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PubMed2005

Surface modification of monodisperse magnetite nanoparticles for improved intracellular uptake to breast cancer cells.

Nanoparticles have been widely used for a variety of biomedical applications and there is a growing need for highly specific and efficient uptake of the nanoparticles into target cells. Poly(ethylene glycol) (PEG), folic acid (FA), and their conjugate PEG-FA were attached to magnetite nanoparticles to compare their effects on the improvement of intracellular uptake of the nanoparticles to human breast cancer cells, BT-20. AFM and TEM results indicated that the nanoparticles after surface modification were monodisperse, with coatings on individual nanoparticles. The cell culture experiments showed that the PEG-FA coated nanoparticles were internalized into BT-20 cancer cells and exhibited higher efficiency of intracellular uptake than only PEG- or FA-coated nanoparticles. The surface modification protocols can also be used to modify the surfaces of other nanoparticles for targeting intracellular delivery.

Breast Neoplasms↗
PubMed2005

Surface modification and laser pulse length effects on internal energy transfer in DIOS.

Benzyl-substituted benzylpyridinium (BP) chloride salts were used as a source of thermometer ions to probe the internal energy (IE) transfer in desorption/ionization on porous silicon (DIOS). To modify their wetting properties and the interaction energies with the thermometer ions, the DIOS surfaces were silylated to produce trimethylsilyl- (TMS), amine- (NH2), perfluoroalkyl- (PFA), and perfluorophenyl-derivatized (PFP) surfaces. Two laser sources--a nitrogen laser with pulse length of 4 ns and a mode locked 3 x omega Nd:YAG laser with a pulse length of 22 ps--were utilized to induce desorption/ionization and fragmentation at various laser fluence levels. The corresponding survival yields were determined as indicators of the IE transfer and the IE distributions were extracted. In most cases, with increasing the laser fluence in a broad range (approximately 20 mJ/cm2), no change in IE transfer was observed. For ns excitation, this was in remarkable contrast with MALDI, where increasing the laser fluence resulted in sharply (within approximately 5 mJ/cm2) declining survival yields. Derivatization of the porous silicon surface did not affect the survival yields significantly but had a discernible effect on the threshold fluence for ion production. The IE distributions determined for DIOS and MALDI from alpha-cyano-4-hydroxycinnamic acid reveal that the mean IE value is always lower for the latter. Using the ps laser, the IE distribution is always narrower for DIOS, whereas for ns laser excitation the width depends on surface modification. Most of the differences between MALDI and DIOS described here are compatible with the different dimensionality of the plume expansion and the differences in the activation energy of desorption due to surface modifications.

Journal Article↗
PubMed2000

Surface modification of the polymers present in a polysulfone hollow fiber hemodialyser by covalent binding of heparin or endothelial cell surface heparan sulfate: flow characteristics and platelet adhesion.

The present study addresses the problem of simultaneous surface modification of various polymers, i.e. polysulfone (PSU), polycarbonate (PC), and polyurethane (PU), which constitute the Ultraflux AV 600 S hollow fibre hemodialyser. An investigation was first made into six different chemical routes aimed at introducing carboxyl groups onto the surface of PSU, PC, and PU model polymers to which heparin (HE) or endothelial cell surface heparan sulfate (ESHS) was covalently bound via the reaction of residual amino groups and a coupling reagent. Carboxyl groups were introduced using three specific reactions based on their nucleophilic or electrophilic introduction into aromatic repeating units of the polymers and three non-specific carboxylation reactions, i.e. UV, heat or redoxactivation via nitrene or radical species. Concentrations of 1-20 nmol COOH groups per cm(-2) led to HE or ESHS surface concentrations corresponding to one or several layers. Two nonspecific carboxylation reactions followed by HE- or ESHS-coupling provided the lowest change in membrane pore structure according to cut off, clearance (urea, phosphate, maltose), ultrafiltration, and diafiltration assessments. In some cases the introduction of excess negatively-charged carboxyl groups and HE improved the flux properties of the modified membranes. The various methods were applied to the dialysis module. Platelet adhesion was not observed in the case of the ESHS-coating of PSU membrane at shear rates of 1050 s(-1), whereas HE and subendothelial matrix showed 56 and 100% coverage, respectively, under similar conditions. The coating of PSU or of other high-flux membranes by ESHS appears a promising method for improving membrane properties and to generate biocompatibility characteristics similar to those of natural blood vessels, i.e. inertness to platelet adhesion and no level effects for complement and intrinsic coagulation cascade activation. The ESHS coating may be used without anticoagulants.

Biocompatible Materials↗
PubMed1990

Hydroxyl radical generating activity of hydrous but not calcined kaolin is prevented by surface modification with dipalmitoyl lecithin.

The catalytic activity of kaolin, an aluminum silicate, for generating hydroxyl radicals (.OH) from hydrogen peroxide (H2O2) was studied in a chemical system that measured .OH as evolution of methane (CH4) from dimethyl sulfoxide. In the presence of a reducing agent and 10 mM H2O2, hydrous and calcined kaolin generated mean +/- SE CH4 concentrations of 1634 +/- 328 and 1395 +/- 29 ppm, respectively. Surface modification with dipalmitoyl lecithin, the lipid of pulmonary surfactant, blocked generation of .OH in hydrous kaolin (38 +/- 38 ppm CH4) but not in calcined kaolin (875 +/- 262 ppm CH4). The catalytic activity of kaolin for producing .OH from H2O2 may be important in the pathogenesis of kaolin toxicity, and calcined kaolin may be more toxic than hydrous kaolin because the calcined form is resistant to surface modification by lipids of pulmonary surfactant.

Humans↗
PubMed2005

Bulk and surface modifications of polylactide.

This article reviews various methods of modifying the bulk and surface properties of poly(lactic acid) (PLA) so that the polymer may be used as a drug carrier in a drug delivery system (DDS) and as a cell scaffold in tissue engineering. Copolymerization of lactide with other lactone-type monomers or monomers with functional groups such as malic acid, copolymerization of lactide with macromolecular monomer such as poly(ethylene glycol) (PEG) or dextran, as well as blending polylactide and natural derivatives and other methods of bulk modification are discussed. Surface modifications of PLA-type copolymers, such as surface coating, chemical modification, and plasma treatment are described. Cell culture technology proves the efficiency of bulk and surface modification and the potential application of PLA in tissue engineering.

Absorbable Implants↗
PubMed2002

Surface modification of liposomes for selective cell targeting in cardiovascular drug delivery.

Cardiovascular disease processes such as atherosclerosis, restenosis, and inflammation are typically localized to discrete regions of the vasculature, affording great opportunity for targeted pharmacological treatment. Liposomes are potentially advantageous targeted drug carriers for such intravascular applications. To facilitate their use as drug delivery vehicles, we have considered three components of liposome design: (i) identification of candidate cell surface receptors for targeting; (ii) identification of ligands that maintain binding specificity and affinity; and (iii) prevention of rapid nonspecific clearance of liposomes into the reticuloendothelial organs. In this report, we describe our work in developing liposomal surface modifications that address both targeting and clearance. An arginine-glycine-aspartic acid (RGD) containing peptide was used as a model ligand to target liposomes to the integrin GPIIb-IIIa on activated platelets. Additionally, oligodextran surfactants incorporated into liposomes provided insight into the effect of vesicle perturbations on liposome clearance, and the importance of molecular geometry in designing oligosaccharide surface modifications. Together these studies demonstrate the feasibility of using peptides to guide liposomes to desired receptors, and illustrate the influence of vesicle stability on liposome interactions in vivo. Furthermore, they underscore the importance of simultaneously considering both targeting specificity and vesicle longevity in the design of effective targeted drug delivery systems.

Animals↗
PubMed2005

Influence of surface modification on the luminescence of colloidal ZnO nanocrystals.

The influence of surface modification on the luminescence of colloidal ZnO nanocrystals is described, with particular emphasis given to factors increasing excitonic emission quantum yields. Changes in nanocrystal size, shape, and luminescence intensities have been measured for nanocrystals capped by dodecylamine (DDA) and trioctylphosphine oxide after different growth times. Green trap emission intensities show a direct correlation with surface hydroxide concentrations. Contrary to expectations, there is no direct correlation between excitonic emission quenching and surface hydroxide concentrations. The nearly pure excitonic emission observed after heating in DDA is attributed to the removal of surface defects from the ZnO nanocrystal surfaces and to the relatively high packing density of DDA on the ZnO surfaces. Rapid, nondispersive ripening of ZnO nanocrystals upon heating in DDA is observed and explained using a colloidal growth model.

Journal Article↗
PubMed2004

Integrated optical-fiber capillary electrophoresis microchips with novel spin-on-glass surface modification.

This paper presents a novel micro-capillary electrophoresis (CE) chip with embedded optical fibers for the on-line detection of DNA samples. The optical fibers are pre-etched and then inserted directly into fiber channels incorporated within low-cost soda-lime glass substrates. The embedded optical fibers are precisely aligned with the microfluidic channels such that the induced fluorescence signals from labeled bio-samples can be detected. This arrangement avoids the requirement for delicate optical alignment procedures and equipment. Surface modification of the CE channels is accomplished by means of a simple and reliable organic-based spin-on-glass (SOG) method. The zeta potential distribution and the corresponding electroosmotic mobility of the fluid are simulated numerically for the modified and non-modified channel surfaces, and then both sets of results are verified experimentally. The present results indicate that the value of the zeta potential for a surface with an SOG coating is 19.3 times smaller than that of an untreated surface. A phiX-174 DNA marker fluid is used to evaluate the injection and separation performance of the developed micro-CE device. Furthermore, the long-term stability of the SOG-coated surface is also investigated. The experimental data reveal that the microchip device is capable of providing highly efficient separations of bio-molecules, and that the SOG layer retains its low zeta potential characteristics for at least 45 days. The present results confirm the effectiveness of the proposed micro-CE chip in performing the on-line detection of DNA samples, and indicate that the SOG process represents a simple and reliable solution for the surface modification of glass-based microchannels.

Bacteriophages↗
PubMed2002

Surface modification by alkali and heat treatments in titanium alloys.

Pure titanium and titanium alloys are normally used for orthopedic and dental prostheses. Nevertheless, their chemical, biological, and mechanical properties still can be improved by the development of new preparation technologies. This has been the limiting factor for these metals to show low affinity to living bone. The purpose of this study is to improve the bone-bonding ability between titanium alloys and living bone through a chemically activated process and a thermally activated one. Two kinds of titanium alloys, a newly designed Ti-In-Nb-Ta alloy and a commercially available Ti-6Al-4V ELI alloy, were used in this study. In this study, surface modification of the titanium alloys by alkali and heat treatments (AHT), alkali treated in 5.0M NaOH solution, and heat treated in vacuum furnace at 600 degrees C, is reported. After AHT, the effects of the AHT on the bone integration property were evaluated in vitro. Surface morphologies of AHT were observed by optical microscopy (OM) and scanning electron microscopy (SEM). Chemical compositional surface changes were investigated by X-ray diffractometry (XRD), energy dispersive spectroscopy (EDS), and auger electron spectroscopy (AES). Titanium alloys with surface modification by AHT showed improved bioactive behavior, and the Ti-In-Nb-Ta alloy had better bioactivity than the Ti-6Al-4V ELI alloy in vitro.

Alkalies↗
PubMed2005

Band gap engineering of CdTe nanocrystals through chemical surface modification.

We demonstrate band gap control of CdTe nanocrystals by selective surface modification using alkanethiol molecules. Both absorption and emission wavelengths can be tuned simply by mixing a dispersion of the nanocrystals with alkanethiol at room temperature, resulting in blue shifts in the optical spectra during reaction. The degree of blue shift depends on both the concentration of alkanethiols and the reaction time, thereby providing kinetic control over the emission peak wavelength of the nanocrystals in mild conditions. The observed spectral changes are suggested to be caused by a decrease in the size of the CdTe core through formation of CdTe1-x(SC10)x shells because of specific exchange of Te with alkanethiolates. The results reported herein provide a new band gap engineering scheme for semiconductor nanocrystals and offer opportunities for the design of ligand-stabilized semiconductor nanocrystals with tunable composition and optical properties.

Journal Article↗
PubMed2006

Surface modification of functional self-assembled monolayers on 316L stainless steel via lipase catalysis.

Lipase catalyzed esterification of therapeutic drugs to functional self-assembled monolayers (SAMs) on 316L stainless steel (SS) after assembly has been demonstrated. SAMs of 16-mercaptohexadecanoic acid (-COOH SAM) and 11-mercapto-1-undecanol (-OH SAM) were formed on 316L SS, and lipase catalysis was used to attach therapeutic drugs, perphenazine and ibuprofen, respectively, on these SAMs. The reaction was carried out in toluene at 60 degrees C for 5 h using Novozyme-435 as the biocatalyst. The FTIR spectra after surface modification of -OH SAMs showed the presence of the C=O stretching bands at 1745 cm(-1), which was absent in the FTIR spectra of -OH SAMs. Similarly, the FTIR spectra after the reaction of the -COOH SAM with perphenazine showed two peaks in the carbonyl region, a peak at 1764 cm(-1), which is the representative peak for the C=O stretching for esters. The second peak at 1681 cm(-1) is assigned to the C=O stretching of the remaining unreacted terminal COOH. XPS spectra after lipase catalysis with ibuprofen showed a photoelectron peak evolving at 288.5 eV which arises from the carbon (C=O) of the carboxylic acid of the drug (ibuprofen). Similarly for -COOH SAMs, after esterifiation we see a small, photoelectron peak evolving at 286.5 eV which corresponds to the C in the methylene groups adjacent to the oxygen (C-O), which should evolve only after the esterification of perphenazine with the -COOH SAM. Thus, lipase catalysis provides an alternate synthetic methodology for surface modification of functional SAMs after assembly.

Catalysis↗
PubMed1994

Inhibition of in vitro calcium phosphate precipitation in presence of polyurethane via surface modification and drug delivery.

Biomaterial associated calcification is the principal cause of the clinical failure of bioprosthetic implants. The present investigation describes the mineralization of polymeric substrate in an extracirculatory environment and the possible methods of prevention. Calcification was examined on various polyurethane films (and bioprosthetic tissue) incubated in metastable solutions of calcium phosphate and the role of polymer casting and precipitation was evaluated. The formulation and the in vitro efficacy of prolonged controlled-release chitosan matrices, containing the novel anticalcification agents, such as Fe +++ or protamine sulfate (PS), were also attempted. The in vitro release profiles of PS from chitosan beads was performed in a rotating shaker (100 rpm) in 0.1 M phosphate buffer (pH 7.4) and was monitored spectrophotometrically. The amount and percentage of drug release were much higher initially, which was controlled with the incorporation of egg phosphatidyl choline (EPC). The PS loaded chitosan beads (coincubated in calcium phosphate solution with the calcifiable polyurethane films) significantly inhibited biomaterial calcification (about 40-50% inhibition). Surface modification of polyurethanes with Fe +++ or PS also inhibited the calcification profile of the material. These findings suggest the possibility of a combination therapy for prevention of biomaterial associated calcification via surface modifications in conjunction with long-term controlled release of the anticalcifying drugs.

Calcification, Physiologic↗
PubMed2005

Effects of surface modification of poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) on physicochemical properties and on interactions with MC3T3-E1 cells.

As a new member of the polyhydroxyalkanoate (PHA) family, poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) has better mechanical and processible properties than poly (3-hydroxybutyrate) (PHB). Still, it is difficult to introduce functional groups to the polyester carbon chain of PHBHHx, which restricts the modification of PHBHHx for a wide range. In this study, a procedure for the modification of the surface of PHBHHx films under strongly alkaline conditions was described. Through this kind of modification, carboxyl and hydroxyl groups were introduced to the surface and the total surface free energy was increased, which was mainly due to the increased polar components. Meanwhile, this process makes the surface rougher, resulting in larger total surface areas. After mineralization in simulated body fluids (SBFs), the apatite nucleation and growth on the surface-hydrolyzed PHBHHx films were significantly faster than on the unmodified PHBHHx films. This phenomenon should have a close relationship with the increased carboxyl and hydroxyl groups. The physicochemical properties also influenced the cell response to PHBHHx films. Compared to unmodified PHBHHx, fibronectin adsorption, and MC3T3-E1 cell attachment and proliferation were significantly greater on surface-hydrolyzed PHBHHx, which may be due to the increased surface free energy and rougher surface. Therefore, surface hydrolysis makes PHBHHx more suitable for osteoblast cell response and for application in bone-tissue engineering.

3-Hydroxybutyric Acid↗
PubMed1993

Polyurethane surface modification by graft polymerization of acrylamide for reduced protein adsorption and platelet adhesion.

Surface modification of polyurethane by glow-discharge treatment and subsequent graft polymerization of acrylamide was studied. The modified hydrophilic surfaces were characterized by the measurements of dynamic contact angle and zeta potentials and examined for protein adsorption behaviour and platelet adhesion. Data from in vitro and ex vivo experiments indicated a reduction of protein adsorption and platelet adhesion for the hydrophillic graft polymers, the extent of which was correlated to polymer graft density.

Acrylamides↗
PubMed2006

[Study on surface modification and biocompatibility of NiTi alloy intravascular stents].

This paper introduces the surface modification of NiTi alloy intravascular stents for roughness by chemical erosion and plasma deposition technology. The stent which had been granulated with chemical erosion was treated with TiO2 film prepared with Gel-sol. The study on the biocompatibility of the modified stent by the above two ways shows that the modified stent is rougher, and its anticoagulation and hydrophilicity are improved. However, the capability of erosion resistance is not enhanced significantly.

Alloys↗
PubMed2005

[Effect of surface modification using laser on wear resistance of titanium].

PURPOSE: Severe wear of cast commercial pure (CP) titanium teeth was observed in a clinical survey. This study evaluated the wear resistance of cast CP titanium and titanium alloy teeth after the surface was modified using laser technology. METHODS: Teeth patterns were duplicated from artificial first molars (Livdent FB30, GC, Japan). All teeth specimens were cast with CP Ti grade 3 (T-Alloy H, GC) and Ti-6Al-7Nb (T-Alloy Tough, GC). After the occlusal surface was blasted with Al(2)O(3), the occlusal contact points were modified using a laser (Neo laser L, Girrbach, Germany) at the following irradiation conditions (voltage: 260 V; pulse: 7 ms; focus: 1.5 mm). These parameters were determined by preliminary study. As a control, Type IV gold alloy (PGA-3, Ishifuku, Japan) was also cast conventionally. Both maxillary and mandibular teeth were worn using an in vitro two-body wear testing apparatus that simulated chewing function (60 strokes/min; grinding distance: 2 mm under flowing water). Wear resistance was assessed as volume loss (mm(3)) at 5 kgf (grinding force) after 50,000 strokes. The results (n=5) were analyzed by ANOVA/Scheffé's test (alpha=0.05). RESULTS: The gold alloy showed the best wear resistance of all the metals tested. Of all the titanium specimens tested, the modified surface indicated significantly greater wear resistance than did conventional titanium teeth without surface modification (p<0.05). CONCLUSIONS: Wear resistance was increased by modification of the surface using a laser. If severe wear of titanium teeth was observed clinically, little wear occurred when the occlusal facets were irradiated using a laser.

Dental Materials↗
PubMed2005

Photocatalytic degradation of N-nitrosodimethylamine: mechanism, product distribution, and TiO2 surface modification.

The photocatalytic degradation (PCD) reaction of N-nitrosodimethylamine (NDMA) in water was investigated using pure and surface-modified TiO2. The PCD products of NDMA were methylamine (MA), dimethylamine (DMA), nitrite, nitrate, and ammonium, and their distribution could be changed by modifying the surface of TiO2. The PCD reaction of NDMA seems to be initiated mostly by OH radicals, not valence band holes, because the addition of excess oxalates (hole scavengers) only moderately retarded the PCD rate. The presence of oxalate, however, enabled a new reductive transformation path in which the CO2-* radicals generated from the oxalate converted NDMA into DMA. In acidic suspensions of pure TiO2, the formation of MA was highly favored over DMA and NH3, whereas all degradation products (MA, DMA, and NH3) were generated at comparable concentrations at basic pH. It is suggested that there are three parallel paths depending on the position of the initial attack of OH radical on NDMA and the product distribution is closely related with which path is favored under a specific condition. DMA production is related to the OH radical attack on the nitrosyl nitrogen. Platinum deposition, silica loading, Nafion coating, and surface fluorination were tested to investigate the effects of TiO2 surface modification on the product distribution. The surface platinization of TiO2 had little effect on the PCD reaction of NDMA under air-equilibrated conditions but accelerated the PCD reaction under deaerated conditions. An enhanced PCD reaction of NDMA was achieved with the silica-loaded TiO2 and Nafion-coated TiO2, both of which favored the formation of DMA over MA. The PCD of NDMA on surface-fluorinated TiO2 was also highly enhanced but favored the formation of MA over the formation of DMA.

Carbon Dioxide↗
PubMed2005

Synthesis of photoreactive pullulan for surface modification.

Photoreactive pullulan was prepared, the polymer was photoimmobilized on polymeric or organic surfaces, and its interactions with a protein and a cell type were investigated. The photoreactive pullulan was synthesized by a coupling reaction with 4-azidobenzonic acid. Surface modification was carried out in the presence or absence of a micropatterned photomask containing 100 microm transparent stripes with 150 microm gaps, making it easy to confirm the immobilization. By the micropatterning method, immobilization of the photoreactive pullulan on polystyrene, polyethylene, and silane-coupled glass was confirmed. Contact angles were measured on the unpatterned surfaces. Although the original surfaces have different contact angles, the contact angle on Az-pullulan-immobilized surface was the same on all surfaces. This result demonstrated that photoimmobilization completely covered the surface with Az-pullulan. Protein adsorption was investigated using fluorescently labeled albumin applied to the micropatterned surface: fluorescence microscopy demonstrated that adsorption was reduced on the pullulan-immobilized regions. Culture of RAW264 cells, derived from mouse leukemic monocytes, on the micropatterned surface for 22 h showed that cells did not adhere to the immobilized pullulan regions. In conclusion, photoreactive pullulan was covalently immobilized on various surfaces and tended to reduce interactions with proteins and cells.

Adsorption↗