Alena Reznickova

Grafting of gold nanoparticles and nanorods on plasma-treated polymers by thiols

Grafting of gold nanoparticles and nanorods on the surface of polymers, modified by plasma discharge, is studied with the aim to create structures with potential applications in electronics or tissue engineering. Surfaces of polyethyleneterephthalate and polytetrafluoroethylene were modified by plasma discharge and subsequently, grafted with 2-mercaptoethanol, 4,4′-biphenyldithiol, and cysteamine. The thiols are expected to be fixed via one of –OH, –SH or –NH2 groups to reactive places on the polymer surface created by the plasma treatment. “Free” –SH groups are allowed to interact (graft) with gold nanoparticles and nanorods. Gold nano-objects were characterized before grafting by transmission electron microscopy and UV–Vis spectroscopy. X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and electrokinetic analysis (zeta potential determination) were used for the characterization of polymer surface at different modification phases. It was proved by FTIR and XPS measurements that the thiols were chemically bonded on the surface of the plasma-treated polymers, and they mediate subsequent grafting of the gold nano-objects. On the surfaces, modified polymers were indicated some objects by AFM, size of which was dramatically larger in comparison with that of original nanoparticles and nanorods. This result and the other results of UV–Vis spectroscopy indicate an aggregation of deposited gold nano-objects.

Enhanced adherence of mouse fibroblast and vascular cells to plasma modified polyethylene.

Since the last decade, tissue engineering has shown a sensational promise in providing more viable alternatives to surgical procedures for harvested tissues, implants and prostheses. Biomedical polymers, such as low-density polyethylene (LDPE), high-density polyethylene (HDPE) and ultra-high molecular weight polyethylene (UHMWPE), were activated by Ar plasma discharge. Degradation of polymer chains was examined by determination of the thickness of ablated layer. The amount of an ablated polymer layer was measured by gravimetry. Contact angle, measured by goniometry, was studied as a function of plasma exposure and post-exposure aging times. Chemical structure of modified polymers was characterized by angle resolved X-ray photoelectron spectroscopy. Surface chemistry and polarity of the samples were investigated by electrokinetic analysis. Changes in surface morphology were followed using atomic force microscopy. Cytocompatibility of plasma activated polyethylene foils was studied using two distinct model cell lines; VSMCs (vascular smooth muscle cells) as a model for vascular graft testing and connective tissue cells L929 (mouse fibroblasts) approved for standardized material cytotoxicity testing. Specifically, the cell number, morphology, and metabolic activity of the adhered and proliferated cells on the polyethylene matrices were studied in vitro. It was found that the plasma treatment caused ablation of the polymers, resulting in dramatic changes in their surface morphology and roughness. ARXPS and electrokinetic measurements revealed oxidation of the polymer surface. It was found that plasma activation has a positive effect on the adhesion and proliferation of VSMCs and L929 cells.

Gold nanoparticles deposited on glass: physicochemical characterization and cytocompatibility

Properties of gold films sputtered under different conditions onto borosilicate glass substrate were studied. Mean thickness of sputtered gold film was measured by gravimetry, and film contact angle was determined by goniometry. Surface morphology was examined by atomic force microscopy, and electrical sheet resistance was determined by two-point technique. The samples were seeded with rat vascular smooth muscle cells, and their adhesion and proliferation were studied. Gold depositions lead to dramatical changes in the surface morphology and roughness in comparison to pristine substrate. For sputtered gold structures, the rapid decline of the sheet resistance appears on structures deposited for the times above 100 s. The thickness of deposited gold nanoparticles/layer is an increasing function of sputtering time and current. AFM images prove the creation of separated gold islands in the initial deposition phase and a continuous gold coverage for longer deposition times. Gold deposition has a positive effect on the proliferation of vascular smooth muscle cells. Largest number of cells was observed on sample sputtered with gold for 20 s and at the discharge current of 40 mA. This sample exhibits lowest contact angle, low relative roughness, and only mild increase of electrical conductivity.

Tailoring of PEEK bioactivity for improved cell interaction: plasma treatment in action

Despite the extensive use of polyetheretherketone (PEEK) in biomedical applications, information about cell adhesion on this biomaterial is limited. This study focuses on PEEK tuned by argon plasma treatment with the aim to enhance its wettability and cytocompatibility. Changes in surface properties of the plasma treated surface were studied in relation to the adhesion, proliferation and metabolic activity of mouse fibroblasts (L929) and human osteoblast (U-2 OS) in vitro. Moreover, the expression profiles of two proteins (talin 1 and vinculin) responsible for cell adhesion, were determined at 2 time points in dependence on the PEEK treatment. Plasma treatment increased the surface wettability of PEEK and led to changes in its surface morphology and chemistry. The XPS method showed a decrease in carbon content and augmentation of oxygen concentration with increasing effect of the plasma. Plasma treatment of PEEK significantly enhanced cell adhesion, proliferation and metabolic activity of both cell lines when compared to pristine PEEK. Moreover, special attention was devoted to filopodia of L929 cell adhered on PEEK studied by means of scanning electron microscopy. The most abundant filopodia were present on PEEK plasma treated for “longer” times.

Immobilization of silver nanoparticles on polyethylene terephthalate

Two different procedures of grafting with silver nanoparticles (AgNP) of polyethylene terephthalate (PET), activated by plasma treatment, are studied. In the first procedure, the PET foil was grafted with biphenyl-4,4′-dithiol and subsequently with silver nanoparticles. In the second one, the PET foil was grafted with silver nanoparticles previously coated with the same dithiol. X-ray photoelectron spectroscopy and electrokinetic analysis were used for characterization of the polymer surface at different modification steps. Silver nanoparticles were characterized by ultraviolet-visible spectroscopy and by transmission electron microscopy (TEM). The first procedure was found to be more effective. It was proved that the dithiol was chemically bonded to the surface of the plasma-activated PET and that it mediates subsequent grafting of the silver nanoparticles. AgNP previously coated by dithiol bonded to the PET surface much less.

Copper–gold sandwich structures on PE and PET and their SERS enhancement effect

A Surface Enhanced Raman Spectroscopy (SERS) system with the coupling between surface plasmon polaritons (SPPs) supported by a gold grating and localized surface plasmons (LSPs) excited on grafted copper nanoparticles (CuNPs) was designed and characterized. The excitation of copper nanoparticles–molecules–gold layer sandwich structures was studied under 633 nm wavelength irradiation. Rhodamine 6G (R6G) molecules were added onto SERS substrates and located above and between the CuNPs. Prepared samples were studied by several experimental techniques: goniometry, X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), atomic force microscopy (AFM) and electrokinetic analysis. Aging of the modified PE and PET was accompanied by an increase in the contact angle, which was due to a reorientation of the molecular polar segments produced during the plasma treatment. XPS and zeta potential measurements indicated that the thiols were chemically bonded to the gold coated polymer surfaces and that the thiols mediate subsequent grafting of Cu nanoparticles. Both XPS and EDS analyses revealed that a higher concentration of grafted copper nanoparticles was achieved on the PET substrate. EDS showed that Cu nanoparticles are homogeneously distributed over the whole polymer surface. The enhancement factor was higher for PE (1.7 × 103) compared to PET (0.9 × 102).

Preparation and characterization of silver nanoparticles in methyl cellulose matrix and their antibacterial activity

In this work we present in situ preparation of silver nanoparticles (NPs) by reduction of silver nitrate by methyl cellulose (MC). The aim of this study was to prepare a stable solution of MC-Ag, convert it to solid film, redissolve it and determine how this process influences the form and properties of the prepared NPs. MC was analysed by UV–vis spectrometry, transmission electron microscopy and X-ray photoelectron spectroscopy; it was studied in forms of a solution and as a solid film. We also evaluated the antibacterial activity and material properties of prepared films. Our results indicate that the size and distribution of particles are not negatively influenced by the conversion process. These findings can be used for preparation of antibacterial films or as a way of nanoparticle storage.

Physicochemical properties of gold nanostructures deposited on glass

Properties of gold films sputtered onto borosilicate glass substrate were studied. UV-Vis absorption spectra were used to investigate optical parameters. XRD analysis provided information about the gold crystalline nanostructure, the texture, and lattice parameter and biaxial tension was also determined by the XRD method.The surface morphology was examined by atomic force microscopy (AFM); chemical structure of sputtered gold nanostructures was examined by X-ray photoelectron spectroscopy (ARXPS). The gold crystallites are preferentially [111] oriented on the sputtered samples. Gold deposition leads to dramatic changes in the surface morphology in comparison to pristine glass substrate. Oxygen is not incorporated into the gold layer during gold deposition. Experimental data on lattice parameter were also confirmed by theoretical investigations of nanoclusters using tight-binding potentials.