Improved Adhesion, Growth and Maturation of Vascular Smooth Muscle Cells on Polyethylene Grafted with Bioactive Molecules and Carbon Particles

High-density polyethylene (PE) foils were modified by an Ar+ plasma discharge and subsequent grafting with biomolecules, namely glycine (Gly), polyethylene glycol (PEG), bovine serum albumin (BSA), colloidal carbon particles (C) or BSA and C (BSA + C). As revealed by atomic force microscopy (AFM), goniometry and Rutherford Backscattering Spectroscopy (RBS), the surface chemical structure and surface morphology of PE changed dramatically after plasma treatment. The contact angle decreased for the samples treated by plasma, mainly in relation to the formation of oxygen structures during plasma irradiation. A further decrease in the contact angle was obvious after glycine and PEG grafting. The increase in oxygen concentration after glycine and PEG grafting proved that the two molecules were chemically linked to the plasma-activated surface. Plasma treatment led to ablation of the PE surface layer, thus the surface morphology was changed and the surface roughness was increased. The materials were then seeded with vascular smooth muscle cells (VSMC) derived from rat aorta and incubated in a DMEM medium with fetal bovine serum. Generally, the cells adhered and grew better on modified rather than on unmodified PE samples. Immunofluorescence showed that focal adhesion plaques containing talin, vinculin and paxillin were most apparent in cells on PE grafted with PEG or BSA + C, and the fibres containing α-actin, β-actin or SM1 and SM2 myosins were thicker, more numerous and more brightly stained in the cells on all modified PE samples than on pristine PE. An enzyme-linked immunosorbent assay (ELISA) revealed increased concentrations of focal adhesion proteins talin and vinculin and also a cytoskeletal protein β-actin in cells on PE modified with BSA + C. A contractile protein α-actin was increased in cells on PE grafted with PEG or Gly. These results showed that PE activated with plasma and subsequently grafted with bioactive molecules and colloidal C particles, especially with PEG and BSA + C, promotes the adhesion, proliferation and phenotypic maturation of VSMC

Wettability and Other Surface Properties of Modified Polymers

Surface wettability is one of the crucial characteristics for determining of a material’s use in specific application. Determination of wettability is based on the measurement of the material surface contact angle. Contact angle is the main parameter that characterizes the drop shape on the solid surface and is also one of the directly measurable properties of the phase interface. In this chapter, the wettability and its related properties of pristine and modified polymer foils will be described. The wettability depends on surface roughness and chemical composition. Changes of these parameters can adjust the values of contact angle and, therefore, wettability. In the case of pristine polymer materials, their wettability is unsuitable for a wide range of applications (such as tissue engineering, printing, and coating). Polymer surfaces can easily be modified by, e.g., plasma discharge, whereas the bulk properties remain unchanged. This modification leads to oxidation of the treated layer and creation of new chemical groups that mainly contain oxygen. Immediately after plasma treatment, the values of the contact angles of the modified polymer significantly decrease. In the case of a specific polymer, the strongly hydrophilic surface is created and leads to total spreading of the water drop. Wettability is strongly dependent on time from modification

Substrate Effects of Noble Metal Nanostructures Prepared by Sputtering

Cathode sputtering is a well-established technique for preparation of metal nanostructures. However, the substrate properties are very important in this process. On glass substrates, there is a difficulty with poor adhesion of the metal layers, but thanks to this, metal nanostructures can be produced using solid state dewetting process. Thin metal films on polymer substrates are strongly influenced by the surface properties of the polymers, which originate in the method of their preparation. A recent focus is direct sputtering of metal nanoparticles (NPs) into liquid substrates and their characterizations and applications. Polyethylene glycol (PEG) is one of the most commonly used liquid, which provides “stealth” character to nanostructures. Recent results in this area are reviewed in this chapter. PEGylated NPs could find application in drug delivery systems, therapy, imaging, biosensing, and tissue regeneration

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

Thin Surface Layer of Plasma Treated Polyethylene

This paper reports on the effect of argon plasma on the high density polyethylene surface. The aim is to alter the surface in a manner and scale resulting in a stronger metal/polymer valence. The specimens are exposed to the direct current discharge, the irradiation time and power being variables. Electron paramagnetic resonance and X-ray photoelectron spectroscopy (EPR and XPS, respectively) are employed to determine the plasma effect. The surface wettability is studied by goniometry. The plasma treatment leads to radical generation and activation of such agents as oxygen, thus the surface wettability is significantly increased. The evolution ofthe treated surface in different media is studied. The influence of an increased oxygen concentration and the storage medium on the concentration gradient within the surface monolayers is proved. The EPR data show a gradual and very slow decrease in the number of radicals present on the treated surface after 2000 h. Also evidence is given for partial dissolution of the treated surface in water.Представлены результаты изучения влияния плазмы аргона на поверхность полиэтилена высокой плотности. Целью исследования является изменение поверхности таким образом, чтобы увеличить валентность ме­талла/полимера. Образцы подвергали воз­действию разряда постоянного тока, при этом время воздействия и мощность являлись переменными величинами. Для опре­деления влияния плазмы использовали электронный парамагнитный резонанс (ЭПР) и фотоэлектронную рентгеновскую спектроскопию. Смачиваемость поверхнос­ти изучали с использованием гониометрии. Плазменная обработка ведет к образованию радикалов и активизации таких реагентов, как кислород и таким образом, значительно увеличивается смачиваемость поверхности. Исследована эволюция обработанной по­верхности в различных средах. Приведено подтверждение влияния повышенной кон­центрации кислорода и среды на градиент концентрации в поверхностных монослоях. Данные ЭПР свидетельствуют о постепен­ном и очень медленном уменьшении коли­чества радикалов на обработанной поверхности после 2000 ч. Приведены также дан­ные о частичном растворении обработанной поверхности в воде

Application of a 2D Molybdenum Telluride in SERS Detection of Biorelevant Molecules

Two-dimensional (2D) transition-metal dichalcogenides have become promising candidates for surface-enhanced Raman spectroscopy (SERS), but currently very few examples of detection of relevant molecules are available. Herein, we show the detection of the lipophilic disease marker beta-sitosterol on few-layered MoTe2 films. The chemical vapor deposition (CVD)-grown films are capable of nanomolar detection, exceeding the performance of alternative noble-metal surfaces. We confirm that the enhancement occurs through the chemical enhancement (CE) mechanism via formation of a surface-analyte complex, which leads to an enhancement factor of approximate to 10(4), as confirmed by Fourier transform infrared (FTIR), UV-vis, and cyclic voltammetry (CV) analyses and density functional theory (DFT) calculations. Low values of signal deviation over a seven-layered MoTe2 film confirms the homogeneity and reproducibility of the results in comparison to noble-metal substrate analogues. Furthermore, beta-sitosterol detection within cell culture media, a minimal loss of signal over 50 days, and the opportunity for sensor regeneration suggest that MoTe2 can become a promising new SERS platform for biosensing.Peer reviewe

Chiral Metafilms and Surface Enhanced Raman Scattering For Enantiomeric Discrimination of Helicoid Nanoparticles

Chiral nanophotonic platforms provide a means of creating near fields with both enhanced asymmetric properties and intensities. They can be exploited for optical measurements that allow enantiomeric discrimination at detection levels greater than 6 orders of magnitude than is achieved with conventional chirally sensitive spectroscopic methods based on circularly polarized light. The optimal approach for exploiting nanophotonic platforms for chiral detection would be to use spectroscopic methods that provide a local probe of changes in the near field environment induced by the presence of chiral species. Here we show that surface enhanced Raman spectroscopy (SERS) is such a local probe of the near field environment. We have used it to achieve enantiomeric discrimination of chiral helicoid nanoparticles deposited on left and right-handed enantiomorphs of a chiral metafilm. Hotter electromagnetic hotspots are created for matched combinations of helicoid and metafilms (left-left and right-right), while mismatched combinations leads to significantly cooler electromagnetic hotspots. This large enantiomeric dependency on hotspot intensity is readily detected using SERS with the aid of an achiral Raman reporter molecule. In effect we have used SERS to distinguish between the different EM environments of the plasmonic diastereomers produced by mixing chiral nanoparticles and metafilms. The work demonstrates that by combining chiral nanophotonic platforms with established SERS strategies new avenues in ultrasensitive chiral detection can be opened

Enhanced Growth and Osteogenic Differentiation of Human Osteoblast-Like Cells on Boron-Doped Nanocrystalline Diamond Thin Films

Intrinsic nanocrystalline diamond (NCD) films have been proven to be promising substrates for the adhesion, growth and osteogenic differentiation of bone-derived cells. To understand the role of various degrees of doping (semiconducting to metallic-like), the NCD films were deposited on silicon substrates by a microwave plasma-enhanced CVD process and their boron doping was achieved by adding trimethylboron to the CH4:H2 gas mixture, the B∶C ratio was 133, 1000 and 6700 ppm. The room temperature electrical resistivity of the films decreased from >10 MΩ (undoped films) to 55 kΩ, 0.6 kΩ, and 0.3 kΩ (doped films with 133, 1000 and 6700 ppm of B, respectively). The increase in the number of human osteoblast-like MG 63 cells in 7-day-old cultures on NCD films was most apparent on the NCD films doped with 133 and 1000 ppm of B (153,000±14,000 and 152,000±10,000 cells/cm2, respectively, compared to 113,000±10,000 cells/cm2 on undoped NCD films). As measured by ELISA per mg of total protein, the cells on NCD with 133 and 1000 ppm of B also contained the highest concentrations of collagen I and alkaline phosphatase, respectively. On the NCD films with 6700 ppm of B, the cells contained the highest concentration of focal adhesion protein vinculin, and the highest amount of collagen I was adsorbed. The concentration of osteocalcin also increased with increasing level of B doping. The cell viability on all tested NCD films was almost 100%. Measurements of the concentration of ICAM-1, i.e. an immunoglobuline adhesion molecule binding inflammatory cells, suggested that the cells on the NCD films did not undergo significant immune activation. Thus, the potential of NCD films for bone tissue regeneration can be further enhanced and tailored by B doping and that B doping up to metallic-like levels is not detrimental for cells

Chiral plasmonic response of 2D Ti3C2Tx flakes: realization and applications

The circularly polarized light sensitive materials response can be reached at plasmon wavelengths through the coupling of intrinsically non-chiral plasmonic nanostructure with chiral organic molecules. As a plasmonic background, the different types of metal nanoparticles of various shapes and sizes are successfully tested and an apparent circular dichroism (CD) signal is measured in both, nanoparticles suspensions and after nanoparticle immobilization in substrate. In this work, the creation of plasmon-active 2D flakes of MXenes (Ti3C2Tx) is proposed, with the apparent CD response at plasmon wavelength, through the coupling of intrinsically non-chiral flakes with helically shaped helicene enantiomers. This work provides the first demonstration of chiral and plasmon-active 2D material, which shows the absorption sensitive to light intrinsic circular polarization even in plasmon wavelengths range. The appearance of the induced CD signal is additionally confirmed by several theoretical calculations. After the experimental and theoretical confirmation of the optical chirality at plasmon wavelengths, the flakes are utilized for the polarization sensitive conversion of light to heat, as well as for polarization dependent triggering of plasmon-assisted chemical transformation

Hydroxyapatite reinforcement of different starch-based polymers affects osteoblast-like cells adhesion/spreading and proliferation

The aim of this study was to determine which, from a range of the starch-based biomaterials, would be more suitable to be used in orthopaedic applications. This included blends of corn starch and ethylene vinyl alcohol (SEVA-C), corn starch and cellulose acetate (SCA), corn starch and polycaprolactone (SPCL) and its composites with increasing percentages of hydroxyapatite (HA). Osteoblast-like cells (SaOs-2) were cultured in direct contact with the polymers and composites and the effect of the incorporation and of increasing percentages of the ceramic in osteoblast adhesion/proliferation was assessed. In the evaluation of cell adhesion and proliferation rate, two variables were considered; cells adhered to the bottom of the tissue culture polystyrene wells (TCPS) and cells adhered to the surface of the materials, in order to distinguish, respectively: (i) the effect of possible degradation products released from the materials to the culture medium and (ii) the effect of the surface properties on the osteoblast-like cells. In addition, the morphology of cells adherent to the surface of the starch-based polymers was analysed and correlated with their topography and with other chemical properties previously evaluated. The proliferation rate was found to differ from blend to blend as well as with the time of culture and with the presence of HA depending on the material. SEVA-C and respective composites systematically presented the higher number of cells comparatively to the other two blends. SPCL composites were found to be less suitable for cell proliferation. The amount of cells quantified after 7 days of culture, both on the surface and on the wells showed a delay in the proliferation of the cells cultured with SPCL composites comparatively to other materials and to TCPS. SCA composites, however, did support cell adhesion but also induce a slight level of toxicity, which results in delayed proliferation on the cells adhered to the wells. Cell morphology on the surface of the materials was also, in almost every case, found to be appropriate. In fact, cells were well adhered and spread on the majority of the surfaces. Thus, starch-based biomaterials can be seen as good substrates for osteoblast-adhesion and proliferation that demonstrates their potential to be used in orthopaedic applications and as bone tissue engineering scaffolds.Fundação para a Ciência e a Tecnologia (FCT