UV Irradiation of Polyethylene Terephthalate and Polypropylene and Detection of Formed Microplastic Particles Down to 1†µm.

The degradation of plastics upon UVC irradiation in aqueous solution and the formation of microplastic (MP) particles were investigated. Polypropylene (PP) and recycled and virgin polyethylene terephthalate (PET) were irradiated with a UV lamp emitting light at 254 nm. Irradiation was performed for 15 and 30 min, respectively, at an intensity of about 0.3 W cm-2 . The formation of MP was studied by Raman spectroscopy. The results showed that MP particles were formed after irradiation and that their number was significantly higher in the recycled PET than in the virgin material. The number of PP MP formed was lower compared to PET and was not significantly different after 15 and 30 min. In addition, ethanol was used as an alternative solvent to investigate how its chemical properties and interactions with UVC irradiation affect the degradation of PET and PP plastics. The use of ethanol and recycled PET resulted in a lower number of MP particles at both irradiation times. When ethanol was used after 30 min of irradiation, significantly more PP MP formed. The different chemical structures of PET and PP combined with the different solvent properties of water and ethanol contribute to the differences in their susceptibility to UVC degradation.

Microwave-Assisted Synthesis of Pt/SnO2 for the Catalytic Reduction of 4-Nitrophenol to 4-Aminophenol.

In this study, we present a new approach for the synthesis of Pt/SnO2 catalysts using microwave radiation. Pt(IV) and Sn(IV) inorganic precursors (H2PtCl6 and SnCl4) and ammonia were used, which allowed the controlled formation of platinum particles on the anisotropic SnO2 support. The synthesized Pt/SnO2 samples are mesoporous and exhibit a reversible physisorption isotherm of type IV. The XRD patterns confirmed the presence of platinum maxima in all Pt/SnO2 samples. The Williamson-Hall diagram showed SnO2 anisotropy with crystallite sizes of ~10 nm along the c-axis (< 00l >) and ~5 nm along the a-axis (< h00 >). SEM analysis revealed anisotropic, urchin-like SnO2 particles. XPS results indicated relatively low average oxidation states of platinum, close to Pt metal. 119Sn Mössbauer spectroscopy indicated electronic interactions between Pt and SnO2 particles. The synthesized samples were used for the catalytic reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) in the presence of excess NaBH4. The catalytic activity of the Pt/SnO2 samples for the reduction of 4-NP to 4-AP was optimized by varying the synthesis parameters and Pt loading. The optimal platinum loading for the reduction of 4-NP to 4-AP on the anisotropic SnO2 support is 5 mol% with an apparent rate constant k = 0.59 × 10-2 s-1. The Pt/SnO2 sample showed exceptional reusability and retained an efficiency of 81.4% after ten cycles.

Antifungal Effect of Polymethyl Methacrylate Resin Base with Embedded Au Nanoparticles.

Full and partial restorations in dentistry must replicate the characteristics of the patient's natural teeth. Materials must have good mechanical properties and be non-toxic and biocompatible. Microbes, which can form biofilms, are constantly in contact with restorations. In this study, we investigate how well Candida albicans adheres to a polymethyl methacrylate (PMMA) resin base with gold (Au) nanoparticles. We synthesized Au nanoparticles and characterized them. The average size of Au nanoparticles embedded in PMMA was 11 nm. The color difference ΔE between PMMA and PMMA/Au composites was 2.7 and was still esthetically acceptable to patients. PMMA/Au surfaces are smoother and more hydrophilic than pure PMMA surfaces, and the isoelectric point of both types of surfaces was 4.3. Above the isoelectric point, PMMA/Au surfaces are more negatively charged than PMMA surfaces. The added Au nanoparticles decreased the tensile strength, while the hardness did not change significantly. Adhesion measurements showed that PMMA surfaces modified with Au nanoparticles reduced the extent of microbial adhesion of Candida albicans.

Synthesis and In Vitro Characterization of Ascorbyl Palmitate-Loaded Solid Lipid Nanoparticles.

Antitumor applications of ascorbic acid (AA) and its oxidized form dehydroascorbic acid (DHA) can be quite challenging due to their instability and sensitivity to degradation in aqueous media. To overcome this obstacle, we have synthesized solid lipid nanoparticles loaded with ascorbyl palmitate (SLN-AP) with variations in proportions of the polymer Pluronic F-68. SLNs were synthesized using the hot homogenization method, characterized by measuring the particle size, polydispersity, zeta potential and visualized by TEM. To investigate the cellular uptake of the SLN, we have incorporated coumarin-6 into the same SLN formulation and followed their successful uptake for 48 h. We have tested the cytotoxicity of the SLN formulations and free ascorbate forms, AA and DHA, on HEK 293 and U2OS cell lines by MTT assay. The SLN-AP in both formulations have a cytotoxic effect at lower concentrations when compared to ascorbate applied the form of AA or DHA. Better selectivity for targeting tumor cell line was observed with 3% Pluronic F-68. The antioxidative effect of the SLN-AP was observed as early as 1 h after the treatment with a small dose of ascorbate applied (5 µM). SLN-AP formulation with 3% Pluronic F-68 needs to be further optimized as an ascorbate carrier due to its intrinsic cytotoxicity.

Solid-State Dispersions of Platinum in the SnO2 and Fe2O3 Nanomaterials.

The dispersion of platinum (Pt) on metal oxide supports is important for catalytic and gas sensing applications. In this work, we used mechanochemical dispersion and compatible Fe(II) acetate, Sn(II) acetate and Pt(II) acetylacetonate powders to better disperse Pt in Fe2O3 and SnO2. The dispersion of platinum in SnO2 is significantly different from the dispersion of Pt over Fe2O3. Electron microscopy has shown that the elements Sn, O and Pt are homogeneously dispersed in α-SnO2 (cassiterite), indicating the formation of a (Pt,Sn)O2 solid solution. In contrast, platinum is dispersed in α-Fe2O3 (hematite) mainly in the form of isolated Pt nanoparticles despite the oxidative conditions during annealing. The size of the dispersed Pt nanoparticles over α-Fe2O3 can be controlled by changing the experimental conditions and is set to 2.2, 1.2 and 0.8 nm. The rather different Pt dispersion in α-SnO2 and α-Fe2O3 is due to the fact that Pt4+ can be stabilized in the α-SnO2 structure by replacing Sn4+ with Pt4+ in the crystal lattice, while the substitution of Fe3+ with Pt4+ is unfavorable and Pt4+ is mainly expelled from the lattice at the surface of α-Fe2O3 to form isolated platinum nanoparticles.

Rheological, Microstructural and Thermal Properties of Magnetic Poly(Ethylene Oxide)/Iron Oxide Nanocomposite Hydrogels Synthesized Using a One-Step Gamma-Irradiation Method.

Magnetic polymer gels are a new promising class of nanocomposite gels. In this work, magnetic PEO/iron oxide nanocomposite hydrogels were synthesized using the one-step -irradiation method starting from poly(ethylene oxide) (PEO) and iron(III) precursor alkaline aqueous suspensions followed by simultaneous crosslinking of PEO chains and reduction of Fe(III) precursor. -irradiation dose and concentrations of Fe3+, 2-propanol and PEO in the initial suspensions were varied and optimized. With 2-propanol and at high doses magnetic gels with embedded magnetite nanoparticles were obtained, as confirmed by XRD, SEM and Mössbauer spectrometry. The quantitative determination of -irradiation generated Fe2+ was performed using the 1,10-phenanthroline method. The maximal Fe2+ molar fraction of 0.55 was achieved at 300 kGy, pH = 12 and initial 5% of Fe3+. The DSC and rheological measurements confirmed the formation of a well-structured network. The thermal and rheological properties of gels depended on the dose, PEO concentration and initial Fe3+ content (amount of nanoparticles synthesized inside gels). More amorphous and stronger gels were formed at higher dose and higher nanoparticle content. The properties of synthesized gels were determined by the presence of magnetic iron oxide nanoparticles, which acted as reinforcing agents and additional crosslinkers of PEO chains thus facilitating the one-step gel formation.

Deposition of Thin Alumina Films Containing 3D Ordered Network of Nanopores on Porous Substrates.

Self-supporting thin films containing nanopores are very promising materials for use for multiple applications, especially in nanofiltration. Here, we present a method for the production of nanomembranes containing a 3D ordered network of nanopores in an alumina matrix, with a diameter of about 1 nm and a body centered tetragonal structure of the network nodes. The material is produced by the magnetron sputtering deposition of a 3D ordered network of Ge nanowires in an alumina matrix, followed by a specific annealing process resulting in the evaporation of Ge. We demonstrate that the films can be easily grown on commercially available alumina substrates containing larger pores with diameters between 20 and 400 nm. We have determined the minimal film thickness needed to entirely cover the larger pores. We believe that these films have the potential for applications in the fields of filtration, separation and sensing.

Nanostructured Silicon as Potential Anode Material for Li-Ion Batteries.

Commercial micrometer silicon (Si) powder was investigated as a potential anode material for lithium ion (Li-ion) batteries. The characterization of this powder showed the mean particle size of approx.75.2 nm, BET surface area of 10.6 m2/g and average pore size of 0.56 nm. Its band gap was estimated to 1.35 eV as determined using UV-Vis diffuse reflectance spectra. In order to increase the surface area and porosity which is important for Li-ion batteries, the starting Si powder was ball-milled and threatened by metal-assisted chemical etching. The mechanochemical treatment resulted in decrease of the particle size from 75 nm to 29 nm, an increase of the BET surface area and average pore size to 16.7 m2/g and 1.26 nm, respectively, and broadening of the X-ray powder diffraction (XRD) lines. The XRD patterns of silver metal-assisted chemical etching (MACE) sample showed strong and narrow diffraction lines typical for powder silicon and low-intensity diffraction lines typical for silver. The metal-assisted chemical etching of starting Si material resulted in a decrease of surface area to 7.3 m2/g and an increase of the average pore size to 3.44 nm. These three materials were used as the anode material in lithium-ion cells, and their electrochemical properties were investigated by cyclic voltammetry and galvanostatic charge-discharge cycles. The enhanced electrochemical performance of the sample prepared by MACE is attributed to increase in pore size, which are large enough for easy lithiation. These are the positive aspects of the application of MACE in the development of an anode material for Li-ion batteries.

Bone Tissue Engineering in a Perfusion Bioreactor Using Dexamethasone-Loaded Peptide Hydrogel.

The main goal of this study was the formation of bone tissue using dexamethasone (DEX)-loaded [COCH3]-RADARADARADARADA-[CONH2] (RADA 16-I) scaffold that has the ability to release optimal DEX concentration under perfusion force. Bone-marrow samples were collected from three patients during a hip arthroplasty. Human mesenchymal stem cells (hMSCs) were isolated and propagated in vitro in order to be seeded on scaffolds made of DEX-loaded RADA 16-I hydrogel in a perfusion bioreactor. DEX concentrations were as follows: 4 × 10-3, 4 × 10-4 and 4 × 10-5 M. After 21 days in a perfusion bioreactor, tissue was analyzed by scanning electron microscopy (SEM) and histology. Markers of osteogenic differentiation were quantified by real-time polymerase chain reaction (RT-PCR) and immunocytochemistry. Minerals were quantified and detected by the von Kossa method. In addition, DEX release from the scaffold in a perfusion bioreactor was assessed. The osteoblast differentiation was confirmed by the expression analysis of osteoblast-related genes (alkaline phosphatase (ALP), collagen I (COL1A1) and osteocalcin (OC). The hematoxylin/eosin staining confirmed the presence of cells and connective tissue, while SEM revealed morphological characteristics of cells, extracellular matrix and minerals-three main components of mature bone tissue. Immunocytochemical detection of collagen I is in concordance with given results, supporting the conclusion that scaffold with DEX concentration of 4 × 10-4 M has the optimal engineered tissue morphology. The best-engineered bone tissue is produced on scaffold loaded with 4 × 10-4 M DEX with a perfusion rate of 0.1 mL/min for 21 days. Differentiation of hMSCs on DEX-loaded RADA 16-I scaffold under perfusion force has a high potential for application in regenerative orthopedics.

Near-Infrared Surface-Enhanced Raman Scattering on Silver-Coated Porous Silicon Photonic Crystals.

Surface-enhanced Raman scattering (SERS) with near-infrared (NIR) excitation offers a safe way for the detection and study of fragile biomolecules. In this work, we present the possibility of using silver-coated porous silicon photonic crystals as SERS substrates for near-infrared (1064 nm) excitation. Due to the deep penetration of NIR light inside silicon, the fabrication of photonic crystals was necessary to quench the band gap photoluminescence of silicon crystal, which acts as mechanical support for the porous layer. Optimal parameters of the immersion plating process that gave maximum enhancement were found and the activity of SERS substrates was tested using rhodamine 6G and crystal violet dye molecules, yielding significant SERS enhancement for off-resonant conditions. To our knowledge, this is the first time that the 1064 nm NIR laser excitation is used for obtaining the SERS effect on porous silicon as a substrate.

Sensing Properties of Oxidized Nanostructured Silicon Surface on Vaporized Molecules.

Porous silicon has been intensely studied for the past several decades and its applications were found in photovoltaics, biomedicine, and sensors. An important aspect for sensing devices is their long⁻term stability. One of the more prominent changes that occur with porous silicon as it is exposed to atmosphere is oxidation. In this work we study the influence of oxidation on the sensing properties of porous silicon. Porous silicon layers were prepared by electrochemical etching and oxidized in a tube furnace. We observed that electrical resistance of oxidized samples rises in response to the increasing ambient concentration of organic vapours and ammonia gas. Furthermore, we note the sensitivity is dependent on the oxygen treatment of the porous layer. This indicates that porous silicon has a potential use in sensing of organic vapours and ammonia gas when covered with an oxide layer.

Syntheses of gold nanoparticles and their impact on the cell cycle in breast cancer cells subjected to megavoltage X-ray irradiation.

Gold nanoparticles (AuNPs) were synthesized in the presence of citrate (Au-CIT), glutathione (Au-GSH) and aminodextran (Au-DEX) in order to modify AuNPs surfaces and to increase their cellular uptake in the breast cancer cells MDA-MB-231. AuNPs were characterized with respect to their particle size, shape and colloidal stability in an aqueous solution and cell media. The mass accumulation of each AuNP type inside cancer cells was determined quantitatively, using Inductive Coupled Plasma - mass spectroscopy. The sub-cellular accumulation was studied using Transmission Electron Microscopy (TEM). It was found that gold nanoparticles applied to cancer cells were localized in cytoplasmic vesicles and that the highest uptake was shown in the presence of Au-GSH nanoparticles. The effect of AuNPs on the cell cycle was investigated using flow cytometry and Western blot analysis. The gold nanoparticles alone did not affect the cell cycle, as shown by flow cytometry. Furthermore, the cancer cells were irradiated using conventional clinically relevant high-energy X-ray radiation of 6 MV in the dose of 4 Gy. The results on cells only irradiated showed an S phase arrest six and 8 h after irradiation, and a G2/M arrest 24 and 48 h after irradiation. The irradiation of breast cancer cells treated with AuNPs has shown no significant variation in cell cycle distribution as opposed to X-ray radiation alone.

The compatible solute ectoine reduces the exacerbating effect of environmental model particles on the immune response of the airways.

Exposure of humans to particulate air pollution has been correlated with the incidence and aggravation of allergic airway diseases. In predisposed individuals, inhalation of environmental particles can lead to an exacerbation of immune responses. Previous studies demonstrated a beneficial effect of the compatible solute ectoine on lung inflammation in rats exposed to carbon nanoparticles (CNP) as a model of environmental particle exposure. In the current study we investigated the effect of such a treatment on airway inflammation in a mouse allergy model. Ectoine in nonsensitized animals significantly reduced the neutrophilic lung inflammation after CNP exposure. This effect was accompanied by a reduction of inflammatory factors in the bronchoalveolar lavage. Reduced IL-6 levels in the serum also indicate the effects of ectoine on systemic inflammation. In sensitized animals, an aggravation of the immune response was observed when animals were exposed to CNP prior to antigen provocation. The coadministration of ectoine together with the particles significantly reduced this exacerbation. The data indicate the role of neutrophilic lung inflammation in the exacerbation of allergic airway responses. Moreover, the data suggest to use ectoine as a preventive treatment to avoid the exacerbation of allergic airway responses induced by environmental air pollution.

Carbon nanoparticles induce ceramide- and lipid raft-dependent signalling in lung epithelial cells: a target for a preventive strategy against environmentally-induced lung inflammation.

BACKGROUND: Particulate air pollution in lung epithelial cells induces pathogenic endpoints like proliferation, apoptosis, and pro-inflammatory reactions. The activation of the epidermal growth factor receptor (EGFR) is a key event responsible for signalling events involving mitogen activated protein kinases specific for these endpoints. The molecular events leading to receptor activation however are not well understood. These events are relevant for the toxicological evaluation of inhalable particles as well as for potential preventive strategies in situations when particulate air pollution cannot be avoided. The current study therefore had the objective to elucidate membrane-coupled events leading to EGFR activation and the subsequent signalling cascade in lung epithelial cells. Furthermore, we aimed to identify the molecular target of ectoine, a biophysical active substance which we described to prevent carbon nanoparticle-induced lung inflammation. METHODS: Membrane signalling events were investigated in isolated lipid rafts from lung epithelial cells with regard to lipid and protein content of the signalling platforms. Using positive and negative intervention approaches, lipid raft changes, subsequent signalling events, and lung inflammation were investigated in vitro in lung epithelial cells (RLE-6TN) and in vivo in exposed animals. RESULTS: Carbon nanoparticle treatment specifically led to an accumulation of ceramides in lipid rafts. Detailed analyses demonstrated a causal link of ceramides and subsequent EGFR activation coupled with a loss of the receptor in the lipid raft fractions. In vitro and in vivo investigations demonstrate the relevance of these events for carbon nanoparticle-induced lung inflammation. Moreover, the compatible solute ectoine was able to prevent ceramide-mediated EGFR phosphorylation and subsequent signalling as well as lung inflammation in vivo. CONCLUSION: The data identify a so far unknown event in pro-inflammatory signalling and contribute to the understanding of particle cell interaction and therefore to risk identification and risk assessment of inhalable xenobiotics. Moreover, as this cellular reaction can be prevented by the well tolerated substance ectoine, a molecular preventive strategy for susceptible persons against airway inflammation is proposed.

Cytotoxicity of nanosize V(2)O(5) particles to selected fibroblast and tumor cells.

Two kinds of nanosize V(2)O(5) particles were synthesized in our own laboratory and concomitantly applied to V79 and L929 fibroblasts and SCCVII, B16F10 and FsaR tumor cells. The morphologies of the cells were monitored using an inverted inverse microscope equipped with digital camera, while quantitative determination of the cytotoxicity of nanosize V(2)O(5) particles was measured using crystal violet bioassay. Twenty four hours after the addition of nanosize V(2)O(5) particles (20muM), noticeable changes in the morphology and density of fibroblast and cancer cells were observed. Reculturing in a freshly prepared medium for the next 24h showed a high recovery effect on V79, SCCVII and B16F10 cells, while FsaR and L929 cells were seriously damaged and unable to recover. At a higher concentration of nanosize V(2)O(5) particles (100muM), the cytotoxicity of V(2)O(5) prevailed against the recovery effect in all cell types. Quantitative measurements have shown that the resistance of investigated cell cultures to the cytotoxicity of nanosize V(2)O(5) particles decreases in the order V79>SCCVII>B16F10>FsaR>L929. The high cytotoxic effect found on FsaR cells suggests that nanosize V(2)O(5) particles could be regarded as poisoning material in the treatment of FsaR fibrosarcoma cells. Possible mechanisms involved in the cytotoxicity of nanosize V(2)O(5) particles were discussed.