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Surface modification of silica nanoparticles by UV-induced graft polymerization of methyl methacrylate.

In this study we modified the surface of silica nanoparticles with methyl methacrylate by UV-induced graft polymerization. It is a surface-initiated polymerization reaction induced by ultraviolet irradiation. The resulting organic-inorganic nanocomposites were near-monodisperse and fabricated without homopolymerization of the monomer. Substantial increase in mean particle size was observed by SEM image analysis after UV-induced grafting of methyl methacrylate onto pure silica particles. FT-Raman spectroscopy and X-ray photoelectron spectroscopy studies of these materials revealed the successful grafting of methyl methacrylate onto the silica surface. The formation of a covalent bond between the grafted PMMA chains and silica surface was indicated by FT-Raman spectra. Thermogravimetric analysis of the PMMA-grafted silica particles indicated the polymer contents in good agreement with SEM photographs.

Nanoparticles↗

Enhancement of bone apposition to stainless steel cortical screws by surface modification using heat treatment: an experimental study.

OBJECTIVE: The purpose of the present study was to test whether the surface of stainless steel cortical screws modified by an oxidation process (heat treatment) resulted in enhancement of bone apposition as a consequence of better bone apposition to the metal surface. DESIGN: Control and heat-treated commercial cortical screws (stainless steel 316L) were inserted alternately into the tibiae of eight goats with a fixed insertion torque. Fluorochrome bone label was given during the six-week experimental period, after which the goats were killed and the extraction torque force measured. The screws and the adjacent bone were processed for histology. MAIN OUTCOME MEASURE: It was hypothesized that the heat-treated transcortical metal screws would have a greater extraction torque than untreated control screws. RESULTS: The extraction torque of the heat-treated screws was 0.59 +/- 0.06 newton-meters, which was significantly (p < 0.0001) higher (1.7-fold) than that of the control screws (0.35 +/- 0.02 newton-meters). Histomorphometric measurements demonstrated a 65 percent, significant (p < 0.05), increase in the area of fluorescence (indication of new bone deposition) adjacent to the heat-treated implant versus the control screws. CONCLUSIONS: Heat treatment of the cortical screws prior to insertion significantly increases fixation strength to the host bone in a large animal model. The clinical applicability will be to achieve bone apposition similar to that seen with titanium implants but with a stiff low-cost material.

Animals↗

Surface modification for DNA and protein microarrays.

Microarrays of biomolecules are emerging as powerful tools for genomics, proteomics, and clinical assays, since they make it possible to screen biologically important binding events in a parallel and high throughput fashion. Because the microarrays are fabricated on a solid support, coating of the surface and immobilization strategy of the biomolecules are major issues for successful microarray fabrication. This review deals with both DNA microarrays and protein microarrays, and focuses on the various modification approaches for the two-dimensional surface materials and three-dimensional ones. In addition, the immobilization strategies including adsorption, covalent attachment, physical entrapment, and affinity attachment of the biomolecules are summarized, and advantage and limitation of representative efforts are discussed.

Manufactured Materials↗

Study on mono-dispersed nano-size silica by surface modification for underfill applications.

In order to improve the rheological behavior of the nanosilica composite no-flow underfill, filler surface treatment using silane coupling agents was investigated to reduce the filler-filler interaction and to achieve the mono-dispersity of the nanosilica in the underfill resin. The experimental conditions of the surface treatment were investigated in a design of experiment (DOE) in terms of the pre-treatment methods, coupling agent types, concentrations, and treatment durations. The particle dispersion after treatment was evaluated by the laser particle analyzer and the transmission electron microscopy (TEM). A mono-dispersed nanosilica solution in the polar medium was achieved using optimal experimental condition. The surface chemistry of the nanosilica was studied using Fourier transformed infrared spectroscopy (FTIR). The wettability of underfill resin and water on the silane treated glass slides was studied using a goniometer. Based on the investigations, the silane-treated nanosilica fillers were incorporated into an underfill resin to formulate a nanocomposite no-flow underfill. It was found that the proper filler treatment could significantly reduce the viscosity of the nanocomposite.

Hydrolysis↗

Surface and chemical properties of surface-modified UHMWPE powder and mechanical and thermal properties of it impregnated PMMA bone cement, III: effect of various ratios of initiator/inhibitor on the surface modification of UHMWPE powder.

From our previous study, 3 wt% of ultra-high-molecular-weight polyethylene (UHMWPE) powder surface-modified by various ratios of methyl methacrylate (MMA) and poly(methyl methacrylate) (PMMA) solution was impregnated to improve the poor mechanical and thermal properties of conventional PMMA bone cement. In this study, various amounts of benzoyl peroxide (BPO) and hydroquinone were used for the adhesion reinforcement of UHMWPE powder with PMMA polymerized from MMA monomer (polyMMA) by the mixture of BPO and hydroquinone and ultimately to strengthen the poor mechanical and thermal properties of conventional PMMA bone cement. The tensile strengths of 3 wt% of UHMWPE powders surface-precoated with polyMMA prepared by various amounts of BPO- and hydroquinone-impregnated composite PMMA bone cements were similar to that of conventional PMMA bone cement. In particular, 3 wt% of UHMWPE powder surface precoated with polyMMA prepared with 0.75 wt% of BPO and 300 ppm of hydroquinone impregnated composite PMMA bone cement revealed the maximum tensile strength. However, no obvious significant difference was revealed, although the curing temperatures of the composite PMMA bone cements decreased from 103 degrees C to 91-97 degrees C. From these results, it was determined that the mixture of BPO and hydroquinone plays an important role in improving the poor mechanical properties of conventional PMMA bone cement. However, the thermal properties of the composite PMMA bone cements were not remarkably improved. The mechanical, chemical and thermal properties were individually confirmed using a scanning electron microscope (SEM), universal transverse mercator (UTM), Fourier transform infrared-attenuated total reflectance (FT-IR-ATR) and digital thermometer, respectively.

Bone Cements↗

Controlling modulus and morphology of hydrogel tubes through surface modification.

Crosslinked, porous poly(2-hydroxyethyl methacrylate-co-methyl methacrylate) (PHEMA-MMA) tubes were prepared in cylindrical glass molds using a new centrifugal casting process developed in our group. The resulting hydrogel tubes have a bi-phasic wall structure, with a spongy inner layer and a gel-like outer layer, the latter of which provides mechanical strength to the tube. While many factors influence wall morphology and, thus, mechanical properties, we focused on the effect of the surface properties of the glass mold in which tubes are synthesized. Specifically, we investigated the impact of a diverse set of silane modifications of the glass mold on tube morphology, elastic modulus and mold release. We treated activated glass surfaces with one of three alkoxysilanes having either ethoxy, amine or fluorocarbon end-groups. Silane-modified glass surfaces were found to be more hydrophobic than the unmodified glass mold, with the most hydrophobic surface being that of the fluorocarbon-terminated silane. The presence of the silane layer on the mold was confirmed by X-ray photoelectron spectroscopy and the stability of this modification was confirmed by examining the surface chemistry of the hydrogel tubes. The biphasic hydrogel tube wall structure was observed for all tubes, yet those tubes synthesized in unmodified molds had a cracked outer morphology, whereas those synthesized in silane-modified molds had a smooth outer morphology. This influenced the mechanical properties of the tubes where tubes synthesized in silane-modified molds had a significantly greater elastic modulus than those tubes synthesized in unmodified molds. Release from the molds was easiest with ethoxy- and amine-functionalized silane mold modifications.

Biocompatible Materials↗

The effect of glow discharge plasma surface modification of polymers on the osteogenic differentiation of committed human mesenchymal stem cells.

Little is known of the effect of material surfaces on stem cell differentiation. The present study has addressed the hypothesis that the interaction of mesenchymal stem cells (MSCs) with material surfaces modified by glow discharge plasma is a major regulator of osteogenic differentiation. We found that biaxially oriented polypropylene (BOPP) plasma treated in ammonia significantly reduced up-regulation of expression of osteogenic marker genes, such as alkaline phosphatase (ALP), bone sialoprotein (BSP) and osteocalcin (OC). In contrast, ALP expression was up-regulated when cultured on treated Nylon-6 polyamide (Ny-t) but was substantially reduced when cultured on its pristine counterpart (Ny-p) on day 3. On day 7, ALP expression was down-regulated with MSCs cultured on Ny-t although its expression level was up again on day 14. BSP was expressed weakly on day 3, but was up-regulated when cultured on Ny-t and Ny-p. Its expression reached its maximum on day 14 when cultured on a polystyrene control, while it was cyclically up-regulated on Ny-t. Similarly, there was a slight increase in OC expression when MSCs were cultured on Ny-t and Ny-p on day 3, when compared to control. Thus, the nature of the surface can directly influence MSCs differentiation, ultimately affecting the quality of new tissue formation with BOPP-t suppressing osteogenic differentiation.

Aged↗

Surface modification of magnetite nanoparticles using lactobionic acid and their interaction with hepatocytes.

In the current study, superparamagnetic magnetite nanoparticles were surface-modified with lactobionic acid (LA) to improve their intracellular uptake and ability to target hepatocytes. Maltotrionic acid (MA)-modified nanoparticles were also synthesized as a control. Cell culture experiment showed that LA-modified nanoparticles were internalized into hepatocytes and atomic absorption spectrometer (AAS) measurement indicated that the uptake amount of LA-modified magnetite into hepatocytes was higher than that of unmodified and MA-modified nanoparticles. LA-modified nanoparticle solution was injected in rabbit and the magnetic resonance (MR) images obtained showed that LA-coated nanoparticles were selectively accumulated onto the hepatocytes. This result demonstrates that the LA-modified magnetite nanoparticles have a great potential to be used as contrast agent for liver diagnosis.

Animals↗

Surface modification of A12O3 bioceramic by NH2+ ion implantation.

Ion implantation technique was applied to graft the -NH2 amidogen radicals onto the surface of Al2O3 bioceramic. Fourier transform infrared spectroscopy (FTIR) was used to confirm the presence of the implanted radicals on the Al2O3 ceramic surface. It was found that the amount of grafted amidogen radicals was proportional to the dosage of NH2+ ions used during the ion implantation. Furthermore, when implantation energy of 100 keV was used, maximum amount of -NH2 radicals would be grafted on the Al2O3 ceramic surface. The biocompatibility of the implanted Al2O3 ceramic was also investigated, and the results indicate that the implanted surface has better biocompatibility with animal bone tissue than the plain ceramic surface.

Aluminum Oxide↗

Surface modification of poly(tetrafluoroethylene) films via grafting of poly(ethylene glycol) for reduction in protein adsorption.

Poly(tetrafluoroethylene) (PTFE) films with surface grafted poly(ethylene glycol) (PEG) chains were prepared by two methods: (1) UV-induced graft copolymerization of methoxy poly- (ethylene glycol) monomethacrylate (PEGMA) onto the plasma-pretreated PTFE films; and (2) coupling of the hydroxyl groups of PEG via ester linkages with the carbonyl chloride groups which were introduced onto the acrylic acid (AAc) graft-copolymerized PTFE surface through reaction with thionyl chloride (SOCl2). The UV-induced graft copolymerization of PEGMA onto the plasma-pretreated PTFE film was explored with different macromonomer concentrations and different UV graft copolymerization time. The coupling reaction, on the other hand, was explored with PEG of different molecular weights. The surface microstructures and compositions of the PEG-modified PTFE films from both processes were characterized by contact angle, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM) measurements. In general, higher macromonomer concentration and longer UV graft copolymerization time led to a higher graft yield for the UV-induced graft copolymerization with PEGMA. Contact angle measurements revealed that the hydrophilicity of the PTFE film surface was greatly enhanced by the grafting of the PEG chains. The PTFE surface with a high density of grafted PEG was very effective in preventing bovine serum albumin adsorption.

Adsorption↗

Surface modification of titanium carbide with carbyne-containing nanocoatings.

The aim of this research is to investigate a novel approach to surface engineering of biomaterials that are based on transition metals of the groups IVA-VIA. The approach taken relies on the fact that, during the electropolishing of TiC surfaces, the removal of Ti atoms from the TiC surface surpasses that of C atoms. This leads to enrichment of the TiC surface with carbon. Transmission electron microscopic investigation showed that carbon-based films contain carbynes in the form of nanorod-like clusters with lengths in the range of 5-100 nm. This carbyne-containing layer is 50-100 nm thick. It was generalized that carbyne-containing nanofilms are formed on the carbide surface of transition metals of groups IVA-VIA during electropolishing. Since carbynes, being one-dimensional chain-like structures [(-C identical to C-)n/(=C=C=)n] with sp1 carbon-carbon hybridization, have the highest degree of biocompatibility because of their biological activity, the development of such surface bioengineering with carbynes extends applications of biomaterials based on transition metals of the groups IVA-VIA.

Carbamates↗

Surface modifications created by using engineered hydrophobins.

Hydrophobins are small (ca. 100 amino acids) secreted fungal proteins that are characterized by the presence of eight conserved cysteine residues and by a typical hydropathy pattern. Class I hydrophobins self-assemble at hydrophilic-hydrophobic interfaces into highly insoluble amphipathic membranes, thereby changing the nature of surfaces. Hydrophobic surfaces become hydrophilic, while hydrophilic surfaces become hydrophobic. To see whether surface properties of assembled hydrophobins can be changed, 25 N-terminal residues of the mature SC3 hydrophobin were deleted (TrSC3). In addition, the cell-binding domain of fibronectin (RGD) was fused to the N terminus of mature SC3 (RGD-SC3) and TrSC3 (RGD-TrSC3). Self-assembly and surface activity were not affected by these modifications. However, physiochemical properties at the hydrophilic side of the assembled hydrophobin did change. This was demonstrated by a change in wettability and by enhanced growth of fibroblasts on Teflon-coated with RGD-SC3, TrSC3, or RGD-TrSC3 compared to bare Teflon or Teflon coated with SC3. Thus, engineered hydrophobins can be used to functionalize surfaces.

Amino Acid Sequence↗

Peptide surface modification of poly(tetrafluoroethylene-co-hexafluoropropylene) enhances its interaction with central nervous system neurons.

Poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP) film surfaces were chemically surface modified to introduce one of three laminin adhesive peptides: GYIGSR, GRGDS, or SIKVAV. FEP film surfaces were first reduced with sodium naphthalide to introduce surface carbon-carbon double bonds at two reaction conditions: 20 min at -78 degrees C, and 3 h at 25 degrees C. Scanning electron microscopy and atomic force microscopy indicated that surface topography was unaffected by the reaction conditions. Reduced FEP film surfaces were further modified to introduce hydroxyl groups via hydroboration/oxidation or carboxylic acid groups via oxidation. The hydroxyl (FEP-CHxOH) and carboxylic acid (FEP-COOH) functionalized surfaces provided reactive handles for peptide coupling using tresyl chloride. Surface elemental composition data, determined from X-ray protoelectron spectroscopy, indicated that equivalent amounts of GYIGSR, GRGDS, and SIKVAV were introduced. Two additional coupling reagents, SMCC and TSU, were compared to tresyl chloride for the coupling of radio-labeled tyrosine of GYIGSR. Between 8 and 150 fmol/cm2 of peptide was introduced to the hydroxyl and carboxylic acid functionalized surfaces, with the tresyl coupling reagent showing the greatest amount of peptide incorporated. The tresyl-coupled peptide-modified surfaces were compared in terms of the response of primary, embryonic hippocampal neurons plated from serum-free medium for 4 days. The number and length of neurites extending from the cell bodies were averaged over 50 cells after 1 and 4 days FEP-CHxO-peptide surfaces had either a greater or equivalent hippocampal neuron interaction than the corresponding FEP-COO-peptide surfaces. All peptide-functionalized surfaces had a greater hippocampal neuron interaction than the corresponding FEP-CHxOH, FEP-COOH, and FEP controls after 4 days underlying the importance of the peptides over hydrophilic or hydrophobic surfaces. After 4 days differences in neurite extension were evident among the peptide-functionalized surfaces, with the longest neurites observed on the SIKVAV-functionalized surfaces.

Animals↗

Surface modification of poly(ethylene-co-vinyl alcohol) (EVA). Part I. Introduction of carboxyl groups and immobilization of collagen.

To enhance the surface biocompatibility of poly(ethylene-co-vinyl alcohol) (EVA) and high-density polyethylene (HDPE), carboxyl groups were introduced by ozone exposure. Type I collagen was immobilized onto the surface through polyion complexing. The carboxyl groups on the EVA were characterized by electron spectroscopy for chemical analysis and neutralization. The amounts of the carboxylic group and collagen increased with increases in time and temperature of exposure. Water-soluble fragments were produced by ozone exposure to EVA, and they acted as collagen crosslinkers. The differences in charge distribution of carboxyl groups affected the amount of collagen immobilization. Graft polymerization of acrylic acid was also carried out onto EVA and HDPE surfaces. The amount of collagen immobilized by graft polymerization was much higher than that by ozone exposure despite the introduction of almost the same amounts of carboxylic groups. It was suggested that the negative charge distribution influences the amount of collagen immobilized onto films.

Biocompatible Materials↗

From colloidal Co/CoO core/shell nanoparticles to arrays of metallic nanomagnets: surface modification and magnetic properties.

The magnetic properties of nanoparticles can be subject to strong variations as the chemical composition of the particle surface is modified. To study this interrelation of surface chemistry and magnetism, self-assembled layers of colloidal 9.5 nm Co/CoO core/shell nanoparticles were exposed to mild reactive hydrogen and oxygen plasmas. The consecutive oxygen/hydrogen plasma treatment transforms the particle layer into an array of metallic nanomagnets with complete reduction of the oxide and removal of the organic surfactants. The original arrangement of the particle array and the number of Co atoms per particle remains unchanged within the experimental error, and thus this is a possible route for the fabrication of ultrahigh-density magnetic bit structures from colloidal dispersions. The magnetic properties can be tuned by controlling the thickness of the surface oxide layer, which magnetically hardens the particles, as evidenced by element-specific magnetic hysteresis loops.

Journal Article↗

Surface modification of poly(L-lactic acid) to improve its cytocompatibility via assembly of polyelectrolytes and gelatin.

Poly(L-lactide) (PLLA) surface was modified via aminolysis by poly(allylamine hydrochloride) (PAH) at high pH and subsequent electrostatic self-assembly of poly(sodium styrenesulfonate) (PSS) and PAH, and the process was monitored by X-ray photoelectron spectroscopy (XPS) and contact angle measurement. These modified PLLAs were then used as charged substrates for further incorporation of gelatin to improve their cytocompatibility. The amphoteric nature of the gelatin was exploited and the gelatin was adsorbed to the negatively charged PLLA/PSS and positively charged PLLA/PAH at pH=3.4 and 7.4, respectively. XPS and water contact angle data indicated that the gelatin adsorption at pH=3.4 resulted in much higher surface coverage by gelatin than at pH=7.4. All the modified PLLA surfaces became more hydrophilic than the virgin PLLA. Chondrocyte culture was used to test the cell attachment, cell morphology and cell viability on the modified PLLA substrates. The results showed that the PAH and PSS modified PLLA exhibited better cytocompatibility than virgin PLLA, and the incorporation of the gelatin on these modified PLLA substrates further improved their cytocompatibility, with the PLLA/PSS substrate treated with the gelatin at pH=3.4 being the best, exceeding the chondrocyte compatibility of the tissue culture polystyrene.

Adsorption↗

Organic plasma process for simple and substrate-independent surface modification of polymeric BioMEMS devices.

A polymeric bio micro electromechanical systems (BioMEMS) device was fabricated using organic plasma polymerization, by which the surface of a polymeric substrate could easily be modified through vapor-phase deposition of organic thin films. This technique, capable of polymeric deposition of any kind of monomer, can serve the purpose of anti-fouling coating, wettability control, or layer-to-layer interface creation, on the surface of any given chemically-inert polymeric substrate without involving cumbersome surface organic reactions. A prototype device was fabricated to have an array of electrochemical glucose biosensors with the three electrode configuration, each of which has a microfluidic channel (500 microm x 800 microm) for capillary-action-driven sample delivery and the concerned enzymatic reaction. Stressing the advantages of the plasma polymerization process using a polymeric substrate together with some additional features accomplished in our device fabrication, new possibilities in the field of polymeric BioMEMS are discussed.

Biosensing Techniques↗