Plasma Polymerized Acrylic Acid Research Articles

Electron Beam Lithography Nanopatterning of Plasma Polymers

AbstractChemically patterned surfaces for biotechnology applications often require sub‐micron patterns to match specific sub‐cellular structures and control the presentation of proteins to single cell arrays. Plasma polymer coatings are used extensively in the biotechnology sector for biomaterials, cell culture and tissue engineering, but their patterning has not been investigated at the sub‐micron level. The resolution limit of plasma polymerized patterns with designed line widths of 900 to 20 nm is investigated via dual chemistry patterns of plasma polymerized acrylic acid and allylamine created with poly (methyl methacrylate) resist and electron beam lithography (EBL). Line widths are characterized via scanning electron microscopy and atomic force microscopy with surface chemistry analysis via time‐of‐flight secondary‐ion mass spectrometry (ToF‐SIMS). The smallest line width measured is 29 nm for a designed line width of 20 nm. High‐resolution nanoscale imaging is achieved using ToF‐SIMS, with lines down to ≈60 nm in width visible. This work demonstrates the successful fabrication and characterization of sub 100 nm dual plasma polymer patterns using EBL, establishing a clear route for large scale production of plasma polymerized nanopatterning.

Improving the effects of plasma polymerization on carbon fiber using a surface modification pretreatment

Plasma and electrochemical treatments of carbon fibers for enhanced properties are often presented in opposition to each other. This work demonstrates the combination of these methodologies through the electrochemical attachment of nitroaryl moieties to the surface of the carbon fiber, prior to the deposition of plasma polymerized acrylic acid to the surface. Notably, the tensile strength of fibers having undergone both surface modification and plasma polymerization showed a significant increase (3.76 ± 0.08 GPa), relative to control fibers (3.31 ± 0.11 GPa), while plasma polymerization alone showed no change (3.39 ± 0.09 GPa). Additional benefits resulting from both treatments were observed when determining the fiber-to-matrix adhesion. Plasma polymerization of acrylic acid alone returned a 49% increase in interfacial shear strength (IFSS) compared to control (28.3 ± 1.2 MPa vs 18.9 ± 1.2 MPa, respectively). While the presence of nitrophenyl groups on the fiber prior to polymerization conferred an additional 24% improvement over plasma polymerization alone and a 73% improvement relative to control fibers (32.7 ± 0.5 MPa vs 18.9 ± 1.2 MPa, respectively). Finally, we present the first comparison of scanning electron microscopy (SEM) and helium ion microscopy (HIM) to visualize polymers on the carbon fiber surface. HIM shows a clear advantage over conventional SEM in visualizing non-conductive coatings on carbon fibers. Analysis of the samples by X-ray photoelectron spectroscopy (XPS) confirmed the desired chemistry had been imparted onto the surface, consistent with the plasma-polymerized acrylic acid coating and presence of nitro-aryl moieties.

Exploiting Reactor Geometry to Manipulate the Properties of Plasma Polymerized Acrylic Acid Films.

A number of different reactor geometries can be used to deposit plasma polymer films containing specific functional groups and result in films with differing properties. Plasma polymerization was carried out in a low-pressure custom-built stainless steel T-shaped reactor using a radio frequency generator. The internal aluminium disk electrode was positioned in two different geometries: parallel and perpendicular to the samples at varying distances to demonstrate the effect of varying the electrode position and distance from the electrode on the properties of plasma polymerized acrylic acid (ppAAc) films. The surface chemistry and film thickness before and after aqueous immersion were analysed via X-ray photoelectron spectroscopy and spectroscopic ellipsometry, respectively. For a perpendicular electrode, the ppAAc film thicknesses and aqueous stability decreased while the COOH/R group concentrations increased as the distance from the electrode increased due to decreased fragmentation. For films deposited at similar distances from the electrode, those deposited with the parallel electrode were thicker, had lower COOH/R group concentrations and greater aqueous stability. These results demonstrate the necessity of having a well characterized plasma reactor to enable the deposition of films with specific properties and how reactor geometry can be exploited to tailor film properties.

Multitechnique investigation into the aqueous behavior of plasma polymers.

Plasma polymers are often used in applications requiring aqueous immersion; therefore, it is important to understand how this exposure affects the physical and chemical properties of the films. Three different plasma polymer films were deposited at different distances from the electrode, and the film properties were characterized using contact angle, ellipsometry, and x-ray photoelectron spectroscopy. The film behaviors in aqueous solutions were studied via quartz crystal microbalance with dissipation (QCM-D). Exposure to buffer solutions produced significant swelling of the plasma polymerized acrylic acid films, with swelling increasing with distance from the powered electrode, results that could be correlated with changes in film chemistry. Plasma polymerized octadiene and allylamine exhibited little swelling. These films exhibited changes in thickness and contact angle with respect to distance from the electrode, but this had little influence on their behavior in aqueous solution. By combining QCM-D with the more traditional surface chemical analysis techniques, the authors have been able to explore both swelling behavior and the effect that sample position and thus deposition parameters have on film properties and aqueous behavior. This approach gives the authors the basis to define deposition parameters to assist the engineering of thin films for applications such as biosensing and tissue engineering applications where specific chemistries and film behaviors are desired.

Properties, ageing behavior and stability of bipolar films containing nano-layers of allylamine and acrylic acid plasma polymers

In this work, a dielectric barrier discharge (DBD) has been used for the deposition of bipolar films containing alternating nano-layers of plasma polymerized allylamine (PPAam) and acrylic acid (PPAac). Various films were obtained by varying the single-layer thickness of each plasma polymer while maintaining a constant total film thickness and two kinds of films were fabricated via different depositing sequences (PPAam/Aac and PPAac/Aam). Films properties, ageing in air and stability in water over a 7 days period were investigated. Results showed that, COO− and NH3+ polar entities, generated from the interaction of PPAam and PPAac, are present in the bipolar films. Concerning the films stability, the different reaction mechanisms involved in the formation of each kind of films resulted in a higher amount of polar groups in the PPAam/Aac films; this conferred these films a higher stability than PPAac/Aam. Concerning the films ageing behavior, all prepared samples underwent some kind of ageing which was found to be dependent on the deposition sequence. Results also showed that bipolar coatings exhibited better cell-material interactions compared to PPAam and PPAac films; with a better cell viability observed on PPAam/Aac coatings after 1 and 7 days culture.

PH-dependent lipid vesicle interactions with plasma polymerized thin films.

Model lipid vesicle and supported lipid bilayer (SLB) systems are used in a variety of applications including biosensing, cell membrane mimics, and drug delivery. Exposure of a surface to a vesicle solution provides a straightforward method for creating such systems via vesicle adsorption and collapse. However, this process is complex and the relationship between the surface physicochemical properties and vesicle collapse is poorly understood. Plasma polymers are thin conformal films that can be applied to a variety of materials to modify surface properties. This paper uses quartz crystal microbalance with dissipation and fluorescence recovery after photobleaching (FRAP) to explore lipid vesicle interactions with plasma polymerized acrylic acid (ppAAc), allylamine (ppAAm), and ppAAc/ppAAm micropatterns. Vesicle interactions were dependent on plasma polymer chemistry and pH of the buffer solution. Vesicles readily and stably adsorbed to ppAAm over a wide pH range. ppAAc demonstrated limited interactions at pH 7 and vesicle adsorption at pH 4. Vesicle collapse and SLB formation could be induced using a pH change. FRAP was used to explore the fluidity of the lipid structures on both the patterned and unpatterned plasma polymer films. On ppAAm/ppAAc micropatterns, pH transitions combined with the presence of chemically distinct regions on the same substrate enabled immobile lipid islands on ppAAc to be surrounded by fluid lipid regions on ppAAm. This work demonstrates that plasma polymer films could enable spatially controlled vesicle adsorption and SLB formation on a wide variety of different substrates.

A stability study of plasma polymerized acrylic acid films

A medium pressure parallel-plate DBD set-up was used for the deposition of carboxylic acid-rich films using acrylic acid as precursor. A variety of discharge powers (21–33W) and monomer flow rates (0.25–0.5g/h) were applied to develop a range of coatings from highly unstable to completely stable in aqueous solutions. FT-IR and XPS were used to identify which coatings were stable under dynamic incubation conditions and what influence plasma operating parameters had on functional group preservation. White light interferometry was also used to calculate deposition rates (66–126nm/min) and to determine the deposition regime (monomer deficient). Human foreskin fibroblasts were seeded onto the complete range of investigated samples and the effects of coating (in)stability on cell adhesion, viability and morphology were systematically studied. Results showed that the 27 W-0.25g/h treatment conditions resulted in the most stable coatings. Although a concentration of only 0.7% of carboxylic acid groups was found under these experimental conditions, the positive effects of a highly acid-rich surface were still maintained as cell-material interactions were significantly enhanced.

Inhomogeneous Growth of Micrometer Thick Plasma Polymerized Films.

Plasma polymerization is traditionally recognized as a homogeneous film-forming technique. It is nevertheless reasonable to ask whether micrometer thick plasma polymerized structures are really homogeneous across the film thickness. Studying the properties of the interfacial, near-the-substrate (NTS) region in plasma polymer films represents particular experimental challenges due to the inaccessibility of the buried layers. In this investigation, a novel non-destructive approach has been utilized to evaluate the homogeneity of plasma polymerized acrylic acid (PPAc) and 1,7-octadiene (PPOD) films in a single measurement. Studying the variations of refractive index throughout the depth of the films was facilitated by a home-built surface plasmon resonance (SPR)/optical waveguide (OWG) spectroscopy setup. It has been shown that the NTS layer of both PPAc and PPOD films exhibits a significantly lower refractive index than the bulk of the film that is believed to indicate a higher concentration of internal voids. Our results provide new insights into the growth mechanisms of plasma polymer films and challenge the traditional view that considers plasma polymers as homogeneous and continuous structures.

Study of the adhesive properties versus stability/aging of hernia repair meshes after deposition of RF activated plasma polymerized acrylic acid coating

In order to confer adhesive properties to commercial polypropylene (PP) meshes, a surface plasma-induced deposition of poly-(acrylic acid) (PPAA) is performed. Once biomaterials were functionalized, different post-deposition treatments (i.e. water washing and/or thermal treatments) were investigated with the aim of monitoring the coating degradation (and therefore the loss of adhesion) after 3months of aging in both humid/oxidant (air) and inert (nitrogen) atmospheres. A wide physicochemical characterization was carried out in order to evaluate the functionalization effectiveness and the adhesive coating homogeneity by means of static water drop shape analysis and several spectroscopies (namely, FTIR, UV–Visible and X-ray Photoemission Spectroscopy). The modification of the adhesion properties after post-deposition treatments as well as aging under different storage atmospheres were investigated by means of Atomic Force Microscopy (AFM) used in Force/Distance (F/D) mode. This technique confirms itself as a powerful tool for unveiling the surface adhesion capacity as well as the homogeneity of the functional coatings along the fibers. Results obtained evidenced that post-deposition treatments are mandatory in order to remove all oligomers produced during the plasma-treatment, whereas aging tests evidenced that these devices can be simply stored in presence of air for at least three months without a meaningful degradation of the original properties.

Optimization and characterization of a homogeneous carboxylic surface functionalization for silicon-based biosensing

A well-organized immobilization of bio-receptors is a crucial goal in biosensing, especially to achieve high reproducibility, sensitivity and specificity. These requirements are usually attained with a controlled chemical/biochemical functionalization that creates a stable layer on a sensor surface. In this work, a chemical modification protocol for silicon-based surfaces to be applied in biosensing devices is presented. An anhydrous silanization step through 3-aminopropylsilane (APTES), followed by a further derivatization with succinic anhydride (SA), is optimized to generate an ordered flat layer of carboxylic groups. The properties of APTES/SA modified surface were compared with a functionalization in which glutaraldehyde (GA) is used as crosslinker instead of SA, in order to have a comparison with an established and largely applied procedure. Moreover, a functionalization based on the controlled deposition of a plasma polymerized acrylic acid (PPAA) thin film was used as a reference for carboxylic reactivity. Advantages and drawbacks of the considered methods are highlighted, through physico-chemical characterizations (OCA, XPS, and AFM) and by means of a functional Protein G/Antibody immunoassay. These analyses reveal that the most homogeneous, reproducible and active surface is achieved by using the optimized APTES/SA coupling.

Acrylic acid plasma polymerized poly(3-hydroxybutyrate) membranes for methanol/MTBE separation by pervaporation

Plasma polymerized acrylic acid (AA) thin films on poly(3-hydroxybutyrate) (PHB) membranes were evaluated as composite membranes for methanol/methyl tert-butyl ether (MTBE) separation by pervaporation (PV). Composite membranes were prepared in an inductively coupled radiofrequency plasma reactor. Experiments were performed at different powers (7.2 to 29.2W) and pressures, using pure AA monomer, as well as AA/air and AA/argon mixtures. Depositions chemical characteristics were determined through FTIR spectroscopy, hydrophilic character through contact angle measurements, and SEM images were also taken to analyze surface morphology. In PV measurements, membranes were methanol selective; the separation factor exceeded that of pure PHB membranes in all cases. Fluxes were lower than the original membrane but the performance separation index (PSI) was always higher. Results presented in terms of permeability were between 660 and 4045barrer for methanol, while for MTBE they were markedly lower, between 10.5 and 57.7barrer. These large differences in permeabilities caused high selectivities which ranged from 24 to 79.

Reaction of CO2Gas with (radicals in) Plasma-Polymerized Acrylic Acid (and Formation of COOH-Rich Polymer Layers)

In contrast to most of the existing literature on plasma polymerization of acrylic acid (AA), not only the chemical structure and film thickness of the deposits were studied, but also a new way to obtain COOH-rich surfaces were studied. This is an important aspect when applying the obtained coatings for biomedical and electronics applications. Therefore, acrylic acid/CO2 polymer films with a thickness of ca. 150 nm were deposited in the pulsed plasma regime onto polyethylene and aluminum. Their structure–property relationships were studied in dependence on the mixture ratio of acrylic acid monomer and CO2 gas. The influence of the CO2 gas on the regularity and functionality of plasma-deposited poly(acrylic acid) (PAA) was studied in detail using bulk-sensitive (FTIR) as well as surface-sensitive methods, such as X-ray photoelectron spectroscopy. Results obtained show, in presence of a small amount of CO2 gas within the acrylic acid plasma, a structure of PAA with high concentration of COOH groups was estimated. A polymer network is obtained with an increasing abundance of branched groups for AA/CO2 with increasing CO2 gas in the mixture.

Immobilization and controlled release of drug using plasma polymerized thin film

In this study, plasma polymerization of acrylic acid was employed to immobilize drug and control its release. Doxorubicin (DOX) was immobilized covalently on the glass surface deposited with plasma polymerized acrylic acid (PPAAc) thin film containing the carboxylic group. At first, the PPAAc thin film was coated on a glass surface at a pressure of 1.33Pa and radio frequency (RF) discharge power of 20W for 10min. DOX was immobilized on the PPAAc deposition in a two environment of phosphate buffer saline (PBS) and dimethyl sulfoxide (DMSO) solutions. The DOX immobilized surface was characterized by scanning electron microscope, atomic force microscope and attenuated total reflection Fourier transform infrared spectroscopy. The DOX molecules were more immobilized in PBS than DMSO solution. The different immobilization and release profiles of DOX result from the solubility of hydrophobic DOX in aqueous and organic solutions. Second, in order to control the release of the drug, PPAAc thin film was covered over DOX dispersed layer. Different thicknesses and cross-linked PPAAc thin films by adjusting deposition time and RF discharge power were covered on the DOX layer dispersed. PPAAc thin film coated DOX layer reduced the release rate of DOX. The thickness control of plasma deposition allows controlling the release rate of drug.

Fabrication of a platform to isolate the influences of surface nanotopography from chemistry on bacterial attachment and growth.

Billions of dollars are spent annually worldwide to combat the adverse effects of bacterial attachment and biofilm formation in industries as varied as maritime, food, and health. While advances in the fabrication of antifouling surfaces have been reported recently, a number of the essential aspects responsible for the formation of biofilms remain unresolved, including the important initial stages of bacterial attachment to a substrate surface. The reduction of bacterial attachment to surfaces is a key concept in the prevention or minimization of biofilm formation. The chemical and physical characteristics of both the substrate and bacteria are important in understanding the attachment process, but substrate modification is likely the most practical route to enable the extent of bacterial attachment taking place to be effectively controlled. The microtopography and chemistry of the surface are known to influence bacterial attachment. The role of surface chemistry versus nanotopography and their interplay, however, remain unclear. Most methods used for imparting nanotopographical patterns onto a surface also induce changes in the surface chemistry and vice versa. In this study, the authors combine colloidal lithography and plasma polymerization to fabricate homogeneous, reproducible, and periodic nanotopographies with a controllable surface chemistry. The attachment of Escherichia coli bacteria onto carboxyl (plasma polymerized acrylic acid, ppAAc) and hydrocarbon (plasma polymerized octadiene, ppOct) rich plasma polymer films on either flat or colloidal array surfaces revealed that the surface chemistry plays a critical role in bacterial attachment, whereas the effect of surface nanotopography on the bacterial attachment appears to be more difficult to define. This platform represents a promising approach to allow a greater understanding of the role that surface chemistry and nanotopography play on bacterial attachment and the subsequent biofouling of the surface.

In Vitro Antibacterial Activity of Nano Silver Ion Substituted Poly Acrylic Acid Films on Titanium by Plasma Polymerization.

Antibacterial activity of oral pathogens such as Streptococcus mutans, Streptococcus sobrinus when silver ion immobilized on commercially pure (CP) titanium (Ti) surface was investigated in this study. Plasma-polymerized acrylic acid to have carboxyl group was deposited on CP-Ti surface and then ion-exchanged with Ag+ ions in 0.1 N AgNO3. In anti-adherent experiment, antibacterial activity was tested using broth culture methods. The biofilm formation assay was performed using semi-defined biofilm medium with sucrose. The silver coated CP-Ti completely inhibited the growth of S. mutans and S. sobrinus. In addition, the biofilm formation was significantly inhibited in silver-coated CP-Ti group.

Semiconductor nanorod-carbon nanotube biomimetic films for wire-free photostimulation of blind retinas.

We report the development of a semiconductor nanorod-carbon nanotube based platform for wire-free, light induced retina stimulation. A plasma polymerized acrylic acid midlayer was used to achieve covalent conjugation of semiconductor nanorods directly onto neuro-adhesive, three-dimensional carbon nanotube surfaces. Photocurrent, photovoltage, and fluorescence lifetime measurements validate efficient charge transfer between the nanorods and the carbon nanotube films. Successful stimulation of a light-insensitive chick retina suggests the potential use of this novel platform in future artificial retina applications.

Plasma Surface Modification for Immobilization of Bone Morphogenic Protein-2 on Polycaprolactone Scaffolds

The immobilization of recombinant human bone formation protein-2 (rhBMP-2) on polycaprolactone (PCL) scaffolds was performed by plasma polymerization. RhBMP-2, which induces osteoblast differentiation in various cell types, is a growth factor that plays an important role in bone formation and repair. The surface of the PCL scaffold was functionalized with the carboxyl groups of plasma-polymerized acrylic acid (PPAA) thin films. Plasma polymerization was carried out at a discharge power of 60 W at an acrylic acid flow rate of 7 sccm for 5 min. The PPAA thin film exhibited moderate hydrophilic properties and possessed a high density of carboxyl groups. Carboxyl groups and rhBMP-2 on the PCL scaffolds surface were identified by attenuated total reflection Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy, respectively. The alkaline phosphatase activity assay showed that the rhBMP-2 immobilized PCL scaffold increased the level of MG-63 cell differentiation. Plasma surface modification for the preparation of biomaterials, such as biofunctionalized polymer scaffolds, can be used for the binding of bioactive molecules in tissue engineering.

Effect of plasma surface functionalization on preosteoblast cells spreading and adhesion on a biomimetic hydroxyapatite layer formed on a titanium surface

This study examined the plasma surface modification of biomimetic hydroxyapatite (HAp) formed on a titanium (Ti) surface as well as its influence on the behavior of preosteoblast cells. Ti substrates pre-treated with a plasma-polymerized thin film rich in carboxyl groups were subjected to a biomimetic process in a simulated body fluid solution to synthesize the HAp. The HAp layer grown on Ti substrate was then coated with two types of plasma polymerized acrylic acid and allyl amine thin film. The different types of Ti substrates were characterized by attenuated total reflection Fourier transform infrared spectroscopy, energy dispersive spectroscopy and X-ray diffraction. HAp with a Ca/P ratio from 1.25 to 1.38 was obtained on the Ti substrate and hydrophilic carboxyl (COOH) and amine (NH2) functional groups were introduced to its surface. Scanning electron microscopy was used to observe the surface of the HAp coatings and the morphology of MC3T3-E1 cells. These results showed that the COOH-modified HAp surfaces promoted the cell spreading synergistically by changing the surface morphology and chemical state.NH2 modified HAp had the lowest cell spreading and proliferation compared to HAp and COOH-modified HAp. These results correspond to fluorescein analysis, which showed many more cell spreading of COOH/HAp/Ti surface compared to HAp and NH2 modified HAp. A MTT assay was used to evaluate cell proliferation. The results showed that the proliferation of MC3T3-E1 cells increased in the order of COOH/HAp/Ti>HAp/Ti>NH2/Ti>Ti, corresponding to the effect of cell spreading for 6 days. The change in morphology and the chemical surface properties of the biomaterial via plasma polymerization can affect the behavior of MC3T3-E1 cells.

Surface Modification of Ultra-high Molecular Weight Polyethylene Membranes Using Underwater Plasma Polymerization

Ultra-high molecular weight polyethylene membranes were modified and subsequently polymer coated using the underwater plasma produced by glow discharge electrolysis. This plasma pretreatment generated various O-functional groups among them OH groups have dominated. This modified inner (pore) surface of membranes showed complete wetting and strong adhesion to a hydrogel copolymerized by glow discharge electrolysis also. The deposited hydrogel consists of plasma polymerized acrylic acid crosslinked by copolymerization with the bifunctional N,N′-methylenebis(acrylamide). Tuning the hydrogel hydrophilicity and bio-compatibility poly(ethylene glycol) was chemically inserted into the copolymer. Such saturated polymer could only be inserted on a non-classic way by (partial) fragmentation and recombination thus demonstrating the exotic properties of the underwater plasma. The modification of membrane was achieved by squeezing the reactive plasma solution into the pores by plasma-induced shock waves and supported by intense stirring. The deposited copolymer hydrogel has filled all pores also in the inner of membrane as shown by scanning electron microscopy of cross-sections. The copolymer shows the characteristic units of acrylic acid and ethylene glycol as demonstrated by infrared spectroscopy. A minimum loss in carboxylic groups of acrylic acid during the plasma polymerization process was confirmed by X-ray photoelectron spectroscopy. Additional cell adhesion tests on copolymer coated polyethylene using IEC-6 cells demonstrated the bio-compatibility of the plasma-deposited hydrogel.

Effects of gas atmospheres on poly(lactic acid) film in acrylic acid plasma treatment

Plasma polymerized acrylic acid (AA) coatings were deposited on poly(lactic acid) (PLA) films in various gas atmospheres during the pre-treatment of PLA and the deposition of AA, respectively. Therefore, this work was twofold: the argon pretreated PLA films followed by a deposition in argon were investigated against the mixture of argon and oxygen pretreated ones under the same deposition conditions; the plasma deposition of AA operating in different atmospheres (argon, oxygen and nitrogen) was employed to modify the pretreated PLA in oxygen. Chemical and physical changes on the plasma-treated surfaces were examined using contact angle, X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM) and attenuated total reflection infrared (ATR-FTIR) analysis. The results showed that the discharge gas can have a significant influence on the chemical composition of the PLA surfaces: oxygen plasmas introduced oxygen-containing groups in company with surface etching in pretreatment and deposition, while argon discharges was able to achieve much better hydrophilic behavior and high retention ratio of poly(acrylic acid) (PAA) coating before and after washing in water.