Ferencz S. Denes

Plasma-Enhanced Synthesis of Bactericidal Quaternary Ammonium Thin Layers on Stainless Steel and Cellulose Surfaces

We have investigated bottom-up chemical synthesis of quaternary ammonium (QA) groups exhibiting antibacterial properties on stainless steel (SS) and filter paper surfaces via nonequilibrium, low-pressure plasma-enhanced functionalization. Ethylenediamine (ED) plasma under suitable conditions generated films rich in secondary and tertiary amines. These functional structures were covalently attached to the SS surface by treating SS with O 2 and hexamethyldisiloxane plasma prior to ED plasma treatment. QA structures were formed by reaction of the plasma-deposited amines with hexyl bromide and subsequently with methyl iodide. Structural compositions were examined by electron spectroscopy for chemical analysis and Fourier transform infrared spectroscopy, and surface topography was investigated with atomic force microscopy and water contact angle measurements. Modified SS surfaces exhibited greater than a 99.9% decrease in Staphylococcus aureus counts and 98% in the case of Klebsiella pneumoniae. The porous filter paper surfaces with immobilized QA groups inactivated 98.7% and 96.8% of S. aureus and K. pneumoniae, respectively. This technique will open up a novel way for the synthesis of stable and very efficient bactericidal surfaces with potential applications in development of advanced medical devices and implants with antimicrobial surfaces.

Surface fluorination of paper in CF4-RF plasma environments

Plasma-based technologies are an exciting alternative for cellulose andpaper modification. Barrier coatings and surface functionalization of celluloseenhances properties and creates new possibilities for cellulose-based products.A parallel plate radio frequency (RF)-plasma reactor was used to modify papersubstrates under discharge parameters such as power, time and pressure. Carbontetrafluoride RF-plasma treatment of paper caused intense fluorination and itwas demonstrated that the fluorination reaction mechanisms can be controlled bythe external plasma parameters. Fluorine contents as high as 51.3% (contactangle=147°) were obtained for the treated cellulose. It was shown that eventreatment times as low as 30 s can generate relative surface fluorineatomic concentrations as high as 30%. High resolution ESCA and ATR-FTIRanalysisindicated covalently bound CFx functional groups with CF4treatment. It was found that under certain experimental conditionssuper-hydrophobic paper surfaces are created by combining the high surfacefluorine atomic concentrations with specific plasma-generated surfacetopographies.

Mechanisms of oxygen- and argon-RF-plasma-induced surface chemistry of cellulose

Pure cellulose samples were Ar- and O2-RF-plasma treated under various external plasma parameter conditions. Plasma induced macromolecular chain and pyranosidic ring cleavage mechanisms are discussed based on survey and high resolution ESCA and ATR-FTIR analysis of cellulose, discharge-exposed cellulose, and discharge-exposed and TFAA and PFPH-derivatized cellulose samples. Analyses have also been made of bothin situ andex situ post plasma oxidation reactions. The new plasma created functionalities were identified and their relative ratios were related to plasma parameters. It was found that Ar plasma treatments initiate reactions mainly associated with the cleavage of C1–C2 linkages leading to the formation of C=O and O-CO-O groups, while O2-plasma treatments are associated with more intense pyranosidic ring (C-O-C bonds) splitting mechanisms. As a result of our detailed investigation of the high resolution C1s spectra of cellulose and carbohydrates we have reassigned the nonequivalent carbon bond affiliation (C-OH, C-O-C, and C-C) at 285–287 eV.

Influence of RF-Cold Plasma Treatment on the Surface Properties of Paper

Abstract Unprinted, unsized, and sized security papers (SP) were treated under SiCl4−, O2−, and CF4-cold plasma conditions. The plasma treatments were carried out in a stainless steel, parallel plate RF (30 kHz) reactor. The influence of plasma parameters, such as RF power, pressure, and treatment time, on the surface properties of plasma-modified security paper was examined. The newly gained surface characteristics were evaluated by Wilhelmy wettability measurements, x-ray photoelectron spectroscopy (ESCA), and scanning electron microscopy (SEM). Statistical experimental designs were used to understand the interactive effects of the plasma parameters. It was found that short treatment times and low RF power values produced the highest wettability with both SiCl4 and O2 plasmas regardless of the sizing. Printing and durability characteristics of the plasma-treated substrates were equivalent or superior to the standard samples. Mechanisms of plasma-induced surface modifications are discussed for the paper ...

Improvement of bonding between cellulose and polypropylene by plasma treatment

Plasma treatments can be utilized to upgrade the value of lignocellulosic materials for applications such as biobased composites. Poor adhesion in biobased composites is caused by incompatibility between polar cellulosics and non-polar thermoplastics. Plasma modification of both cellulose and polypropylene was evaluated by a T-peel test for improved compatibility and adhesion between these materials. Oxygen and argon plasmas were used to modify the surface of polypropylene films, while a cyclohexane plasma was used to modify the cellulose surface through deposition of a hydrophobic polymer layer. For plasma treatment of polypropylene, changes in power input had a greater effect on adhesion than changes in pressure. Surface oxidation and increased acid/base characteristics were found on both argon- and oxygen-plasma-treated polypropylene based on ESCA and wetting measurements. With the non-reactive argon plasma the persistence of reactive species, such as free radicals, was very important for enhanced adhesion. The amount of polar carbonyl groups introduced onto the surface was also an important factor for adhesion improvement. Modification of the cellulose (filter paper) surface to a hydrophobic character with a cyclohexane plasma did not improve adhesion to polypropylene.

Surface modification of polypropylene under argon and oxygen-RF-plasma conditions

Polypropylene fabrics samples were surface functionalized under Ar and O2 RF plasma conditions. Survey and high resolution photoelectron spectroscopy and attenuated total reflectance FTIR comparative evaluation of virgin and plasma treated substrat surfaces, and their pentafluorophenyl hydrazine-derivatized correspondents, indicate that both Ar and O2-discharge treated PP surfaces undergo intense oxidation. C=O, O−C=O, and C−O linkages were identified on both inert and reactive gas plasma exposed surfaces. It was found that the relative surface atomic concentrations and the relative ratios of newly created functionalities are controlled by the external plasma parameters (RF power and treatment time). The oxidation of Ar-plasma treated surfaces has been related toex situ post plasma mechanisms. Dynamic contact angle measurements from unmodified and plasma exposed substrates demonstrated the presence of increased surface polarity, and its dependence on plasma parameters. AFM evaluations of plasma treated samples indicate the presence of rough surface morphologies.

HMDSO-plasma modification of polypropylene fabrics

Abstract A hexamethyldisiloxane (HMDSO)-RF plasma was used to treat polypropylene (PP) fabrics to achieve an inorganic type surface. The properties of the plasma modified PP were investigated through demand wettability and contact angle techniques. ESCA and ATR-IR spectroscopy indicated the presence of SiOSi and SiOC based structures. The influence of treatment time on the level of deposition and surface atomic composition was established. Plasma induced molecular fragmentation of HMDSO was determined through GC-MS and high resolution MS analyses of the molecular structures produced from recombination of active species, in the cold trap.

Immobilization of papain on cold-plasma functionalized polyethylene and glass surfaces

Polyethylene and glass surfaces were functionalized under dichlorosilane-RF-cold-plasma environments and were employed as substrates for further in situ derivatization reactions and immobilization of papain. Surface functionality changes of RF-plasma-exposed surfaces were monitored under 40 kHz continuous discharge environments. The nature and morphology of derivatized substrates and the substrates bearing the immobilized enzyme were analyzed using survey and high resolution ESCA, ATR-FTIR, and fluorescence of chemical derivatization techniques. Spacer molecules intercalated between the substrates and the enzyme significantly increased the enzyme activity (comparable with the that of the free enzyme). Computer-aided conformational modeling of the substrate-spacer systems corroborated with experimental data indicated that an optimal distance might exist between the enzyme and the substrate. The activity of free and immobilized papain was monitored using benzoyl arginine ethyl ester assay. The pH data were recorded every 0.3 s over 25 min. The Michaelis-Menten kinetic constants were evaluated for immobilized enzymes. It was shown, that the immobilized papain retains most of its activity after several washing/assay cycles.

Plasma synthesis of carbon magnetic nanoparticles and immobilization of doxorubicin for targeted drug delivery

Using dense medium plasma technology, carbon magnetic nanoparticles (CMNP) were synthesized at room temperature and atmospheric pressure. Based on results from X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and scanning electron microscopy, we conclude that these nanoparticles are composed of spherical particles, 40–50 nm in diameter, with iron/iron oxide particles dispersed in a carbon-based host-structure. Thermal gravimetry/differential thermal gravimetry analysis shows these nanoparticles are stable to temperatures as high as 600°C. The synthesized CMNP were treated by argon-plasma, aminated with ethylene diamine and subsequently activated by generating aldehyde groups on them. Free doxorubicin (DOX) molecules were then immobilized onto the surfaces of activated CMNP particles to form CMNP-DOX conjugates. The corresponding loading efficiency was determined. The in vitro antiproliferative activity of immobilized doxorubicin in the conjugates was demonstrated in tumor cell cytotoxicity assays. It is suggested that this CMNP-DOX system can be used for targeted drug-delivery systems.

Using carbon magnetic nanoparticles to target, track, and manipulate dendritic cells.

Dendritic cells (DCs) are crucial in the initiation of immune responses and are primary targets in vaccination. Here, we describe fluorescent, carbon magnetic nanoparticles (CMNPs) within the 20-80 nm size range that are non-toxic and preferentially endocytosed by DCs. These attributes allow for DC tracing in vitro, ex vivo and in vivo, by both fluorescence and MRI. We show that CMNPs conjugated with an array of proteins are able to induce strong immune responses in mice. The addition of TLR ligand, CpG, to the CMNPs along with protein results in both T cell activation, but also a selective IFNgamma response. The magnetism afforded by the CMNPs facilitates a simple DC enrichment ex vivo by magnetic means from both secondary lymphoid organs, and sites of chronic inflammation. The magnetic and fluorescent properties of the CMNPs allow for visualization, recovery, and potentially the facilitation of directed DC migration. These particles may support more efficient immunization protocols or new diagnostic assays to characterize functionalities of DCs from patients.