypropyltrimethoxysilane (MPS).

The effect of the addition of antimony doped tin oxide (ATO) nanoparticles on the electrical conductivity of acrylate films is described. To enable dispersing of ATO in acrylate matrices, 3-methacryloxypropyltrimethoxysilane (MPS) was grafted on the surface of the filler. The amount of MPS used for this surface modification was found to strongly affect the electrical conductivity. Surface modification with a large amount of MPS resulted in colloidally stable dispersions of ATO, leading to a homogeneous distribution. Surface modification with small amounts of MPS led to instable ATO dispersions and aggregation of ATO into a fractal type network, which gives a much higher conductivity especially at low-volume fractions. For composites with a fractal type ATO network a second effect was found. Decreasing the amount of on ATO grafted MPS resulted in an increase of the electrical conduction between the ATO particles.

Journal Article↗

Surface chemical modification of waxy maize starch nanocrystals.

The surface of waxy maize starch nanocrystals obtained from sulfuric acid hydrolysis of native waxy maize starch granules was chemically modified using two different reagents, namely, alkenyl succinic anhydride and phenyl isocyanate. The occurrence of chemical modification was evaluated by FTIR and X-ray photoelectron spectroscopies. Contact angle measurements from which the surface energy of the materials under investigation was deduced showed that chemical modification led to more hydrophobic particles. Chemical modification altered the morphology of particles, as shown by observation by transmission electron microscopy, but not their crystallinity (X-ray diffraction analysis).

Journal Article↗

Tissue reactions to bacteria-inoculated rat lead samples. II. Effect of local gentamicin release through surface-modified polyurethane tubing.

A surface modification technique was developed to achieve controlled release of gentamicin from implanted polyurethane (PU) rat lead samples. PU tubing first was provided with an acrylic acid/acrylamide copolymer surface graft and then loaded with gentamicin. This surface modification technique resulted in release of gentamicin base (GB) and was applied either to the inner luminal surface only (PU-GB-1x) or to both the inner and outer surfaces (PU-GB-2x). First we investigated whether the early tissue response was harmfully compromised when surface-modified rat lead samples were implanted without any infectious challenge. Additionally, the efficacy of this type of local gentamicin therapy was investigated by establishing its effect on tissue response and its ability to prevent lead-related infections after inoculation with Staphylococcus aureus. It was demonstrated that the applied surface modification(s) did not induce adverse effects although an increase in the infiltration of granulocytes and macrophages and an increase in the formation of wound fluid and fibrin were observed. This effect was stronger with PU-GB-2x than with PU-GB-1x. With bacterial inoculation the applied surface modification successfully suppressed the infectious challenge, PU-GB-2x more effectively than PU-GB-1x. PU-GB-2x also was more effective when compared to the gentamicin-delivery methods discussed in the first part of this two-part study, i.e., release through a vicinal gentamicin-containing collagen sponge and preoperative gentamicin solution-dipping of rat lead samples.

Animals↗

Soft lithographic printing of patterns of stretched DNA and DNA/electronic polymer wires by surface-energy modification and transfer.

Aligned and stretched lambda DNA is directed to specific locations on solid substrates. Surface-energy modification of glass substrates by using patterned polydimethylsiloxane (PDMS) stamps is used to direct DNA onto the surface-energy-modified micrometer-scale pattern through molecular combing. As an alternative, patterned and nonpatterned PDMS stamps modified with polymethylmethacrylate (PMMA) are utilized to direct the stretched DNA to the desired location and the results are compared. The DNA is elongated through molecular combing on the stamp and transfer printed onto the surfaces. PMMA-modified stamps show a more defined length of the stretched DNA, as compared to bare PDMS stamps. A combination of these two methods is also demonstrated. As an application example, transfer printing of DNA decorated with a semiconducting conjugated polyelectrolyte is shown. The resulting patterned localization of stretched DNA can be utilized for functional nanodevice structures, as well as for biological applications.

DNA↗

Development of surface photochemical modification method for micropatterning of cultured cells.

This article reports the development of micropatterning technology of cultured cells by precise surface regional modification via photochemical fixation of phenyl azido-derivatized polymers on polymer surfaces. Photoreactive polymers prepared in this study included poly(N,N-dimethylacrylamide-co-3-azidostyrene), bis-4-azidobenzamide-polyethylene glycol, and poly(styrene-co-3-azidostyrene). The photochemical fixation of these photoreactive polymers consisted of three steps: 1) coating of a photoreactive polymer on a material surface, 2) ultraviolet irradiation through a photomask, and 3) removal of nonreacted polymer by a solvent. Electron spectroscopy for chemical analysis and water contact angle measurement were employed for surface characterization. Two different types of regionally modified surfaces were prepared; one was a hydrophilic polymer regionally fixed on a tissue culture dish and the other was a hydrophobic polymer regionally fixed on poly(vinyl alcohol) (PVA). Photochemical surface microfabrication permits mu-order dimensional precision, which was verified by the micropatterned tissue formation of bovine aorta endothelial cells (ECs) when ECs were seeded on these surfaces. ECs adhered, spread, and confluently proliferated only on uncoated tissue culture dish surfaces or hydrophobic regions on PVA. Thus, the regionally differentiated cell adhesional regions were created by photochemically driven surface microprocessing.

Animals↗

Use of simple and complex in vitro models for multiparameter characterization of human blood-material/device interactions.

Medical devices, intended for blood contacting applications, undergo extensive in vitro testing followed by animal and clinical feasibility studies. Besides the use of materials known to be intrinsically blood-compatible, the surface of such devices is often modified with a coating in order to improve the performance characteristics during blood exposure. In vitro evaluation of blood-device interactions accompanies the product development cycle from the early design phase using basic material geometries until final finished-product testing. Specific test strategies can vary significantly depending on the end application, the particular study objectives and variables of interest, and cost. To examine the degree to which findings derived from two different in vitro approaches complement one another, this report contrasts findings from a simple multipass loop model with findings from a simulated cardiopulmonary bypass (CPB) model. The loop model consists of tubular test materials, with and without surface modification, formed into valved Chandler loops. The CPB model has an oxygenator with and without surface modification connected to a reservoir and a blood pump. The surface modifications studied in this report are the Carmeda BioActive Surface and Duraflo II heparin coatings. Common blood parameters in the categories of coagulation, platelets, hematology, and immunology were monitored in each model. Ideal models employ the optimal level of complexity to study the design variables of interest and to meet practical cost considerations. In the case of medical device design studies, such models should also be predictive of performance. In the more complex and realistic simulated CPB model, experimental design and cost factors prevented easy/optimum manipulation of critical variables such as blood donor (use of paired samples) and heparin level. Testing in the simpler loop model, on the other hand, readily offered manipulation of these variables, and produced findings which overlapped with observations from the more complex CPB model. Thus, the models described here complimented one another. Moreover, conclusions from consistent findings, such as favorable responses associated with the heparin coatings, between the two models were considered to be more robust.

Biocompatible Materials↗

[Surface grafting modification and stabilization of Kevlar fiber].

Chemical disposal was used to bring the activity group onto the surface of Kevlar fiber for the purpose of surface grafting modification. The interfacial constitution of the grafting of toluene-2,4-diisocyanate (TDI) onto Kevlar fiber was determined by Fourier transform infrared spectroscopy. In the mean time, hexyl-lactam stabilization and poly-glycol (400, PEG) stabilization on the grafted product were also studied. The effects of different nTDI:nPEG ratios on the production's interfacial constitution was analysed. It is concluded that the stabilization took place on the surface. The intensity of the bands relented at about 3300 cm(-1) and was reinforced at about 1700-1720 cm(-1) when the ratio of nTDI:nPEG = 1:3, but when the ratio is 1:1 and 1:2, the bands at about 3 300 and 1700-1720 cm(-1) are almost the same.

English Abstract↗

Photoluminescence properties of CdS and CdMnS quantum dots prepared by a reverse-micelle method.

We have investigated photoluminescence properties of CdS and CdMnS quantum dots (QDs) prepared by a reverse-micelle method. Before the surface modification, a broad luminescence band that originates from defects is dominant in CdS QDs. By the modification, the intensity of the band-edge luminescence is remarkably increased. The surface modification also causes drastic changes of decay profiles of the band-edge luminescence. The intensity of Mn2+ luminescence originating from the intra-3d shell transition of Mn2+ is also increased by the surface modification of CdMnS QDs. The decay time of the band-edge luminescence in surface-modified CdMnS QDs is faster than that in CdS QDs, which is due to the energy transfer from excitons to Mn2+.

Journal Article↗

Biomaterials and biomechanics of oral and maxillofacial implants: current status and future developments.

Research in biomaterials and biomechanics has fueled a large part of the significant revolution associated with osseointegrated implants. Additional key areas that may become even more important--such as guided tissue regeneration, growth factors, and tissue engineering--could not be included in this review because of space limitations. All of this work will no doubt continue unabated; indeed, it is probably even accelerating as more clinical applications are found for implant technology and related therapies. An excellent overall summary of oral biology and dental implants recently appeared in a dedicated issue of Advances in Dental Research. Many advances have been made in the understanding of events at the interface between bone and implants and in developing methods for controlling these events. However, several important questions still remain. What is the relationship between tissue structure, matrix composition, and biomechanical properties of the interface? Do surface modifications alter the interfacial tissue structure and composition and the rate at which it forms? If surface modifications change the initial interface structure and composition, are these changes retained? Do surface modifications enhance biomechanical properties of the interface? As current understanding of the bone-implant interface progresses, so will development of proactive implants that can help promote desired outcomes. However, in the midst of the excitement born out of this activity, it is necessary to remember that the needs of the patient must remain paramount. It is also worth noting another as-yet unsatisfied need. With all of the new developments, continuing education of clinicians in the expert use of all of these research advances is needed. For example, in the area of biomechanical treatment planning, there are still no well-accepted biomaterials/biomechanics "building codes" that can be passed on to clinicians. Also, there are no readily available treatment-planning tools that clinicians can use to explore "what-if" scenarios and other design calculations of the sort done in modern engineering. No doubt such approaches could be developed based on materials already in the literature, but unfortunately much of what is done now by clinicians remains empirical. A worthwhile task for the future is to find ways to more effectively deliver products of research into the hands of clinicians.

Biocompatible Materials↗

Platelet-mediated adhesion of Staphylococcus epidermidis to hydrophobic NHLBI reference polyethylene.

The effects of platelets and plasma proteins on the adhesion of Staphylococcus epidermidis strain RP62A to hydrophobic NHLBI reference polyethylene was quantitatively studied using a rotating disk system to generate well-defined shear conditions simulating the hemodynamics of human blood circulation. Bacterial adhesion was quantified by adhesive coefficient, the percentage of bacteria transported to the surface that becomes adherent. The results showed that surface modification by adsorption of plasma proteins reduced the adhesion of S epidermidis as compared to the bare polymer surface. This surface modification was not sufficient to eliminate completely bacterial adhesion, even at the highest physiologic shear stress level. S epidermidis did adhere strongly to polyethylene surface modified by platelets. This is readily evident as approximately 50% of the adherent S epidermidis were bound to contact-activated platelets which occupied only 4% of the surface area. Adhesive coefficients to platelets were significantly greater than to the protein-adsorbed polyethylene surface by at least one order of magnitude (P < or = .01) across the range of physiological shear conditions investigated. These studies show that it is biologic surface modification by contact-activated platelets, and not plasma proteins, which mediates S epidermidis adhesion to polyethylene.

Bacterial Adhesion↗

Diamond-like carbon coating and plasma or glow discharge treatment of mechanical heart valves.

All mechanical heart valves (MHV) are thrombogenic. Application of surface modification technology to reduce the incidence of thrombus formation on MHV is a novel undertaking. This requires collaboration within the bioengineering and cardiothoracic surgery fields. From reviewing results of recent and past investigations, and our own preliminary study with diamond-like carbon coating (DLC) and plasma or glow discharge treatment (GDT) of MHV, we identify and discuss several potentially beneficial effects that may reduce the extent of valve-related thrombogenesis by surface modification. DLC and GDT may affect the surfaces of MHV in many ways, including cleaning of organic and inorganic debris, generating reactive and functional groups on the surface layers without affecting their bulk properties, and making the surfaces more adherent to endothelial cells and albumin and less adherent to platelets. These different effects of surface modification, separately or in combination, may transform the surfaces of MHV to be more thromboresistant in the vascular system.

Animals↗

Synthetic biodegradable microparticles for articular cartilage tissue engineering.

Articular cartilage tissue engineering procedures require the transplantation of chondrocytes that have been expanded in vitro. The expansion is carried out for a considerable time and can lead to a modulation of cell phenotype. However, microcarrier cultures have been shown to allow cell expansion while maintaining the phenotype. Here, we have used the biodegradable polyester poly(lactide-co-glycolide) (PLGA) in the form of microspheres and irregular shaped microparticles with a diameter between 47 and 210 microm. Surface modification of particles was carried out by ammonia plasma treatment and subsequent adsorption of collagen. Alternatively, particles were modified by partial hydrolysis and subsequent immobilization of an amine-terminated dendrimer. Each surface modification step was characterized by X-ray photoelectron spectroscopy. The effectiveness of the surface modification procedures was demonstrated by in vitro cell culture experiments using sheep articular cartilage chondrocytes. A significant influence of both the particle shape and the surface chemistry on the proliferation rate was observed while the phenotype was maintained independent of the surface chemistry or particle shape. Chondrocytes cultured on PLGA microspheres were further assessed for cartilage tissue formation in collagen type I gels in nude mice. The tissue that were formed showed the appearance of a hyaline-like cartilage and the presence of the microspheres substantially reduced the degree of collagen gel contraction over 1-2 months.

Animals↗

Immobilization of glucoamylase on ceramic membrane surfaces modified with a new method of treatment utilizing SPCP-CVD.

Glucoamylase, as a model enzyme, was immobilized on a ceramic membrane modified by surface corona discharge induced plasma chemical process-chemical vapor deposition (SPCP-CVD). Characterizations of the immobilized enzyme were then discussed. Three kinds of ceramic membranes with different amounts of amino groups on the surface were prepared utilizing the SPCP-CVD method. Each with 1-time, 3-times and 5-times surface modification treatments and used for supports in glucoamylase immobilization. The amount of immobilized glucoamylase increased with the increase in the number of surface modification treatments and saturated to a certain maximum value estimated by a two-dimensional random packing. The operational stability of the immobilized glucoamylase also increased with the increase in the number of the surface treatment. It was almost the same as the conventional method, while the activity of immobilized enzyme was higher. The results indicated the possibility of designing the performance of the immobilized enzyme by controlling the amount of amino groups. The above results showed that the completely new surface modification method using SPCP was effective in modifying ceramic membranes for enzyme immobilization.

Journal Article↗

Implant surfaces and interface processes.

The past decades and current R&D of biomaterials and medical implants show some general trends. One major trend is an increased degree of functionalization of the material surface, better to meet the demands of the biological host system. While the biomaterials of the past and those in current use are essentially bulk materials (metals, ceramics, polymers) or special compounds (bioglasses), possibly with some additional coating (e.g., hydroxyapatite), the current R&D on surface modifications points toward much more complex and multifunctional surfaces for the future. Such surface modifications can be divided into three classes, one aiming toward an optimized three-dimensional physical microarchitecture of the surface (pore size distributions, "roughness", etc.), the second one focusing on the (bio) chemical properties of surface coatings and impregnations (ion release, multi-layer coatings, coatings with biomolecules, controlled drug release, etc.), and the third one dealing with the viscoelastic properties (or more generally the micromechanical properties) of material surfaces. These properties are expected to affect the interfacial processes cooperatively, i.e., there are likely synergistic effects between and among them: The surface is "recognized" by the biological system through the combined chemical and topographic pattern of the surface, and the viscoelastic properties. In this presentation, the development indicated above is discussed briefly, and current R&D in this area is illustrated with a number of examples from our own research. The latter include micro- and nanofabrication of surface patterns and topographies by the use of laser machining, photolithographic techniques, and electron beam and colloidal lithographies to produce controlled structures on implant surfaces in the size range 10 nm to 100 microns. Examples of biochemical modifications include mono- or lipid membranes and protein coatings on different surfaces. A new method to evaluate, e.g., biomaterial-protein and biomaterial-cell interactions--the Quartz Crystal Microbalance--is described briefly.

Biocompatible Materials↗

Fabrication and characterization of polysulfone-dicalcium silicate composite films.

Polysulfone (PSU) composite films filled with Beta-dicalcium silicate (Beta-Ca(2)SiO(4)) particles are prepared by the solvent casting-evaporation method. The surface morphologies and mechanical properties of the films are determined. The bioactivity of the composite films is evaluated by soaking them in simulated body fluid (SBF) and the results show that the composites are bioactive as they induce the formation of hydroxyapatite (HAp) on the surface of the composite films. The measurement of the water contact angles suggests that the incorporation of Beta-Ca(2)SiO(4) particles into PSU matrix can improve the hydrophilicity of the composite. PSU composite films filled with modified Beta-dicalcium silicate (Beta-mCa(2)SiO(4)) particles are also prepared after Beta-Ca(2)SiO(4) particles are treated with dodecyl alcohol through surface esterification reactions. The infrared spectra of the Beta-mCa(2)SiO(4) particles before and after aging in water indicate that the surface modification is reversible. The scanning electron microscope (SEM) images (micrographs) of both composites show that the dispersion of inorganic particles in the polymer matrix improves after surface modification. The PSU-Beta-mCa(2)SiO(4) composite is still bioactive and exhibits the same water contact angle after aging in water as compared to that of the PSU-Beta-Ca(2)SiO(4) composite. All these results suggest that the incorporation of Beta-Ca(2)SiO(4) particles is a useful method to prepare composites with improved bioactivity and hydrophilicity, and the surface modification of Beta-Ca(2)SiO(4) particles can improve the dispersion while retaining the bioactivity and hydrophilicity.

Biocompatible Materials↗

Bone tissue responses to surface-modified zirconia implants: A histomorphometric and removal torque study in the rabbit.

BACKGROUND: Zirconia ceramics are biocompatible and have mechanical properties that make them suitable as materials for dental implants. Little is known about how surface modification influences the stability and bone tissue response to zirconia implants. PURPOSE: The objective of the investigation was to histologically and biomechanically evaluate the bone tissue response to zirconia implants with two different surface modifications in comparison with machined, nonmodified zirconia implants and oxidized titanium implants. MATERIALS AND METHODS: Threaded zirconia implants with a diameter of 3.75 mm with either a machined surface (Zr-Ctr) or one of two surface modifications (Zr-A and Zr-B) were manufactured. Oxidized titanium (Ti-Ox) implants 3.75 mm in diameter were also used. The implants were characterized with regard to surface topography using an interferometer. Twelve rabbits received 96 implants using a rotational scheme, two in each tibia and two in each femur. The implants in six rabbits were subjected to removal torque (RTQ) tests after a healing period of 6 weeks. The implants in the remaining six animals were removed en bloc for light microscopic analysis. Back-scatter scanning electron microscopic (BS-SEM) analyses were used to evaluate the state of the bone-implant interface at the modified zirconia implants after RTQ testing. RESULTS: The Ti-Ox and Zr-A implants showed the highest surface roughness, followed by the Zr-B implants and, finally, the Zr-Ctr implants. The nonmodified ZrO2 implants showed statistically significant lower RTQs than all other implants. No significant differences in bone-implant contact or bone area filling the threads were observed. BS-SEM showed intact surface layers of the surface-modified implants after RTQ testing and revealed fracture of the interface bone rather than a separation. CONCLUSION: The present study showed a strong bone tissue response to surface-modified zirconia implants after 6 weeks of healing in rabbit bone. The modified zirconia implants showed a resistance to torque forces similar to that of oxidized implants and a four- to fivefold increase compared with machined zirconia implants. The findings suggest that surface-modified zirconia implants can reach firm stability in bone.

Animals↗

Cell-surface antigenic modifications with trinitrophenyl sulfonate versus trifluoromethyl-dinitrophenyl sulfonate.

The aim of the work was to justify the use of trifluoromethyl-dinitrobenzene sulfonate (CF3-DNBS) modification rather than trinitrobenzene-sulfonate (TNBS) modification, so as to be able to take advantage of the presence of fluorine atoms in the analogue, which allow the analysis of the hapten-carrier bonds by 19F-NMR nuclear magnetic resonance. Cell-surface antigenic modifications brought about by exposure to TNBS or CF3-DNBS were found to be immunologically cross-reactive, both in cell-mediated lymphocytotoxicity and in indirect immunofluorescence. The extent of haptenic derivatizations was found to be of the same order of magnitude, as appraised both by quantitative-absorption studies or by using radioactive hapten, provided that the less chemically reactive CF3-DNBS was used at the concentration of 10 mM and TNBS at the concentration of 1 mM. However, only TNBS-modified cells were sensitive to destruction by antibody-plus-complement-mediated cytotoxicity.

Animals↗

Spatially controlled electro-stimulated DNA adsorption and desorption for biochip applications.

The manipulation of biomolecules at solid/liquid interfaces is important for the enhanced performance of a number of biomedical devices, including biochips. This study focuses on the spatial control of surface interactions of DNA as well as the electro-stimulated adsorption and desorption of DNA by appropriate surface modification of highly doped p-type silicon. Surface modification by plasma polymerisation of allylamine resulted in a surface that supported DNA adsorption and sustained cell attachment. Subsequent high-density grafting of poly(ethylene oxide) formed a low fouling layer resistant to biomolecule adsorption and cell attachment. Spatially controlled excimer laser ablation of the surface produced patterns of re-exposed plasma polymer with high-resolution. On patterned surfaces, preferential electro-stimulated adsorption of DNA to the allylamine plasma polymer surface and subsequent desorption by the application of a negative bias was observed. Furthermore, the concept presented here was investigated for use in transfection chips. Cell culture experiments with human embryonic kidney cells, using the expression of green fluorescent protein as a reporter, demonstrated efficient and controlled transfection of cells. Electro-stimulated desorption of DNA was shown to yield significantly enhanced solid phase transfection efficiencies to values of up to 30%. The ability to spatially control DNA adsorption combined with the ability to control the binding and release of DNA by application of a controlled voltage enables an advanced level of control over DNA bioactivity on solid substrates and lends itself to biochip applications.

Adsorption↗