Nitrogen Dioxide Sensing Using Multilayer Structure of Reduced Graphene Oxide and α-Fe2O3.

Multilayers consisting of graphene oxide (GO) and α-Fe2O3 thin layers were deposited on the ceramic substrates by the spray LbL (layer by layer) coating technique. Graphene oxide was prepared from graphite using the modified Hummers method. Obtained GO flakes reached up to 6 nanometers in thickness and 10 micrometers in lateral size. Iron oxide Fe2O3 was obtained by the wet chemical method from FeCl3 and NH4OH solution. Manufactured samples were deposited as 3 LbL (GO and Fe2O3 layers deposited sequentially) and 6 LbL structures with GO as a bottom layer. Electrical measurements show the decrease of multilayer resistance after the introduction of the oxidizing NO2 gas to the ambient air atmosphere. The concentration of NO2 was changed from 1 ppm to 20 ppm. The samples changed their resistance even at temperatures close to room temperature, however, the sensitivity increased with temperature. Fe2O3 is known as an n-type semiconductor, but the rGO/Fe2O3 hybrid structure behaved similarly to rGO, which is p-type. Both chemisorbed O2 and NO2 act as electron traps decreasing the concentration of electrons and increasing the effective multilayer conductivity. An explanation of the observed variations of multilayer structure resistance also the possibility of heterojunctions formation was taken into account.

Study of optical properties of graphene flakes and its derivatives in aqueous solutions.

In this work, we study optical spectroscopy of graphene flakes and its derivatives such as graphene oxide and reduced graphene oxide in the same surfactant-free aqueous solution. We show that transmittance (T) and absorbance (A) spectra of different graphene suspension is nearly feature-less as a function of wavelength (λ) in the VIS-NIR range (350-1000 nm) except graphene oxide solution and the smallest graphene flakes, and they change linearly with concentration. The optical absorption coefficient (at 660 nm) of pure graphene solution seems to be flake-size dependent, changing from ∼730 mL·mg-1m-1 (for ∼25 µm flake size) to ∼4400 mL·mg-1m-1 (for ∼2 µm flake size), and it is several times higher than in the case of graphene oxide, which also varies with type and level of doping/defects (checked by FTIR and statistical Raman spectroscopy). Finally, we show wavelength-dependent evolution of optical absorption coefficient in the VIS-NIR range, which is roughly mimicking the A(λ) function but is strongly material-dependent. Our study could be useful for application of graphene solution in optofluidic devices, functional inks or printed flexible optoelectronics.

Cationic Porphyrin-Graphene Oxide Hybrid: Donor-Acceptor Composite for Efficient Photoinduced Electron Transfer.

Non-covalent nanohybrids composed of cationic 5,10,15,20-tetra(4-trimethylammoniophenyl)porphyrin tetra(p-toluenesulfonate) (TMAP) and the graphene oxide sheets were prepared under two pH values (6.2 vs. 1.8). The TMAP molecule was positively charged, regardless of the pH value during preparation. However, protonation of the imino nitrogens increased the overall charge of the porphyrin molecule from +4 to +6 (TMAP4+ and TMAP6+ ). It was found that at acidic pH, interaction of TMAP6+ with GO was largely suppressed. On the other hand, results of FTIR, Raman spectroscopy, thermogravimetric analysis, atomic force microscopy (AFM) and elemental analysis confirmed effective non-covalent functionalization of graphene oxide with cationic porphyrin at pH 6.2. The TMAP4+ -GO hybrids exhibited well defined structure with a monolayer of TMAP4+ on the GO sheets as confirmed by AFM. Formation of the ground-state TMAP4+ -GO complex in solution was monitored by the red-shift of the porphyrin Soret absorption band. This ground-state interaction between TMAP4+ and GO is responsible for the static quenching of the porphyrin emission. Fluorescence was not detected for the nanohybrid which indicated that a very fast deactivation process had to take place. Ultrafast time-resolved transient absorption spectroscopy clearly demonstrated the occurrence of electron transfer from the photoexcited TMAP4+ singlet state to GO sheets, as proven by the formation of a porphyrin radical cation.

Fabrication of 3D-Printed Scaffolds with Multiscale Porosity.

3D printing is a promising technique for producing bone implants, but there is still a need to adjust efficiency, facilitate production, and improve biocompatibility. Porous materials have a proven positive effect on the regeneration of bone tissue, but their production is associated with numerous limitations. In this work, we described a simple method of producing polymer or polymer-ceramic filaments for 3D-printing scaffolds by adding micrometer-scale porous structures on scaffold surfaces. Scaffolds included polycaprolactone (PCL) as the primary polymer, ß-tricalcium phosphate (ß-TCP) as the ceramic filler, and poly(ethylene glycol) (PEG) as a porogen. The pressurized filament extrusion gave flexible filaments composed of PCL, ß-TCP, and PEG, which are ready to use in fused filament fabrication (FFF) 3D printers. Washing of 3D-printed scaffolds in ethanol solution removed PEG and revealed a microporous structure and ceramic particles on the scaffold's surfaces. Furthermore, 3D-printed materials exhibit good printing precision, no cytotoxic properties, and highly impact MG63 cell alignment. Although combining PCL, PEG, and ß-TCP is quite popular, the presented method allows the production of porous scaffolds with a well-organized structure without advanced equipment, and the produced filaments can be used to 3D print scaffolds on a simple commercially available 3D printer.

Functionalized Carbon Nanotubes for Delivery of Ferulic Acid and Diosgenin Anticancer Natural Agents.

It was investigated whether loading multi-wall carbon nanotubes (CNTs) with two natural anticancer agents: ferulic acid (FUA) and diosgenin (DGN), may enhance the anticancer effect of these drugs. The CNTs were functionalized with carboxylic acid (CNTCOOH) or amine (CNTNH2), loaded with the above pro-drugs, as well as both combined and coated with chitosan or chitosan-stearic acid. Following physicochemical characterization, the drug-loading properties and kinetics of the drug's release were investigated. Their effects on normal human skin fibroblasts and MCF-7 breast carcinoma cells, HepG2 hepatocellular carcinoma cells, and A549 non-small-cell lung cancer cells were evaluated in vitro. Their actions at the molecular level were evaluated by assessing the expression of lncRNAs (HULC, HOTAIR, CCAT-2, H19, and HOTTIP), microRNAs (mir-21, mir-92, mir-145, and mir-181a), and proteins (TGF-ß and E-cadherin) in HepG2 cells. The release of both pro-drugs depended on the glutathione concentration, coating, and functionalization. Release occurred in two stages: a no-burst/zero-order release followed by a sustained release best fitted to Korsmeyer-Peppas kinetics. The combined nanoformulation cancer inhibition effect on HepG2 cancer cells was more pronounced than for A549 and MCF7 cells. The combined nanoformulations had an additive impact followed by a synergistic effect, with antagonism demonstrated at high concentrations. The nanoformulation coated with chitosan and stearic acid was particularly successful in targeting HepG2 cells and inducing apoptosis. The CNT functionalized with carboxylic acid (CNTCOOH), loaded with both FUA and DGN, and coated with chitosan-stearic acid inhibited the expression of lncRNAs and modulated both microRNAs and proteins. Thus, nanoformulations composed of functionalized CNTs dual-loaded with FUA and DGN and coated with chitosan-stearic acid are a promising drug delivery system that enhances the activity of natural pro-drugs.

Co nanoparticles supported on mixed magnesium-lanthanum oxides: effect of calcium and barium addition on ammonia synthesis catalyst performance.

The synthesis of ammonia in the Haber-Bosch process produces millions of tons of ammonia annually needed for producing fertilisers required to feed the growing population. Although this process has been optimised extensively, it still accounts for about 2% of global energy consumption. It is, therefore, desirable to develop an efficient ammonia synthesis catalyst. Over the last decades, many attempts have been made to improve the ammonia synthesis catalyst efficiency under mild conditions. Here, we studied the effect of adding Ca and Ba to the cobalt ammonia synthesis catalyst. The combination of the different experimental results allows concluding that Ca served as an inactive additive, whereas Ba served as an electronic promoter. The Ca addition did not change the textural, structural, and chemisorptive properties of the Ca-doped Co catalyst. On the other hand, the Ba addition had a major effect on the nature of active Co sites. It contributed to the formation of new active sites for hydrogen and nitrogen adsorption and dissociation. Barium addition also contributed to the generation of new basic sites, particularly the strong ones. These unique characteristics were ascribed to the formation of Co(core)-BaO(shell) structures. It is likely that the donation of electrons from BaO to N2 via Co markedly promoted ammonia synthesis. This catalyst exhibited ammonia synthesis activity 4 times higher than that of the undoped Co catalyst and 2 times higher than that of the industrial Fe catalysts under identical conditions.

Differences in the Cell Type-Specific Toxicity of Diamond Nanoparticles to Endothelial Cells Depending on the Exposure of the Cells to Nanoparticles.

Introduction: Diamond nanoparticles are considered to be one of the most cytocompatible carbon nanomaterials; however, their toxicity varies significantly depending on the analysed cell types. The aim was to investigate the specific sensitivity of endothelial cells to diamond nanoparticles dependent on exposure to nanoparticles. Methods: Diamond nanoparticles were characterized with Raman spectroscopy, Fourier-transform infrared spectroscopy (FTIR) and dynamic light scattering (DLS). Toxicity of diamond nanoparticles was assessed for endothelial cells (HUVEC), human mammary epithelial cells (HMEC) and HS-5 cell line. The effect of diamond nanoparticles on the level of ROS, NO, NADPH and protein synthesis of angiogenesis-related proteins of endothelial cells was evaluated. Results and Discussion: Our studies demonstrated severe cell type-specific toxicity of diamond nanoparticles to endothelial cells (HUVEC) depending on nanoparticle surface interaction with cells. Furthermore, we have assessed the effect on cytotoxicity of the bioconjugation of nanoparticles with a peptide containing the RGD motive and a serum protein corona. Our study suggests that the mechanical interaction of diamond nanoparticles with the endothelial cell membranes and the endocytosis of nanoparticles lead to the depletion of NADPH, resulting in an intensive synthesis of ROS and a decrease in the availability of NO. This leads to severe endothelial toxicity and a change in the protein profile, with changes in major angiogenesis-related proteins, including VEGF, bFGF, ANPT2/TIE-2, and MMP, and the production of stress-related proteins, such as IL-6 and IL-8. Conclusion: We confirmed the presence of a relationship between the toxicity of diamond nanoparticles and the level of cell exposure to nanoparticles and the nanoparticle surface. The results of the study give new insights into the conditioned toxicity of nanomaterials and their use in biomedical applications.

Dependence of diamond nanoparticle cytotoxicity on physicochemical parameters: comparative studies of glioblastoma, breast cancer, and hepatocellular carcinoma cell lines.

Reports on the cytotoxicity of diamond nanoparticles (ND) are ambiguous and depend on the physicochemical properties of the material and the tested cell lines. Thus, the aim of this research was to evaluate the influence of thirteen types of diamond nanoparticles, differing in production method, size, and surface functional groups, on their cytotoxicity against four tumor cell lines (T98G, U-118 MG, MCF-7, and Hep G2) and one non-tumor cell line (HFF-1). In order to understand the dependence of diamond nanoparticles on physicochemical properties, the following parameters were analyzed: viability, cell membrane damage, morphology, and the level of intracellular general ROS and mitochondrial superoxide. The performed analyses revealed that all diamond nanoparticles showed no toxicity to MCF-7, Hep G2, and HFF-1 cells. In contrast, the same nanomaterials were moderately toxic for the glioblastoma T98G and U-118 MG cell lines. In general, the effect of the production method did not influence ND toxicity. Some changes in cell response after treatment with modified nanomaterials were observed, with the presence of carboxyl groups having a more detrimental effect than the presence of other functional groups. Although nanoparticles of different sizes caused similar toxicity, nanomaterials with bigger particles caused a more pronounced effect.

Bacterial Surface Disturbances Affecting Cell Function during Exposure to Three-Compound Nanocomposites Based on Graphene Materials.

Combating pathogenic microorganisms in an era of ever-increasing drug resistance is crucial. The aim of the study was to evaluate the antibacterial mechanism of three-compound nanocomposites that were based on graphene materials. To determine the nanomaterials' physicochemical properties, an analysis of the mean hydrodynamic diameter and zeta potential, transmission electron microscope (TEM) visualization and an FT-IR analysis were performed. The nanocomposites' activity toward bacteria species was defined by viability, colony forming units, conductivity and surface charge, cell wall integrity, ATP concentration, and intracellular pH. To ensure the safe usage of nanocomposites, the presence of cytokines was also analyzed. Both the graphene and graphene oxide (GO) nanocomposites exhibited a high antibacterial effect toward all bacteria species (Enterobacter cloacae, Listeria monocytogenes, Salmonella enterica, and Staphylococcus aureus), as well as exceeded values obtained from exposure to single nanoparticles. Nanocomposites caused the biggest membrane damage, along with ATP depletion. Nanocomposites that were based on GO resulted in lower toxicity to the cell line. In view of the many aspects that must be considered when investigating such complex structures as are three-component nanocomposites, studies of their mechanism of action are crucial to their potential antibacterial use.

Delivery of Melittin as a Lytic Agent via Graphene Nanoparticles as Carriers to Breast Cancer Cells.

Melittin, as an agent to lyse biological membranes, may be a promising therapeutic agent in the treatment of cancer. However, because of its nonspecific actions, there is a need to use a delivery method. The conducted research determined whether carbon nanoparticles, such as graphene and graphene oxide, could be carriers for melittin to breast cancer cells. The studies included the analysis of intracellular pH, the potential of cell membranes, the type of cellular transport, and the expression of receptor proteins. By measuring the particle size, zeta potential, and FT-IT analysis, we found that the investigated nanoparticles are connected by electrostatic interactions. The level of melittin encapsulation with graphene was 86%, while with graphene oxide it was 78%. A decrease in pHi was observed for all cell lines after administration of melittin and its complex with graphene. The decrease in membrane polarization was demonstrated for all lines treated with melittin and its complex with graphene and after exposure to the complex of melittin with graphene oxide for the MDA-MB-231 and HFFF2 lines. The results showed that the investigated melittin complexes and the melittin itself act differently on different cell lines (MDA-MB-231 and MCF-7). It has been shown that in MDA-MD-231 cells, melittin in a complex with graphene is transported to cells via caveolin-dependent endocytosis. On the other hand, the melittin-graphene oxide complex can reach breast cancer cells through various types of transport. Other differences in protein expression changes were also observed for tumor lines after exposure to melittin and complexes.

Modification of Ceramic Membranes with Carbon Compounds for Pharmaceutical Substances Removal from Water in a Filtration-Adsorption System.

The aim of this work is to develop a new type of carbon-ceramic membranes for the removal of pharmaceutical substances from water. The membranes were prepared by the chemical modification method using an organosilicon precursor-octadecyltrichlorosilane (ODTS). Graphene oxide, multi-walled carbon nanotubes with carboxylic groups, and single-walled carbon nanotubes were used in the modification process. The filtration properties and adsorption properties of the developed membranes were tested. In order to characterize the membrane, the water permeability, the change of the permeate flux in time, and the adsorbed mass of the substance were determined. Additionally, the surface properties of the membranes were characterized by contact angle measurements and porosimetry. The antibiotic tetracycline was used in the adsorption tests. Based on the results, the improved adsorption properties of the modified membrane in relation to the unmodified membrane were noticed. Novel ceramic membranes modified with MWCNT are characterized by 45.4% removal of tetracycline and permeate flux of 520 L·h·m-2·bar-1. We demonstrated the ability of modified membranes to adsorb pharmaceuticals from water streams that are in contact with the membrane. Novel membranes retain their filtration properties. Therefore, such membranes can be used in an integrated filtration-adsorption process.

Improved Laser Ablation Method for the Production of Luminescent Carbon Particles in Liquids.

An improved method for the production of luminescent carbon nanoparticles is proposed in this work. The new method overcomes the disadvantages of commonly used approaches. It involves two-stage laser ablation in water and in aqueous solutions, where the first stage is the laser ablation of a graphite target and the second is the shredding of particles produced in the first step. The two-stage method offers the optimization of the laser pulse fluence for the performance of each process. It was found that the two-stage process of laser ablation allows producing photoluminescent carbon structures in pure water. The additional reagent may be added either in the first or second stage. The first stage performed in pure water allows avoiding the contamination of the target. Moreover, it simplifies the identification of the origin of photoluminescence. Two synthesis routes for the preparation of carbon nanoparticles by the proposed method using pure water as well as urea aqueous solution are investigated. It was found that the use of urea as a reagent results in luminescence properties similar to those obtained with other more hazardous amine-based reagents. The influence of the synthesis approach and process parameters on the structural and luminescent properties of nanoparticles is also explored in this work.

Discharge Plasma Treatment as an Efficient Tool for Improved Poly(lactide) Adhesive-Wood Interactions.

Poly(lactide) (PLA) films obtained by thermoforming or solution-casting were modified by diffuse coplanar surface barrier discharge plasma (300 W and 60 s). PLA films were used as hot-melt adhesive in joints in oak wood. It was demonstrated that lap shear strength increased from 3.4 to 8.2 MPa, respectively, for the untreated and plasma-treated series. Pull-off tests performed on particleboard for the untreated and treated PLA films showed 100% cohesive failure. Pull-off strength tests on solid oak demonstrated adhesion enhancement from 3.3 MPa with the adhesion failure mode to 6.6 MPa with the cohesion failure mode for untreated and treated PLA. XPS revealed that carbonyl oxygen content increased by two-to-three-fold, which was confirmed in the Fourier-transform infrared spectroscopy experiments of the treated PLA. The water contact angle decreased from 66.4° for the pristine PLA to 49.8° after treatment. Subsequently, the surface free energy increased from 47.9 to 61.05 mJ/m2. Thus, it was clearly proven that discharge air plasma can be an efficient tool to change surface properties and to strengthen adhesive interactions between PLA and woody substrates.

Luminescent Carbon Dots Synthesized by the Laser Ablation of Graphite in Polyethylenimine and Ethylenediamine.

Fluorescent carbon dots (CDs) synthesized by pulsed laser ablation in liquid (PLAL) are still interesting materials due to their possible applications. However, unlike CDs produced by the hydrothermal method, CDs produced the synthesis products by the PLAL method were never separated by dialysis, which differentiates the synthesis products and allows the identification of the main source of fluorescence. In this work, the synthesis of fluorescent carbon dots (CDs) was performed by nanosecond laser ablation of a graphite target immersed in polyethyleneimine (PEI) and ethylenediamine (EDA), and the synthesis products were separated by dialysis. The results of optical measurements showed that the main source of luminescence of the obtained nanostructures are fluorescent particles or quasi-molecular fluorophores created in the ablation process. In the case of ablation in PEI, most of the produced molecular fluorophores are associated with carbogenic nanostructures, while in the case of EDA, free fluorescent molecules dominate.

Lerf-Klinowski-type models of graphene oxide and reduced graphene oxide are robust in analyzing non-covalent functionalization with porphyrins.

Graphene-based nanohybrids are good candidates for various applications. However, graphene exhibits some unwanted features such as low solubility in an aqueous solution or tendency to aggregate, limiting its potential applications. On the contrary, its derivatives, such as graphene oxide (GO) and reduced graphene oxide (RGO), have excellent properties and can be easily produced in large quantities. GO/RGO nanohybrids with porphyrins were shown to possess great potential in the field of photocatalytic hydrogen production, pollutant photodegradation, optical sensing, or drug delivery. Despite the rapid progress in experimental research on the porphyrin-graphene hybrids some fundamental questions about the structures and the interaction between components in these systems still remain open. In this work, we combine detailed experimental and theoretical studies to investigate the nature of the interaction between the GO/RGO and two metal-free porphyrins 5,10,15,20-tetrakis(4-aminophenyl) porphyrin (TAPP) and 5,10,15,20-tetrakis(4-hydroxyphenyl) porphyrin (TPPH)]. The two porphyrins form stable nanohybrids with GO/RGO support, although both porphyrins exhibited a slightly higher affinity to RGO. We validated finite, Lerf-Klinowski-type (Lerf et al. in J Phys Chem B 102:4477, 1998) structural models of GO ([Formula: see text]) and RGO ([Formula: see text]) and successfully used them in ab initio absorption spectra simulations to track back the origin of experimentally observed spectral features. We also investigated the nature of low-lying excited states with high-level wavefunction-based methods and shown that states' density becomes denser upon nanohybrid formation. The studied nanohybrids are non-emissive, and our study suggests that this is due to excited states that gain significant charge-transfer character. The presented efficient simulation protocol may ease the properties screening of new GO/RGO-nanohybrids.

Effect of Grinding and the Mill Type on Magnetic Properties of Carboxylated Multiwall Carbon Nanotubes.

The influence of the grinding process on the magnetic properties of as prepared and functionalized multiwall carbon nanotubes (MWCNTs) is presented. We have observed that 3 h mechanical grinding at 400 rpm in contrast to functionalization does not remove the iron contamination from MWCNTs. However, it changes the Fe chemical states. The magnetic properties of iron nanoparticles (Fe-NPs) embedded in the carbon matrix of MWCNTs have been analyzed in detail. We have proven that single-domain non-interacting Fe(C,O)-NPs enriched in the Fe3C phase (~10 nm) enclosed inside these nanotubes are responsible for their magnetic properties. Mechanical grinding revealed a unique impact of -COOH groups (compared to -COONH4 groups) on the magnetism of functionalized MWCNTs. In MWCNT-COOH ground in a steel mill, the contribution of the Fe2O3 and α-Fe phases increased while the content of the magnetically harder Fe3C phase decreased. This resulted in a 2-fold coercivity (Hc) decrease and saturation magnetization (MS) increase. A 2-fold remanence (Mr) decrease in MWCNT-COOH ground in an agate mill is related to the modified Fe(C,O)-NP magnetization dynamics. Comparison of the magnetostatic exchange and effective anisotropy length estimated for Fe(C,O)-NPs allows concluding that the anisotropy energy barrier is higher than the magnetostatic energy barrier. The enhanced contribution of surface anisotropy to the effective anisotropy constant and the unique effect of the -COOH groups on the magnetic properties of MWCNTs are discussed. The procedure for grinding carboxylated MWCNTs with embedded iron nanoparticles using a steel mill has a potential application for producing Fe-C nanocomposites with desired magnetic properties.

Effect of Microwave Treatment in a High Pressure Microwave Reactor on Graphene Oxide Reduction Process-TEM, XRD, Raman, IR and Surface Electron Spectroscopic Studies.

Reduced graphene oxide (rGO) was prepared by chemical reduction of graphene oxide (GO) (with a modified Hummers method) in aqueous solutions of hydrazine (N2H4), formaldehyde (CH2O), formic acid (HCO2H) accompanied by a microwave treatment at 250 °C (MWT) by a high pressure microwave reactor (HPMWR) at 55 bar. The substrates and received products were investigated by TEM, XRD, Raman and IR spectroscopies, XPS, XAES and REELS. MWT assisted reduction using different agents resulted in rGOs of a large number of vacancy defects, smaller than at GO surface C sp3 defects, oxygen groups and interstitial water, interlayer distance and diameter of stacking nanostructures (flakes). The average number of flake layers obtained from XRD and REELS was consistent, being the smallest for CH2O and then increasing for HCO2H and N2H4. The number of layers in rGOs increases with decreasing content of vacancy, C sp3 defects, oxygen groups, water and flake diameter. MWT conditions facilitate formation of vacancies and additional hydroxyl, carbonyl and carboxyl groups at these vacancies, provide no remarkable modification of flake diameter, what results in more competitive penetration of reducing agent between the interstitial sites than via vacancies. MWT reduction of GO using a weak reducing agent (CH2O) provided rGO of 8 layers thickness.

Well-defined Graphene Oxide as a Potential Component in Lung Cancer Therapy.

BACKGROUND: Graphene oxide (GO) has unique physical and chemical properties that can be used in anticancer therapy - especially as a drug carrier. Graphene oxide, due to the presence of several hybrid layers of carbon atoms (sp2), has a large surface for highly efficient drug loading. In addition, GO with a large number of carboxyl, hydroxyl and epoxy groups on its surface, can charge various drug molecules through covalent bonds, hydrophobic interactions, hydrogen bonds and electrostatic interactions. OBJECTIVE: The aim of our work was to evaluate the possibility of future use of graphene oxide as an anticancer drug carrier. METHODS: In this paper, we present GO synthesis and characterization, as well as a study of its biological properties. The cytotoxic effect of well-defined graphene oxide was tested on both carcinoma and non-malignant cells isolated from the same organ, which is not often presented in the literature. RESULTS: The performed research confirmed that GO in high concentrations (> 300 µgmL-1) selectively decreased the viability of cancer cell line. Additionally, we showed that the GO flakes have a high affinity to cancer cell nucleus which influences their metabolism (inhibition of cancer cell proliferation). Moreover, we have proved that GO in high concentrations can cause cell membrane damage and generate reactive oxygen species on a low level mainly in cancer cells. CONCLUSION: The proposed GO could be useful in anticancer therapy. A high concentration of GO selectively causes the death of tumor cells, whereas GO with low concentration could be a potential material for anticancer drug loading.

Sulfonated Pentablock Copolymer Membranes and Graphene Oxide Addition for Efficient Removal of Metal Ions from Water.

Nowadays heavy metals are among the higher environmental priority pollutants, therefore, the identification of new, effective, reusable and easy-to-handle adsorbent materials able to remove metal ions from water is highly desired. To this aim, in this work for the first time, sulfonated pentablock copolymer (s-PBC, Nexar™) membranes and s-PBC/graphene oxide (GO) nanocomposite membranes were investigated for the removal of heavy metals from water. Membranes were prepared by drop casting and their chemical, structural and morphological properties were characterized using scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectroscopy, dynamic mechanical analysis (DMA) and small-angle X-ray scattering (SAXS). The adsorption abilities and adsorption kinetics of both the polymer and the s-PBC/GO nanocomposite were investigated for the removal of different heavy metal ions (Ni2+, Co2+, Cr3+ and Pb2+) from aqueous solutions containing the corresponding metal salts at different concentrations. The investigated s-PBC membrane shows a good efficiency, due to the presence of sulfonic groups that play a fundamental role in the adsorption process of metal ions. Its performance is further enhanced by embedding a very low amount of GO in the polymer allowing an increase by at least three times of the adsorption efficiencies of the polymer itself. This can be ascribed to the higher porosity, higher roughness and higher lamellar distances introduced by GO in the s-PBC membrane, as evidenced by the SEM and SAXS analysis. Both the polymeric materials showed the best performance in removing Pb2+ ions.

Graphene Oxide with Controlled Content of Oxygen Groups as a Filler for Polymer Composites Used for Infrared Radiation Shielding.

Infrared (IR) shielding materials are commonly used for different applications, such as smart windows or optical filters. Infrared radiation is responsible for about 50% of the energy coming from the sun. During a hot summer or cold winter a lot of energy is needed to keep the optimal temperature inside buildings and means of transport. To reduce the heat transmission and save energy IR shielding materials can be used as coatings made of polymer composites. Graphene oxide (GO) and its reduced forms have interesting IR absorption properties and might be used as a filler in a polymer matrix for IR shielding applications. Graphene oxide can be reduced by different methods. Depending on the reduction method reduced graphene oxide (rGO) with a different content of oxygen can be obtained exhibiting different properties. In this work we propose new polymer nanocomposites with poly(vinyl alcohol) as the matrix and 0.1 wt.% addition of graphene materials with different oxygen content to be used for IR shielding applications. The results show that the properties of the graphene filler strongly influence the infrared shielding properties of the obtained nanocomposites. The best IR shielding properties were obtained for the composites where rGO with the lowest oxygen content was used.