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Direct patterning of copper on polyimide using ion exchangeable surface templates generated by site-selective surface modification.

We demonstrate site-selective chemical surface modification by dispensing potassium hydroxide solution onto polyimide, which confines source metallic ions that can subsequently be used in resist- and mask-free fabrication of copper circuit patterns. Metallization can be achieved by a wet chemical method, providing control over metal/polymer interfacial structures. Because the approach is compatible with other existing printing technologies and much simpler than conventional lithography-based methods, we propose that the present surface template method may be of general application in fabrication of metallized polymers as well as in development of integrated circuits with a variety of electronic circuit elements.

Journal Article↗

The influence of surface modification techniques on the performance of a Y-TZP dental ceramic.

OBJECTIVES: The purpose of the current study was to examine the influence of the pre-cementation surface modification techniques, namely alumina abrasion and surface grinding, routinely employed by dental practitioners prior to cementation and placement of crown and bridge restorations on the performance of a Y-TZP dental ceramic. METHODS: Twelve sets of 30 Lava ceramic discs (13 mm diameter, 1.5mm thickness) supplied by the manufacturer were randomly selected. Six groups were abraded utilising 25, 50 and 110 microm alumina and stored dry or in a water bath at 37+/-1 degrees C for 24 h. Four groups were ground utilising a fine or a coarse grit diamond bur, specimens were ground dry or while using water as a coolant. The mean bi-axial flexure strengths, standard deviations and associated Weibull moduli (m) were determined. The surface roughness, hardness and phase composition were assessed utilising profilometry, the Vicker's hardness indentation and X-ray diffraction, respectively. RESULTS: No significant difference (P > 0.05) was identified in the bi-axial flexure strength of the 25, 50 and 110 microm alumina-abraded and the control specimens stored dry and wet for 24h. However, a significant increase in m was identified for the alumina-abraded specimens stored dry (10.7+/-1.9, 10.6+/-1.9 and 10.6+/-1.9) compared with the control (7.5+/-1.3) and the specimens stored in a water bath. In addition, the alumina abrasion regimes reduced the surface roughness compared with the controls. The coarse grinding regime significantly reduced both the bi-axial flexure strength and the associated m compared with the control whilst no significant difference was identified for the fine grinding regimes. The surface modification techniques initiated a phase transformation mechanism and resulted in the formation of a layer of compressive stresses on the surface of the disc-shaped specimens. CONCLUSIONS: The combination of the reduced surface roughness and the formation of a surface layer of compressive stress as a result of the alumina abrasion regimes investigated increased the reliability of the bi-axial flexure strength. The presence of water in the current study did not detrimentally influence the performance of the Y-TZP ceramic under investigation. Coarse grinding significantly reduced the bi-axial flexure strength and m due to the increased surface roughness. The Y-TZP specimens in the current investigation underwent a toughening mechanism as a result of a phase transformation mechanism which generated a transformation compressive stress that opposes the externally applied, crack-propagating tensile stress.

Air Abrasion, Dental↗

Plasma surface modification of synthetic absorbable sutures.

The aim of the study was to examine the feasibility of using plasma surface modification technology to alter the hydrolytic degradation rate of commercial synthetic absorbable sutures. Size 2-0 Dexon, Vicryl, PDSII, and Maxon sutures were tested. They were treated by two different surface modification techniques: parylene deposition and plasma gases (Methane, trimethylsilane, and tetrafluoroethene). The thickness of surface treatment ranged from 200 to 1000 A. The treated sutures were subject to in vitro hydrolytic degradation in phosphate buffer of pH = 7.4 at 37 degrees C for up to 120 days. The tensile breaking strength, weight loss, surface wettability, bending stiffness, and surface morphology were evaluated. The results indicated that the concept of plasma surface treatment for altering the hydrolytic degradation of synthetic absorbable sutures was feasible, and the level of improvement depended on the type of sutures, the treatment conditions, and the duration of hydrolysis. Vicryl and PDSII sutures showed overall the best improvement in tensile strength retention among the four commercial sutures. Dexon and Maxon sutures, however, exhibited only marginal improvement. The observed improvement in tensile strength retention appeared to be related to the increasing hydrophobicity of the sutures. The surface treatments did not adversely affect the bending stiffness of the sutures and no visible surface morphological changes were observed. Refinements and optimization of the surface treatment conditions are needed for achieving the maximum advantage of the proposed concept, particularly shielding the harmful effect of uv during plasma treatment.

Biodegradation, Environmental↗

Surface modification and characterization of magnetic polymer nanospheres prepared by miniemulsion polymerization.

A novel and effective protocol for the surface modification and quantitative characterization of magnetic polymeric nanospheres prepared by miniemulsion polymerization is reported. Composite nanospheres consisting of polymer-coated iron oxide nanoparticles were prepared by the miniemulsion polymerization of methyl methacrylate and divinylbenzene in the presence of magnetic fluid. Surface modification reaction of the magnetic polymer with poly(ethylene glycol) (PEG) was employed to obtain a hydrophilic hydroxyl-group-functionalized magnetic nanospheres. An affinity dye, Cibacron blue F3G-A (CB), was then coupled covalently to prepare a magnetic nonporous affinity adsorbent. The morphology and magnetic property of the polymer nanospheres obtained were examined by transmission electron microscopy and a vibrating sample magnetometer. The contents of surface groups modified were quantitatively measured by using diffusive reflectance Fourier transform infrared spectroscopy on the basis of a linear relationship between the intensity ratio of IC-O-C/IC=O and the content of PEG. X-ray photoelectron spectroscopy (XPS) was used to examine the surface of magnetic nanospheres. It was confirmed by the comparison of XPS spectra of both dye-coated and uncoated magnetic nanospheres to which the CB ligand was coupled, and the surface of the PEG-modified nanospheres had an exact 3:7 atomic ratio of sulfur to nitrogen.

Journal Article↗

[Effects of surface modification of intraocular lenses on foreign body reaction ].

PURPOSE: In order to improve biocompatibility, we investigated the effects of surface modification by 2-methacryloyloxyethyl phosphorylcholine (MPC) on the foreign body reaction of intraocular lens (IOLs). MATERIALS AND METHODS: Materials of the IOLs were polymethylmethacrylate, hydrophobic acryl, and MPC surface-modified hydrophobic IOLs (MPC modified acryl). In an in vitro study, cultured macrophages sampled from mouse intra-abdominal exudate were cultured on a plate for each IOL material. The cell density and morphology of attached cells on the IOL materials were investigated. In an in vivo study, each IOL material was implanted in the peritoneal space of mice and foreign body reaction was investigated with a light microscope and a scanning electron microscope. RESULTS: In the in vitro study, the cells on the MPC modified acryl IOL material were remarkably fewer than those on the plates of the other two IOL materials. Regarding the implanted IOL matrevials, MPC modified acryl IOL material showed more polynuclear giant foreign body cells in the early period than the other two IOL materials. CONCLUSION: MPC surface modification can reduce the foreign body reaction of IOLs and has the potential to improve biocompatibility of IOL materials.

Animals↗

Surface modification and electrostatic charge of polystyrene particles.

Particle surface modification by poloxamer adsorption can significantly alter the electrostatic charge, adhesion behaviour and consequently handling properties of a material. The charge reduction on polystyrene spheres achieved by this modification technique is dependent on the concentration, molecular weight and conformation of poloxamer at the particle surface. Adsorption isotherms of poloxamers on polystyrene particles follow a Langmuir profile and there is an apparent correlation between the extent of adsorption and ability of poloxamer to reduce electrostatic charge. Surface analysis techniques, X-ray photoelectron spectroscopy and Time of Flight Secondary Ion Mass Spectrometry have generated data on the thickness of the adsorbed poloxamer layer and provided evidence to suggest that the polypropylene oxide component of the poloxamer adsorbs to the polystyrene surface and there is a polyethylene oxide rich outer surface which may influence the charge alteration.

Adsorption↗

Surface modification for enhancing antibody binding on polymer-based microfluidic device for enzyme-linked immunosorbent assay.

A novel surface treatment method using poly(ethyleneimine) (PEI), an amine-bearing polymer, was developed to enhance antibody binding on the poly(methyl methacrylate) (PMMA) microfluidic immunoassay device. By treating the PMMA surface of the microchannel on the microfluidic device with PEI, 10 times more active antibodies can be bound to the microchannel surface as compared to those without treatment or treated with the small amine-bearing molecule, hexamethylenediamine (HMD). Consequently, PEI surface modification greatly improved the immunoassay performance of the microfluidic device, making it more sensitive and reliable in the detection of IgG. The improvement can be attributed to the spacer effect as well as the functional amine groups provided by the polymeric PEI molecules. Due to the smaller dimensions (140x125 microm) of the microchannel, the time required for antibody diffusion and adsorption onto the microchannel surface was reduced to only several minutes, which was 10 times faster than the similar process carried out in 96-well plates. The microchip also had a wider detection dynamic range, from 5 to 1000 ng/mL, as compared to that of the microtiter plate (from 2 to 100 ng/mL). With the PEI surface modification, PMMA-based microchips can be effectively used for enzyme linked immunosorbent assays (ELISA) with a similar detection limit, but much less reagent consumption and shorter assay time as compared to the conventional 96-well plate.

Animals↗

Effect of particle size on surface modification of silica nanoparticles by using silane coupling agents and their dispersion stability in methylethylketone.

The effect of particle size on the reactivity of hexyltrimethoxysilane (C6S) with the particle surface was studied by using silica nanoparticles (SNPs) with different diameters (30 or 200 nm). In case of 30-nm SNPs, a large amount of isolated silanol was observed. On the other hand, in the case of 200-nm SNPs, the amount of hydrogen bonded silanol and hydrogen bonded water molecules at the surface of the SNPs increased. Since the hydrogen bonded silanol and the hydrogen bonded water enhanced the reaction of C6S with SNPs, the chemisorbed C6S on 200-nm SNPs was larger than that on 30-nm SNPs. Furthermore, the effects of surface modification on the dispersion stability in MEK were studied using viscosity measurements and surface force measurements by the AFM colloid probe method. The viscosity of the dilute SNPs/MEK suspension did not change by the chemisorptions of C6S; however, the viscosity of dense suspension reduced effectively by surface modification. It was estimated that the suspension viscosity reduced effectively when the mean particle surface distance in the suspension was near to the distance where the repulsive force appeared by the surface force measurements using the colloid probe AFM.

Butanones↗

Antithrombotic and fibrinolytic system of human endothelial cells seeded on PTFE: the effects of surface modification of PTFE by ammonia plasma treatment and ECM protein coatings.

The aim of this study was to determine the effects of ECM protein coatings and surface modification of PTFE on the ability of seeded human endothelial cells (EC) to secrete prostacyclin (PGI2), plasminogen inhibitor-1 (PAI-1) and tissue plasminogen activator (t-PA). PTFE surfaces were modified by a novel surface modification technique based on ammonia plasma. Fibronectin, collagen type-1 and gelatin-coated ammonia plasma modified PTFE and unmodified PTFE surfaces were employed and compared in this study. All ammonia plasma modified surfaces showed similar secretions of PGI2 compared to non-modified PTFE surfaces. With the exception of gelatin-coated modified PTFE, seeded EC seeded on all modified PTFE showed lower levels of PAI-1 secretion compared to those seeded on unmodified PTFE. The specific activity of t-PA secreted by EC seeded on ammonia plasma modified and fibronectin coated modified PTFE showed increases of 100 and 30%, respectively, when compared to their unmodified counterparts. Our studies show that EC seeded on modified PTFE have ability to secrete PGI2 that modulates the early phase of thrombus formation. Furthermore, superior t-PA profile, along with lower levels of PAl-1 suggest that ammonia plasma modification and use of appropriate ECM proteins can modulate antithrombotic and fibrinolytic properties of in vitro endothelialized vascular prostheses. Accordingly, these surfaces may be suitable to further develop protocols and other strategies for arterial and venous reconstruction.

Ammonia↗

A new powder design method to improve inhalation efficiency of pranlukast hydrate dry powder aerosols by surface modification with hydroxypropylmethylcellulose phthalate nanospheres.

PURPOSE: A new particle design method to improve the aerosolization properties of a dry powder inhalation system was developed using surface modification of hydrophobic drug powders (pranlukast hydrate) with ultrafine hydrophilic particles, hydroxypropylmethylcellulose phthalate (HPMCP) nanospheres. The mechanism of the improved inhalation properties of the surface-modified particles and their deposits on carrier particles (lactose) was clarified in vitro. METHODS: Drug particles were introduced to aqueous colloidal HPMCP dispersions prepared by emulsion-solvent diffusion techniques followed by freeze- or spray-drying of the resultant aqueous dispersions. The surface-modified powders obtained with HPMCP nanospheres and their mixture with lactose powders were aerosolized by Spinhaler and their mode of deposition in lung was evaluated in vitro using a twin impinger. To elucidate the inhalation mechanism of these surface modified particles, we measured their modified micromeritic properties, such as surface topography, specific surface area, dissolution rate, and dispersibility in air. RESULTS: Dramatically improved inhalation properties of the surface modified powder, i.e. a two-fold increase in emission and a three-fold increase in delivery to deep lung, were found in vitro compared with the original unmodified powder. Improved inhalation was also found with the surface-modified drug deposited on lactose particles. Those improvements were attributed to the increased surface roughness and hydrophilicity of the surface-modified particles, and the resultant increased dispersibility in air. CONCLUSIONS: Surface modification of hydrophobic drug particles with HPMCP nanospheres to improve hydrophilicity was extremely useful in increasing the inhalation efficiency of the drug itself and the drug deposited on carrier; this was attributed to increased dispersibility in air and emission from the device, for spray- and freeze-dried particles, respectively.

Administration, Inhalation↗

Kinetics of ultraviolet and plasma surface modification of poly(dimethylsiloxane) probed by sum frequency vibrational spectroscopy.

In numerous applications in microfluidics, cell growth, soft lithography, and molecular imprinting, the surface of poly(dimethylsiloxane) (PDMS) is modified from a hydrophobic methyl-terminated surface to a hydrophilic hydroxyl-terminated surface. In this study, we investigated molecular structural and orientational changes at the PDMS-air interface in response to three commonly used surface modification processes: exposure to long-wavelength ultraviolet light (UV), exposure to short-wavelength UV that generates ozone (UVO), and exposure to oxygen plasma (OP). The surfaces of two PDMS compositions (10:1 and 4:1 of base polymer/curing agent) were probed during modification, using monolayer-sensitive IR + visible sum frequency generation (SFG) vibrational spectroscopy, with two different polarization combinations. During PDMS surface modification, the peak intensities of CH3 side groups and CH2 cross-link groups decreased, while peak intensities of Si-OH groups increased. There was no significant change in the average orientation of the CH3 groups on the PDMS surface during modification. The concentration of CH3 groups on the surface decreased exponentially with time, for all three UV, UVO, and OP modification processes, with first order kinetics and time constants of approximately 160, 66, and 0.3 min, respectively. At steady state, residual CH3 groups were detected at the PDMS surface for UV and UVO treatments; however, there were negligible CH3 groups detected after OP modification.

Dimethylpolysiloxanes↗

Porogen-induced surface modification of nano-fibrous poly(L-lactic acid) scaffolds for tissue engineering.

In addition to suitable pore architecture of a tissue-engineering scaffold, surface modification after scaffolding fabrication is often needed to enhance the interactions between cells and the synthetic material. In this study, a novel one-step process was developed to fabricate surface-modified nano-fibrous poly(L-lactic acid) (NF-PLLA) scaffolds. First, gelatin spheres with smooth surface were prepared by non-surfactant emulsification, solvent extraction, and freeze-drying. A three-dimensional NF-PLLA scaffold was then fabricated by using gelatin spheres as porogen. Gelatin molecules were entrapped onto the scaffold surface during the fabrication process. Attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) spectroscopy and X-ray photoelectron spectroscopy analysis demonstrated the existence of gelatin molecules on the surface of the polymer scaffold. The amount of gelatin on the scaffold surface was controlled by the composition of the solvent mixture of gelatin solution. The compressive modulus of scaffold prepared with gelatin spheres was more than three times higher than that prepared with irregular gelatin particles of the same size range. The surface modification significantly improved initial cell adhesion and proliferation over a 2-week culture. SEM images indicated that cells spread on the gelatin-entrapped scaffolds in contrast to spherical or spindle morphology on the control 1 day after cell seeding. Furthermore, more matrix secretion was observed on the surface-modified scaffolds than on the control after 2 weeks of in vitro cultivation. In conclusion, this approach provides a simple one-step process to fabricate surface-modified collagen-like NF-PLLA scaffolds, which have improved cell adhesion and proliferation.

3T3 Cells↗

Development of a biodegradable ureteric stent: surface modification and in vitro assessment.

The aim of the present study was to develop a short bioresorbable ureteric stent and to characterize the chosen polymers with respect to surface modification, biocompatibility, and loading of a biologically active compound. As materials for the stent, poly(D,L-lactide) and poly(D,L-lactide-co-glycolide) were chosen. Degradation experiments were carried out and analytical data were obtained by contact angle measurement, X-ray photoelectron spectroscopy (XPS), and infrared spectroscopy in the attenuated reflection mode (FTIR-ATR). Gas loading technology was used to incorporate biologically active compounds, and biocompatibility of the polymers was assessed by in vitro cellular assays, applying measures such as cell morphology, proliferative activity, and membrane integrity. Our results indicate that surface modification of bioresorbable polymers is a suitable and efficient approach to improve the surface properties. Incorporation of biologically active compounds was possible without loss of activity, and in vitro assessment of cellular responses demonstrated the biocompatibility of the chosen polymers and modifications.

Absorption↗

Surface modification of poly(dimethylsiloxane) for retarding swelling in organic solvents.

A method of alleviating swelling problems of poly(dimethysiloxane) (PDMS) molds in organic solvents is developed that allows repeated use of the molds without deleterious solvent effects. The method involves surface modification of PDMS surface with poly(urethaneacrylate) that results in a partially modified PDMS surface. This modification leads to a significant reduction in the rate of solvent absorption into PDMS such that the swelling can be controlled.

Journal Article↗

Effect of surface modification on back electron transfer dynamics of dibromo fluorescein sensitized TiO2 nanoparticles.

Electron injection and back electron transfer (BET) dynamics have been carried out for dibromo fluorescein (DBF) sensitized TiO2 nanoparticles capped (modified) with sodium dodecyl benzene sulfonate using transient absorption techniques in picosecond and microsecond time domain. BET dynamics have been compared with bare (unmodified) nanoparticles for the same DBF/TiO2 system. It has been observed that BET reaction is slow on the modified surface compared to a bare surface in earlier time domain (picosecond). This observation has been explained by the fact that on surface modification the energy levels of the semiconductor nanoparticles are pushed up in energy. As a result, the free energy of reaction (-deltaG zero) for BET reaction of a dye/SM-TiO2 system increases as compared to the dye/bare TiO2 system. High exoergic BET reaction in dye-sensitized TiO2 nanoparticles surfaces fall in the Marcus inverted regime, so with increasing free energy of reaction, BET rate decreases on the modified surface. However, a reversible trend in BET dynamics has been observed for the above systems in the longer time domain (microsecond). In microsecond time domain BET reaction is faster on the modified surface as compared to on the bare surface. Modification of this surface reduces the density of deep trap states. Recombination dynamics between deep-trapped electron and parent cation is slow due to low coupling strength of BET reaction. As the density of deep-trapped electrons is high in bare particles, BET reaction is slow in longer time domain.

Absorption↗

Surface modification of cellulose fibers: towards wood composites by biomimetics.

A biomimetic approach was taken for studying the adsorption of a model copolymer (pullulan abietate, DS 0.027), representing the lignin-carbohydrate complex, to a model surface for cellulose fibers (Langmuir-Blodgett thin films of regenerated cellulose). Adsorption results were assayed using surface plasmon resonance spectroscopy (SPR) and atomic force microscopy (AFM). Rapid, spontaneous, and desorption-resistant surface modification resulted. This effort is viewed as a critical first step towards the permanent surface modification of cellulose fibers with a layer of molecules amenable to either enzymatic crosslinking for improved wood composites or thermoplastic consolidation.

Biomimetics↗

Surface modification of poly(methyl methacrylate) for improved adsorption of wall coating polymers for microchip electrophoresis.

The development of rapid and simple wall coating strategies for high-efficiency electrophoretic separation of DNA is of crucial importance for the successful implementation of miniaturized polymeric DNA analysis systems. In this report, we characterize and compare different methods for the chemical modification of poly(methyl methacrylate) (PMMA) surfaces for the application of wall coating polymers. PMMA surfaces coated with 40 mol% diethylacrylamide and 60 mol% dimethylacrylamide are compared to the PMMA surfaces first oxidized and then coated with hydroxypropylmethyl-cellulose or poly(vinyl alcohol) (PVA). PMMA oxidation was accomplished with UV/ozone or an aqueous solution of HNO(3) to yield hydrogen-bond donors for the spontaneous adsorption of the coating polymers. Contact angle measurements of UV/ozone exposed PMMA surfaces indicate increase in hydrophilicity, and polymer coated surfaces show a strong dependence on the coating polymer and the oxidation method. Fast and repeatable electrophoretic separations of a 10-base and 20-base DNA ladder were performed in PMMA micro CE devices. All analyses were completed in less than 10 min, resulting in the number of theoretical plates as high as 583 000 in a 7.7 cm long separation channel. The duration of UV/ozone treatment was found to have a considerable impact on separation performance. The microchips irradiated with UV for 10 min and coated with PVA as well as the microchips treated with HNO(3) and coated with HPMC were found to have the best separation performance. These results demonstrate facile and robust methods for the surface modification of PMMA enabling low-cost single use devices for electrophoretic DNA separations.

Acrylamides↗

Surface modification of a porous hydroxyapatite to promote bonded polymer coatings.

Porous hydroxyapatite (Hap) blocks were sintered at several temperatures and methyl methacrylate (MMA) grafted onto the surface in a 2-step heterogeneous system as a model example for surface modification. First, sintered porous Hap was modified with 2-methacryloyloxyethylene isocyanate (MOI) monomer in anhydrous dimethyl sulfoxide using di-n-butyltin (IV) dilaurate as a catalyst and hydroquinone as an inhibitor. Amount of the introduction of MOI monomer on porous Hap was 1.62 wt % at sintered temperature 800 degrees C, 0.68 wt % at it of 1000 degrees C, and 0.59 wt % at it of 1200 degrees C. Scanning electron microscopy (SEM) showed that porous Hap pore size and shape before and after MOI treatment were unchanged. Second, graft polymerization with MMA through the vinyl bond on porous Hap was conducted using alpha,alpha'-azobis isobutyronitrile (AIBN) as an initiator. Amount of Grafted PMMA on the MOI modified porous Hap was 2.84 wt % at sintered temperature of 800 degrees C, 6.97 wt % at it of 1000 degrees C, and 6.27 wt % at it of 1200 degrees C. MOI-modified and PMMA-grafted porous Hap were characterized using Fourier transform infrared (FT-IR) spectroscopy. The compressive strength of sintered porous Hap with grafted PMMA increased about 2.7-6.7 times compared to intact porous Hap. This 2-step surface modification on porous Hap is widely applicable to graft polymerization with vinyl polymer and conjugation with a protein or an oligopeptide, such as growth factor or an adhesion molecule, to improve Hap mechanical properties and functionality.

Journal Article↗