Preparation and Characterization of Polyvinyl Alcohol (PVA)/Carbonized Waste Rubber Biocomposite Films.

The technological properties of composite materials (thermal, strength, rheology, electrical and morphology) are very important parameters for high-performance applications. In this study, we aimed to improve the properties of PVA by using carbon materials obtained by the pyrolysis of waste tires, with the aim of recycling them instead of disposing of them. For this purpose, PVA biocomposite films containing carbonized waste rubber at different rates were prepared. The thermal properties of the prepared biocomposite films were examined via thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC) methods. While rheological measurements were carried out with a rheometer, bulk conductivities were measured with a pico-ammeter. In addition, the morphology of biocomposite films was determined via field emission scanning electron microscopy. The nanomechanical properties of biocomposite film was investigated via XPM analyses. According to the rheological measurements and nanoindentation hardness results, it is understood that as the amount of carbonized waste rubber increases, flexibility decreases and harder and brittle structures are observed in biocomposite films. The electrical measurement results showed that electrical conductivity increased as the amount of carbonized waste rubber increased. When all the results obtained were evaluated, it could be concluded that biocomposite films obtained by increasing the electrical conductivity and hardness of PVA can be used in the electronics industry.

Dielectric Spectroscopy and Thermal Properties of Poly(lactic) Acid Reinforced with Carbon-Based Particles: Experimental Study and Design Theory.

In the present study, polylactic acid (PLA) enriched with carbonaceous particles like multi-walled carbon nanotubes (MWCNTs), graphene nanoplates (GNPs) or a combination of both up 12 wt % of loading are used for producing 3D-printed specimens with fused deposition modeling (FDM) technology which are then experimentally and theoretically investigated. The goal is to propose a non-conventional filaments indicated for additive manufacturing process with improved dielectric and thermal properties, compared to the performances exhibited by the unfilled polymer. In the light of the above, a wide dielectric spectroscopy and a thermal analysis, supported by a morphological investigation, are performed. The results highlight that the introduction of 1-dimensional filler (MWCNTs) are more suitable for improving the dielectric properties of the resulting materials, due to the enhancement of the interfacial polarization and the presence of functionalized groups, whereas 2-dimensional nanoparticles (GNPs) better favor the thermal conduction mechanisms thanks to the lower thermal boundary resistance between the two phases, polymer/filler. In particular, with a loading of 12 wt % of MWCNTs the relative permittivity reaches the value of 5.35 × 103 much greater than that of 3.7 measured for unfilled PLA while for the thermal conductivity the enhancement with 12 wt % of GNPs is about 261% respect the thermal behavior of the neat polymer. The experimental results are correlated to theoretical findings, whereas a design of experiment (DoE) approach is adopted for investigating how the different fillers influence the dielectric and thermal performances of the 3D-printed parts, thus assisting the design of such innovative materials that appear promising for development and applications in the electromagnetic (EM) field and heat transfer.

Essential Nanostructure Parameters to Govern Reinforcement and Functionality of Poly(lactic) Acid Nanocomposites with Graphene and Carbon Nanotubes for 3D Printing Application.

Poly(lactic) acid nanocomposites filled with graphene nanoplatelets (GNPs) and multiwall carbon nanotubes (MWCNTs) are studied, varying the filler size, shape, and content within 1.5-12 wt.%. The effects of the intrinsic characteristics of nanofillers and structural organization of nanocomposites on mechanical, electrical, thermal, and electromagnetic properties enhancement are investigated. Three essential rheological parameters are identified, which determine rheology-structure-property relations in nanocomposites: the degree of dispersion, percolation threshold, and interfacial interactions. Above the percolation threshold, depending on the degree of dispersion, three structural organizations are observed in nanocomposites: homogeneous network (MWCNTs), segregated network (MWCNTs), and aggregated structure (GNPs). The rheological and structural parameters depend strongly on the type, size, shape, specific surface area, and functionalization of the fillers. Consequently, the homogeneous and segregated network structures resulted in a significant enhancement of tensile mechanical properties and a very low electrical percolation threshold, in contrast to the aggregated structure. The high filler density in the polymer and the low number of graphite walls in MWCNTs are found to be determinant for the remarkable shielding efficiency (close to 100%) of nanocomposites. Moreover, the 2D shaped GNPs predominantly enhance the thermal conductivity compared to the 1D shaped MWCNTs. The proposed essential structural parameters may be successfully used for the design of polymer nanocomposites with enhanced multifunctional properties for 3D printing applications.

Effects of Filament Extrusion, 3D Printing and Hot-Pressing on Electrical and Tensile Properties of Poly(Lactic) Acid Composites Filled with Carbon Nanotubes and Graphene.

: In this study, the effects of three processing stages: filament extrusion, 3D printing (FDM), and hot-pressing are investigated on electrical conductivity and tensile mechanical properties of poly(lactic) acid (PLA) composites filled with 6 wt.% of multiwall carbon nanotubes(MWCNTs), graphene nanoplatelets (GNPs), and combined fillers. The filaments show several decades' higher electrical conductivity and 50-150% higher values of tensile characteristics, compared to the 3D printed and the hot-pressed samples due to the preferential orientation of nanoparticles during filament extrusion. Similar tensile properties and slightly higher electrical conductivity are found for the hot-pressed compared to the 3D printed samples, due to the reduction of interparticle distances, and consequently, the reduced tunneling resistances in the percolated network by hot pressing. Three structural types are observed in nanocomposite filaments depending on the distribution and interactions of fillers, such as segregated network, homogeneous network, and aggregated structure. The type of structural organization of MWCNTs, GNPs, and combined fillers in the matrix polymer is found determinant for the electrical and tensile properties. The crystallinity of the 3D printed samples is higher compared to the filament and hot-pressed samples, but this structural feature has a slight effect on the electrical and tensile properties. The results help in understanding the influence of processing on the properties of the final products based on PLA composites.

Ozone decomposition.

Catalytic ozone decomposition is of great significance because ozone is a toxic substance commonly found or generated in human environments (aircraft cabins, offices with photocopiers, laser printers, sterilizers). Considerable work has been done on ozone decomposition reported in the literature. This review provides a comprehensive summary of the literature, concentrating on analysis of the physico-chemical properties, synthesis and catalytic decomposition of ozone. This is supplemented by a review on kinetics and catalyst characterization which ties together the previously reported results. Noble metals and oxides of transition metals have been found to be the most active substances for ozone decomposition. The high price of precious metals stimulated the use of metal oxide catalysts and particularly the catalysts based on manganese oxide. It has been determined that the kinetics of ozone decomposition is of first order importance. A mechanism of the reaction of catalytic ozone decomposition is discussed, based on detailed spectroscopic investigations of the catalytic surface, showing the existence of peroxide and superoxide surface intermediates.

Ozone decomposition on Ag/SiO2 and Ag/clinoptilolite catalysts at ambient temperature.

Silver modified zeolite (Bulgarian natural clinoptilolite) and Ag/silica catalysts were synthesized by ion exchange and incipient wet impregnation method respectively and characterized by different techniques. DC arc-AES was used for Ag detection. XRD spectra show that Ag is loaded over the surface of the SiO(2) sample and that after the ion-exchange process the HEU type structure of clinoptilolite is retained. UV-VIS (specific reflection at 310 nm) and IR (band at 695 cm(-1)) spectroscopy analysis proved that silver is loaded as a T-atom into zeolite channels as Ag(+), instead of Na(+), Ca(2+), or K(+) ions, existing in the natural clinoptilolite form. The samples Ag/SiO(2) and Ag-clinoptilolite were tested as catalysts for decomposition of gas phase ozone. Very high catalytic activity (up to 99%) was observed and at the same time the catalysts remained active over time at room temperature.

Increased oxidative/nitrosative stress and decreased antioxidant enzyme activities in prostate cancer.

OBJECTIVES: The study was aimed to evaluate the oxidative/nitrosative stress status in prostate cancer (CaP) and benign prostatic hyperplasia (BPH). DESIGN AND METHODS: 312 men from two different populations were included: 163 men from Macedonia (73 CaP patients, 67 BPH patients and 23 control subjects) and 149 men from Turkey (34 prostate cancer patients, 100 BPH patients and 15 control subjects). We measured erythrocyte malondialdehyde (MDA) levels, erythrocyte activities of superoxide dismutase (CuZn-SOD), glutathione peroxidase (GPX) and catalase (CAT); plasma nitrite/nitrate (NO(2)(-)/NO(3)(-)), cGMP and 8-hydroxy-2'-deoxyguanosine (8-OHdG) levels. RESULTS: A similar pattern of alteration in the oxidative/nitrosative stress-related parameters was found in both, Macedonian and Turkish studied samples: higher MDA concentrations with lower GPX and CuZn-SOD activities in CaP patients versus controls and BPH groups. The CAT activity was decreased in the CaP patients versus controls in the Turkish studied sample. Furthermore, CaP patients had increased plasma NO(2)(-)/NO(3)(-) and cGMP levels versus controls and BPH groups in both studied samples. CONCLUSIONS: This study has confirmed an imbalance in the oxidative stress/antioxidant status and revealed an altered nitrosative status in prostate cancer patients.

Glutathione peroxidase 1 (GPX1) genetic polymorphism, erythrocyte GPX activity, and prostate cancer risk.

Glutathione peroxidase 1 (GPX1) is a ubiquitously expressed selenium-dependent enzyme that protects cells against oxidative damage by reducing hydrogen peroxide and a wide range of organic peroxides. Some epidemiological studies have correlated low GPX activity or particular GPX1 polymorphisms with enhanced risk of cancer, although these correlations have not been consistently observed in all populations. Therefore, we conducted the present study to evaluate the possible association of GPX1 Pro198Leu polymorphism and erythrocyte GPX activity with the risk of developing prostate cancer and to clarify whether erythrocyte GPX activity levels were correlated with the GPX1 Pro198Leu genotype in the Macedonian population. The GPX1 Pro198Leu genotype was determined in 82 prostate cancer cases and 123 control individuals. We found an overall protective effect of the variant Leu allele of the GPX1 polymorphism on the prostate cancer risk. Heterozygous carriers of the variant Leu allele had a significantly lower risk of prostate cancer compared with homozygous wild-type individuals (OR, 0.38; 95% CI, 0.20-0.75; P = 0.004). Erythrocyte GPX activity was analyzed in 73 cases and 91 controls. The erythrocyte GPX activity in the cancer group was lower than in the healthy controls. Additionally, we compared the erythrocyte GPX activity in the control group of 90 subjects and found no significant differences by genotype. These findings suggest that individual susceptibility of prostate cancer may be modulated by GPX1 polymorphism and that the combination of genetic factors involved in oxidative response with environmental carcinogens may play an important role in prostate carcinogenesis.

Manganese superoxide dismutase (MnSOD) genetic polymorphism is associated with risk of early-onset prostate cancer.

Prostate cancer continues to be the most frequently diagnosed neoplasm, and the second leading cause of cancer-related mortality in men. Oxidative stress may enhance prostatic carcinogenesis. Manganese superoxide dismutase (MnSOD) is the only known superoxide scavenger in mitochondria. It plays a key role in antioxidant defense as mitochondria are important for oxidative metabolism coupled to the electron transport chain and oxidative phosphorylation and hence, ROS production. A T-->C single nucleotide substitution, resulting in a Val-->Ala change at position 9 (Ala-9Val), which alters the secondary structure of the protein, has been noted to affect transport of MnSOD into the mitochondria. We have determined the MnSOD genotype in 85 prostate cancer cases and 151 control subjects. Ala-9Val polymorphism was determined using real time polymerase chain reaction (PCR) amplification with fluorescently labeled primers. No significant difference was found in prostate cancer susceptibility in the subjects with Ala/Ala and Val/Ala genotype compared with Val/Val genotype (Odds ratio (OR), 1.3; 95% confidence interval (95% CI), 0.69-2.42; p = 0.416). We did not observe an association of the MnSOD genotype or allele frequency between subgroups of cases divided by disease status (aggressive vs. non-aggressive prostate cancer). However, in the analyses stratified by the age at diagnosis we have observed that men homozygous for Ala had a 5.2-fold increased risk of early-onset prostate cancer (under age of 65) compared to men homozygous for Val allele (p = 0.05). These data suggest that Ala/Ala MnSOD genotype in the Macedonian population could have an influence on early onset of prostate cancer, but no impact on the subsequent development of the disease.