Chemically induced graft copolymerization of 2-hydroxyethyl methacrylate onto polyurethane surface for improving blood compatibility

To improve hydrophilicity and blood compatibility properties of polyurethane (PU) film, we chemically induced graft copolymerization of 2-hydroxyethyl methacrylate (HEMA) onto the surface of polyurethane film using benzoyl peroxide as an initiator. The effects of grafting temperature, grafting time, monomer and initiator concentrations on the grafting yields were studied. The maximum grafting yield value was obtained 0.0275 g/cm² for HEMA. Characterization of the films was carried out by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), water contact angle measurements. ATR-FTIR data showed that HEMA was successfully grafted onto the PU films surface. Water contact angle measurement demonstrated the grafted films possessed a relatively hydrophilic surface. The blood compatibility of the grafted films was preliminarily evaluated by a platelet-rich plasma adhesion test and hemolysis test. The results of platelet adhesion experiment showed that polyurethane grafted polymerization with monomer of 2-hydroxyethyl methacrylate had good blood compatibility featured by the low platelet adhesion. Hemolysis rate of the PU-g-PHEMA films was dramatically decreased than the ungrafted PU films. This kind of new biomaterials grafted with HEMA monomers might have a potential usage for biomedical applications.     

Enhanced cell affinity of poly(l-lactide) film by immobilizing phosphonized chitosan

Graft polymerization of acrylic acid (AA) onto poly(l-lactide) (PLLA) film by UV irradiation was carried out to develop surfaces for N-methylene phosphonic chitosan (NMPC) immobilization. The properties of modified films were discussed by colorimetric method, attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR), contact angles, atomic force microscopy (AFM) and osteoblast incubation. The results showed that AA solution concentration and irradiation time had effect on the graft carboxyl densities. Comparing the ATR-FTIR images, two new peaks at 1561 cm⁻¹ and 1632 cm⁻¹ proved that NMPC was immobilized on the film surface successfully. The water contact-angles were decreased from 90 ± 5° to 37 ± 5° after modification. The AFM images indicated that the surface of the combined film was rougher than that of untreated film. The grafted film provided an excellent substrate for the growth of osteoblast.     

Biocompatibility of polypropylene non-woven fabric membrane via UV-induced graft polymerization of 2-acrylamido-2-methylpropane sulfonic acid

This work described the graft polymerization of a sulfonic acid terminated monomer, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), onto the surface of polypropylene non-woven (NWF PP) membrane by O₂ plasma pretreatment and UV-induced photografting method. The chemical structure and composition of the modified surfaces were analyzed by FTIR-ATR and XPS, respectively. The wettability was investigated by water contact angle and equilibrium water adsorption. And the biocompatibility of the modified NWF PP membranes was evaluated by protein adsorption and platelet adhesion. It was found that the graft density increased with prolonging UV irradiation time and increasing AMPS concentration; the water contact angles of the membranes decreased from 124° to 26° with the increasing grafting density of poly(AMPS) from 0 to 884.2 μg cm⁻², while the equilibrium water adsorption raised from 5 wt% to 75 wt%; the protein absorption was effectively suppressed with the introduction of poly(AMPS) even at the low grafting density (132.4 μg cm⁻²); the number of platelets adhering to the modified membrane was dramatically reduced when compared with that on its virgin surface. These results indicated that surface modification of NWF PP membrane with AMPS was a facile approach to construct biocompatible surface.     

Collagen-grafted temperature-responsive nonwoven fabric for wound dressing

Polypropylene (PP) nonwoven fabric (NWF) was modified by direct current pulsed plasma followed by grafting with acrylic acid (AAc) to improve its surface hydrophilicity and to introduce carboxylic acid group on the surface for further conjugation with bioactive collagen biomolecule. To endow temperature-responsive property, PP-g-collagen NWF was further modified with poly(N-isopropylacrylamide) (PNIPAAm). Experimental results demonstrated that the amount of AAc and collagen grafted were 43.4 nmole/cm², and 35.9 μg/cm², respectively. The amount of PNIPAAm immobilized was 213 μg/cm². The physical properties, surface chemical composition, and microstructure of the NWFs were characterized. From animal study, modified NWFs were found to promote wound healing with bigraft PP-g-collagen-g-PNIPAAm NWF showing the best performance.     

Pulsed electron beam deposition of highly oriented thin films of polytetrafluoroethylene

Thin films of polytetrafluoroethylene (PTFE) were deposited by pulsed electron deposition (PED) technique. The transmission electron microscopy (TEM) image of the RT fabricated (20 Å thick) film on carbon coated copper grid shows crystalline nature. Infrared spectra show one to one correspondence between PED ablated film and the PTFE bulk target. The asymmetrical and symmetrical -CF₂- stretching modes were observed at 1220 and 1156 cm⁻¹, respectively. The -CF₂- wagging and bending modes occur at 644 and 512 cm⁻¹, respectively. X-ray diffraction patterns of the film deposited at room temperature (RT) show oriented film along (1 0 0) plane of hexagonal structure and the crystalline nature is retained up to 300 °C on vacuum annealing. The room temperature fabricated film shows smooth and pin hole free surface whereas post-annealing brings discontinuity, roughness and pin holes.     

An atomic force microscopy study of DNA hairpin probes monolabelled with gold nanoparticle: Grafting and hybridization on oxide thin films

First and original results are reported regarding the surface evolution of two kinds of oxide film after covalent grafting and hybridization of hairpin oligonucleotide probes. These hairpin probes were monolabelled with a 1.4 nm gold nanoparticle. One kind of oxide film was rough Sb doped SnO₂ oxide film and the other kind was smooth SiO₂ film. Same process of covalent grafting, involving a silanization step, was performed on both oxide surfaces. Atomic force microscopy (AFM) was used to study the evolution of each oxide surface after different steps of the process: functionalization, probe grafting and hybridization. In the case of rough SnO₂ films, a slight decrease of the roughness was observed after each step whereas in the case of smooth SiO₂ films, a maximum of roughness was obtained after probe grafting. Step height measurements of grafted probes could be performed on SiO₂ leading to an apparent thickness of around 3.7 ± 1.0 nm. After hybridization, on the granular surface of SnO₂, by coupling AFM with SEM FEG analyses, dispersed and well-resolved groups of gold nanoparticles linked to DNA duplexes could be observed. Their density varied from 6.6 ± 0.3 × 10¹⁰ to 2.3 ± 0.3 × 10¹¹ dots cm⁻². On the contrary, on smooth SiO₂ surface, the DNA duplexes behave like a dense carpet of globular structures with a density of 2.9 ± 0.5 × 10¹¹ globular structures cm⁻².     

The wettability of polytetrafluoroethylene and polymethylmethacrylate by aqueous solutions of Triton X-100 and short chain alcohol mixtures

Measurements of advancing contact angles (θ) were carried out for aqueous solutions of Triton X-100 (TX-100) and methanol and ethanol mixtures at constant TX-100 concentration equal to 1 × 10⁻⁷, 1 × 10⁻⁶, 1 × 10⁻⁵, 1 × 10⁻⁴, 6 × 10⁻⁴ and 1 × 10⁻³ M, respectively, on polytetrafluoroethylene (PTFE) and polymethylmethacrylate (PMMA). Using measured contact angle values the relationships between cos θ, adhesion tension and surface tension of the solutions were determined, and on their basis the critical surface tension of PTFE and PMMA wetting was calculated. The obtained average value of the critical surface tension of PTFE wetting is lying in the range of the PTFE surface tension values which can be found in the literature, while for PMMA it is even lower than the Lifshitz-van der Waals component of its surface tension. From the relationship between the adhesion and surface tension and Lucassen-Reynders equation it results that in the case of PTFE the adsorption at the PTFE-solution and solution-air interfaces is the same, which was confirmed by a linear relationship between the cos θ and 1/γ_LV and intercept on cos θ axis equal to −1. However, for PMMA the adsorption of the surface active agents at solution-air interface is higher than at PMMA-solution. Using the values of the contact angle the values of the adhesion work of solution to the PTFE and PMMA surface were also determined, which are constant for PTFE, but for PMMA decrease with alcohol concentration increase. Next, using the contact angle values in the Young equation, the PTFE(PMMA)-solution interface tension was also calculated. The obtained values of PTFE-solution interface tension were compared with those evaluated from the Szyszkowski, Connors and Fainerman and Miller equations, and good agreement between these values was observed for all series of TX-100 and alcohol mixtures at a low alcohol concentration.     

Surface modification of polyethylene terephthalate with albumin and gelatin for improvement of anticoagulation and endothelialization

The surfaces of polyethylene terephthalate (PET) were modified by oxygen plasma-induced and ultraviolet (UV)-assisted acrylic acid (AAc) grafting polymerization, and the carboxyl (COOH) groups on the PET surface was 5.29 × 10⁻⁹mol/cm². Then using the COOH as reacting sites, the molecules of gelatin and bovine serum albumin (BSA) were further co-immobilized on the PET surface. The modified PET surfaces were characterized by X-ray photoelectron spectroscopy (XPS) and surface chemical quantitative analysis. The results showed that the molecules of gelatin and albumin were immobilized on the PET surface. The concentration of gelatin on the gelatin-immobilized PET surface was 2.02 μg/cm². For the gelatin-immobilized PET surface, the human umbilical vein endothelial cells (HUVECs) culture attachment and proliferation ratios were improved, but the anticoagulation became worse proved by platelet adhesion test in vitro and the lactate dehydrogense (LDH) test. After further co-immobilization of albumin with gelatin biomolecules on the PET surface (PET-Gel-BSA), the percent of platelet adhesion in vitro decreased 28% than that on the gelatin-immobilized PET surface, and the cell density on the PET-Gel-BSA film (1.08 × 10⁵ cells/cm²) was significantly higher than that on the control PET surface. This investigation tries to find a method which can construct the anticoagulant surface before the endothelium formation and also accelerate the endothelialization of polymer surface.     

Formation of functional groups on graphite during oxygen plasma treatment

Improved sample wettability was obtained by oxygen plasma functionalization of pyrolytic graphite. The samples were exposed to highly dissociated oxygen plasma with the density of 1 × 10¹⁶ m⁻³, the electron temperature of about 5.5 eV and the density of neutral oxygen atoms of 8 × 10²¹ m⁻³ for 20 s. The surface wettability was measured by a contact angle of water drop. The contact angle dropped from original 112° down to about 1°. The functional groups were detected by XPS analyses. The survey spectrum showed a substantial increase of oxygen concentration on the surface, while high-resolution analyses showed additional oxygen was bonded onto the graphite surface in the form of C-O polar functional group responsible for the increase of the surface energy.     

Superhydrophobicity of polytetrafluoroethylene thin film fabricated by pulsed laser deposition

Superhydrophobic polytetrafluoroethylene (PTFE) thin films were obtained by pulsed laser deposition (PLD) technique carried out with KrF excimer laser (λ = 248 nm) of about 1 J/cm² at a pressure of 1.33 Pa. The samples exhibit high water contact angle of about 170° and the sliding angle smaller than 2°. From studying the surface morphology of the prepared films, it is believed that the nano-scale surface roughness has enhanced the hydrophobic property of the PTFE. The increase of trapping air and reducing liquid-solid contact area due to the rough surface, as suggested by the Cassie-Baxter's model, should be responsible for superhydrophobicity of the PLD prepared films. This study thus provides a convenient one-step method without using wet-process to produce a superhydrophobic surface with good self-cleaning properties.     

Temperature effect on water desorption from methylcellulose films studied by thermal FT-IR microspectroscopy

Temperature-induced desorption behavior of water from methylcellulose (MC) film was investigated by a novel microscopic Fourier transform infrared (FT-IR) spectroscopy equipped with thermal analyzer (thermal FT-IR microscopic system) and thermogravimetric analysis (TGA). The result indicates that the weight loss of water from MC film was markedly correlated to the IR spectral changes of OH stretching (3000-3800 cm⁻¹) and bending (1649 cm⁻¹) modes of water molecules. The shift of OH stretching mode from 3461 to 3481 cm⁻¹ was accompanied with the water loss from MC film induced by temperature effect. Two stages of water desorption from MC film were proposed: the first stage within the 35-65 °C had a dramatic IR peak shift from 3461 to 3477 cm⁻¹ and accompanied with a largest weight loss of water from MC film, which might be mainly due to the desorption of free water with minor weakly hydrogen-bonded water; the second stage beyond 65 °C would be desorption of moderately hydrogen-bonded bound water, due to the gradual IR spectral shift from 3477 to 3481 cm⁻¹ and a slower weight loss of water from MC film. The changes in peak area ratio of 1649 cm⁻¹/1374 cm⁻¹ with the temperature also confirmed the IR spectral peak shift of the OH stretching mode via the water loss from MC film. The temperature-dependent dissociation of intermolecular and intramolecular hydrogen bonds within water molecules and/or between water/MC interaction might be responsible for the desorption kinetics of water from MC film.     

SiO2 film electret with high surface potential stability

The plasma surface treatment and ion implantation were utilized to improve the stability of charge storage in the SiO₂ film electret. It was found that the SiO₂ films treated by argon plasma with the arcing at 700 V for 15 min, or implanted by 150 keV (kilo electron volt) Ar⁺ with a dose of 2 × 10¹¹ cm⁻², after being negatively charged, showed a remnant negative potential as large as 90% of the primary value after being stored in a glass container with desiccant for 10 days. It was also found that after being negatively charged at room temperature and aged at 200-350 °C for several times, the SiO₂ films implanted by 150 keV Ar⁺ had a relatively high remnant potential and it did not decay significantly even after being heated at the aging temperature of 200-350 °C in room atmosphere for 60 min.     

Characterization of Ti6Al4V implant surface treated by Nd:YAG laser and emery paper for orthopaedic applications

A more noble and biocompatible Ti alloy was achieved at fluence of 140 J cm⁻² where the implant indicated a higher degree of hardness (825HV), higher corrosion resistance (−0.21 V) and highest hydrophilicity (i.e. θ_c = 37°) compared with 70° of the control sample. These values corresponded to 58 and 39 mN m⁻¹ of surface tension respectively. The laser treated samples at 140 J cm⁻² showed higher wettability characteristics than mechanically roughened surface. Cell growth and their spreading condition in a specific area were analyzed by SEM and Image J Program software. Clearly, more cells were attached (1.2 × 10⁵) to and spread (488 μm²) over the surface at 140 J cm⁻² than in any other condition. Pathologically, the treated samples indicated no sign of infection.     

Nitrogen plasma-based ion implantation of poly(tetrafluoroethylene): Effect of the main parameters on the surface properties

The surface of poly(tetrafluoroethylene) (PTFE or Teflon) was treated by nitrogen plasma-based ion implantation. Accelerating voltages between 15 and 30 kV, fluences between 1 × 10¹⁷ and 3 × 10¹⁷ cm⁻² and fluence rates between 3 × 10¹³ and 7 × 10¹³ cm⁻² s⁻¹ were applied. The effects of these main parameters were examined on the evolution of surface chemical composition, mean roughness, abrasive wear, wettability and surface electrical resistance. The aim was to obtain relationships, enabling to control the surface properties examined.The F/C atomic ratio determined by XPS strongly decreased, correlating inversely with voltage. The mean surface roughness characterized by topography measurements, increased, correlating directly with fluence and inversely with voltage. The wear volume obtained by multipass scratch tests did not show clear relationship with the main process parameters, however, it increased upon treatment with the increase of surface roughness and O/C atomic ratio. The water contact angle increased at low voltages and high fluences, due to preferential increase of roughness, and decreased at high voltages and low fluences, owing to intense defluorination and incorporation of N and O. The electrical resistance of the PBII-treated surfaces decreased by several orders of magnitude, showing a significant inverse correlation with fluence. It continued to decrease for samples exposed to air, primarily after treatments performed with low fluences, due to post-treatment type oxidation.     

Ag-N doped ZnO film and its p-n junction fabricated by ion beam assisted deposition

Ag-N doped ZnO film was synthesized by ion beam assisted deposition and its electrical properties and annealing property were investigated. The films remained p-type even after annealing at 400 °C in air for 10 min. While the annealing temperature went up to 500 °C, the conduction type of these films shifted from p-type to n-type. The p-type ZnO film revealed low resistivity (0.0016 Ω cm), low Hall mobility (0.65 cm² V⁻¹ s⁻¹) and high carrier concentration (5.8 × 10²⁰ cm⁻³). ZnO p-n homojunction consisting of a p-type layer (Ag-N doped ZnO film) and an n-type layer (In-doped ZnO film) had been fabricated by ion beam assisted deposition. With electrical measurement, its current-voltage curve had a typical rectifying characteristic with current rectification ratio of 25 at bias ±5 V and a reverse current of 0.01 mA at −5 V. The depletion width was estimated 3.8 nm by using p-n junction equation.     

Thermal stability of alkoxy monolayers grafted on Si(1 1 1)

Direct grafting of organic monolayers on Si is of prime interest in order to give specific properties to a silicon surface. However, for microelectronics applications, this possibility is hampered by the limited stability of the grafted layers. It has been previously established that alkyl layers attached to Si surfaces through Si-C bonds become unstable at 250-300 °C, by desorption of alkenes. Changing the nature of the bonding to the surface might allow one to circumvent this desorption pathway and increase the layer stability. In our work, decanol and decyl aldehyde are reacted with the Si(1 1 1)-H surface at ∼100 °C during 20 h in order to obtain alkoxy monolayers. FTIR measurements performed in ATR geometry show that the grafted molecule surface coverage is on the order of 33% after reaction with decanol and 50% after reaction with decyl aldehyde. Characterization by AFM essentially reveals that the morphology of the grafted surfaces is unaffected as compared to that of Si-H surfaces. However, the edges of the terraces at alcohol-grafted surfaces exhibit some pitting, probably due to the presence of water in the grafting liquid. Thermal stability studies show that alkoxy chains progressively disappear from the Si surface between 200 and 400 °C. From the CH₂/CH₃ ratio in the CH region (2760-3070 cm⁻¹), it appears that the chains undergo progressive dissociation by C-C bond breaking before their complete disappearance from the surface. Therefore, the thermal behaviour of alkoxy monolayers appears quite distinct from that of alkyl monolayers that tend to leave the surface in a much narrower temperature range (250-350 °C), essentially via breaking of the Si-C bonds.     

Surface modification of polyacrylonitrile film by anchoring conductive polyaniline and determination of uricase adsorption capacity and activity

Polyacrylonitrile (PAN) films were modified with chemical polymerization of conductive polyaniline (PANI) in the presence of potassium dichromate as an oxidizing agent. The effect of aniline concentration on the grafting efficiency and on the electrical surface resistance of PAN and (PAN/PANI)-1-3 composite film was investigated. The surface resistances of the conductive composite films were found to be between 6.32 and 0.97 kΩ/cm. As the amount of grafted PANI increased on the PAN films, the electrical resistance of composite film decreased. The PAN/PANI composite films were also characterized using SEM and FTIR. The changes in the surface properties of the films were characterized by contact angle measurements. As expected, the PAN, PAN/PANI and PAN/PANI-uricase immobilized films, exhibited different contact angle values and surface free energy due to different interactive functional groups of the films.The conductive films were well characterized and used for immobilization of uricase. The amount of adsorbed enzyme increases with the increase of surface concentration of grafted fibrous polyaniline polymer. The maximum amount of immobilized enzyme onto composite film containing 2.4% PANI was about 216 μg/cm² (i.e., PAN/PANI-3). The immobilized uricase was reused 24 times in batch wise assay in a day. Finally, the immobilized uricase enzyme system was successfully fabricated and applied to determine the uric acid level in human serum samples.     

Hydrophobic modification of wood via surface-initiated ARGET ATRP of MMA

To convert the hydrophilic surface of wood into a hydrophobic surface, the present study investigated activators regenerated by electron transfer for atom transfer radical polymerization (ARGET ATRP) as a method of grafting methyl methacrylate (MMA) onto the wood surface. The wood treated with 2-bromoisobutyryl bromide and with the subsequently attached MMA via ARGET ATRP under different polymerization times (2 h, 4 h, 6 h, 8 h) were examined using scanning electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. All the analyses confirmed that PMMA had been grafted onto the wood surface. Water contact angle measurement proved that the covering layer of PMMA on wood made the surface hydrophobic. Polymerization time had a positive influence on the contact angle value and higher contact angle can be produced with the prolongation of the polymerization time. When the reaction time was extended to 8 h, the contact angle of treated wood surface reached 130° in the beginning, and remained at 116° after 60 s. The ARGET ATRP method may raise an alteration on the wood surface modification.     

Topological and chemical investigation on super-hydrophobicity of PTFE surface caused by ion irradiation

Super-hydrophobic PTFE surfaces were obtained by irradiation of 200 keV Xe⁺ ion with the fluence of 6.2×10¹³ ions/cm². The contact angle of water on such surface is as large as 161±3°. SEM and XPS were used to investigate how the topological and chemical changes affect the wettability of the irradiated surface. Needle like structures at nanometer scale caused by irradiation are considered to be the reason of the super-hydrophobicity. The formation of oxygen containing group and defluorination effect on the treated surface are inferred to have negative contribution to the hydrophobic optimization of PTFE surface.     

Effect of plasma treatment on interface property of BCN/GaN structure

Interface properties of BCN/GaN metal-insulator-semiconductor (MIS) structures are investigated by X-ray photoelectron spectroscopy (XPS) and capacitance versus voltage (C-V) characteristics measurements. The BCN/GaN samples are fabricated by in situ process consisting of plasma treatment and deposition of BCN film in the plasma-assisted chemical vapor deposition (PACVD) apparatus. XPS measurement shows that the oxide formation at the BCN/GaN interface is suppressed by nitrogen (N₂) and hydrogen (H₂) plasma treatment. The interface state density is estimated from C-V characteristics measured at 1 MHz using Terman method. The minimum interface state density appears from 0.2 to 0.7 eV below the conduction band edge of GaN. The minimum value of the interface state density is estimated to be 3.0 × 10¹⁰ eV⁻¹ cm⁻² for the BCN/GaN structure with mixed N₂ and H₂ plasma treatment for 25 min. Even after annealing at 430 °C for 10 min, the interface state density as low as 6.0 × 10¹⁰ eV⁻¹ cm⁻² is maintained.