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The chemical exfoliation of graphite in liquids is the choice method to produce few-layer graphenes with versatility and scalability. While physical mechanisms have been described, the understanding of the graphene-medium interactions at the molecular level is still a challenge. Here, a systematic experimental and theoretical investigation of factors that control the chemical exfoliation of graphite into graphene was performed using 1-cyclohexyl-2-pyrrolidone (CHP)/water mixtures as model systems. The “molecular wedge” structure of CHP and the reduction of graphene-CHP interfacial energy are critical factors in the exfoliation of graphite, but they are not sufficient for the stabilization of the isolated graphene sheets. We propose that such stabilization occurs by steric forces with the formation of a sandwich-like structure on the surface of graphene with two layers of water molecules interleaved with a monolayer of CHP, and by electrostatic forces resulting from the hybrid surface polarization due to the CHP/H2O-graphene interaction. This stabilization is hampered in CHP/H2O mixtures containing above 10 wt% CHP due to the formation of CHP–CHP aggregates.

The heterogeneous nature of mass-produced 2D material’s nanoflakes requires analysis of size and shape parameters: their distributions around the desired values are essential for production and cha...

The interaction between carbon nanotubes (CNTs) and biological molecules of diagnostic and therapeutic interest, as well as the internalization of the CNTs-biomolecules complexes in different types of cell, has been extensively studied due to the potential use of these nanocomplexes as multifunctional nanoplatforms in a great variety of biomedical applications. The effective use of these nanobiotechnologies requires broad multidisciplinary studies of biocompatibility, regarding, for example, the in vitro and in vivo nanotoxicological assays, the capacity to target specific cells and the evaluation of their biomedical potential. However, the first step to be reached is the careful obtainment of the nanoplatform and the understanding of the actual surface composition and structural integrity of the complex system. In this work, we show the detailed construction of a nanoplatform created by the noncovalent interaction between oxidized multi walled carbon nanotubes (MWCNTs) and a DNA aptamer targeting tumor cells. The excess free aptamer was removed by successive washes, revealing the actual surface of the nanocomplex. The MWCNT-aptamer interaction by π-stacking was evidenced and shown to contribute in obtaining a stable nanocomplex compatible with aqueous media having good cell viability. The nucleotide sequence of the aptamer remained intact after the functionalization, allowing its use in further studies of specificity and binding affinity and for the construction of functional nanoplatforms.

In this work, we report evidences of the improvement of X-ray attenuation efficiency by the addition of a very small amount of Graphene Oxide (GO) in polymer-based nanocomposite. Poly(vinylidene fluoride) (PVDF) homopolymer and barium sulfate (BaSO4) nanoparticles were mixed. PVDF/BaSO4 nanocomposite was found to attenuate 9.14% of a 20 kV X-ray beam. The addition of only 4.0 wt % of GO nanosheets to the nanocomposite improved this X-Ray attenuation efficiency to 24.56%. The respective linear attenuation coefficients (μ) were 39.9 cm−1 and 54.4 cm−1, respectively. The X-ray attenuation gradually decreases until 6.71% and 17.62%, respectively, for the X-ray beam with higher energy (100 kV). Fourier transform infrared data revealed that, due to the lack of the bending vibration modes of CF2 molecule at 656 cm−1, 688 cm−1, 723 cm−1, 776 cm−1and 796 cm−1, characteristics of the γ-crystalline phase of PVDF the nanocomposites casted from solution are mostly in the β-ferroelectric phase of PVDF, besides the γ-paraelectric phase. SEM micrographs were used to evaluate the dispersion state of graphene sheets and the BaSO4 nanoparticles into the polymeric matrix. UV-Vis spectrometry and Differential Scanning Calorimetry (DSC) were also performed in order to complement the structural analysis. The results confirm that the addition of graphene sheets in PVDF polymer-based nanocomposites enhances the X-ray shielding efficiency. The phenomenon is discussed in terms of the reported anomalous negative thermal expansion coefficient of graphene sheets

The genotoxicity of pyrene-polyethylene glycol-modified multi-walled carbon nanotubes (MWCNT-PyPEG), engineered as a nanoplatform for bioapplication, was evaluated. Toxicity was assessed in hamster lung fibroblast cells (V79-4). MTT and Cell Titer Blue methods were used to evaluate cell viability. Genotoxicity was measured by the comet assay and the cytokinesis-block micronucleus cytome (CBMN-Cyt) assay, and fluorescence in situ hybridization (FISH) was used to test induction of structural chromosome aberrations (clastogenic activity) and/or numerical chromosome changes (aneuploidogenic activity). Exogenous metabolic activation enzymes were used in the CBMN-Cyt and FISH tests. Only with metabolic activation, the hybrids caused chromosomal damage, by both clastogenic and aneugenic processes.

Irradiation of tumor cell lines is a useful way to investigate the effects of ionizing radiation on biological molecules. We designed an easy and reproducible approach for in vitro experimental high dose rate brachytherapy, which was simulated by a Monte Carlo code and dosimetrically characterized by experimental methods to evaluate the correspondence between planned doses and doses absorbed by the cells. This approach is an acrylic platform containing T25 tissue culture flasks and multiwell tissue culture plates. It allows nine parallel needles carrying an 192Ir source to irradiate the adherent cells. The whole system composed of the acrylic platform, tissue culture flasks and 192Ir source tracking was simulated by the Monte Carlo N-Particle transport code (MCNPX). Dosimetric measurements were taken by well ionization chamber and radiochromic films. There was a slight difference, averaging from 2% to 7%, between the MCNPX results and film dosimetry results regarding uniform radiation created by the source arrangement. The results showed different values for planned and measured doses in each cell culture plate, which was attributed to the non-equivalent water material used and to the lack of full scattering coming from the top of the platform. This last contribution was different for each tissue culture plate and an individual dose correction factor was calculated. The dose correction factor must be applied to match the planned dose and the actual doses absorbed by the cells. The designed approach is an efficient tool for in vitro brachytherapy experiments for most commercial cell culture plates.

The functionalization of graphene oxide with organosilanes is an important strategy to yield graphene-silica composites as well as to create nanomaterials for use as reinforcement in polymer nanocomposites and corrosion-inhibiting coatings for metals, among other uses. However, depending on the reaction conditions used, the organosilanes tend to self-condense, encapsulating the graphene oxide in a silica-like layer which can impair its properties by hiding its real surface and two-dimensionality. In this paper we describe a facile route for the functionalization of commercial graphene oxide with (3-aminopropyl) triethoxysilane using low concentrations and mild reaction conditions, and yielding amine and silanol surface-modified graphene nanohybrids while preserving its two-dimensional characteristics. The material obtained was characterized by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), potentiometric titration, thermogravimetric analysis and electronic microscopy, evidencing the covalent and superficial nature of the functionalization.

We report an enhanced X-ray shielding effect related to graphene. The mass attenuation coefficients measured for nanocomposites made of poly(vinylidene fluoride) (PVDF) filled with 1.88 wt % functionalized graphene oxides (GO), pyrolytic graphite (PG), multiwalled carbon nanotubes (MWCNT), and amorphous carbon (soot) have been compared. For 6.9 keV photons, the value measured for graphene-based nanocomposite was found to be four times higher than that encountered for the other graphitic-based nanocomposites. The mass attenuation coefficients were measured for X-ray photons with 6.9, 8.1, 17.5, and 22.1 keV, respectively. Fourier transform infrared data revealed that all graphitic composites casted from solution are in the ferroelectric β-phase of PVDF. It is demonstrated that thin films of ferroelectric PVDF/1.88 wt % GO nanocomposite, with thickness of only 0.1 mm, can attenuate 82.9% and 48.5% of X-ray beams with energies of 6.9 and 8.1 keV, respectively. Thus, lightweight, very thin, and lead-free PVDF...

This work describes the production of carbon xerogel/TiO2 nanocomposites by sol-gel polymerization of resorcinol-formaldehyde in the presence of K2TiF6 inorganic titanium salt as TiO2 precursor. The effects of different starting C/Ti molar ratios in the morphology, surface property, and photocatalytic activity on the decomposition of acetaminophen (APP) were investigated. The materials were characterized by thermogravimetric analysis, Fourier transforms infrared spectroscopy, scanning and transmission electron microscopy, X-ray diffractometry, and textural properties. The composites presented heterogeneous structure, and presence of two phases for the introduction of TiO2. A region was formed by amorphous carbon and carbon spheres, where Ti is detected only immersed in the amorphous carbon particles, in the anatase phase. CXTi-4.5 (adopted nomenclature CXTi-n, where n is the number of mmol of titanium salt inserted) composite presented the highest efficiency in the removal of the APP in the aqueous medium, as well as acceptable reusability properties after the washing step.

The production and use of graphene-based nanomaterials is rapidly increasing. However, few data are available regarding the toxicity of these nanomaterials in aquatic organisms. In the present study, the toxicity of few-layer graphene (FLG) (obtained by chemical exfoliation) was evaluated in different tissues of the shrimp Litopenaeus vannamei following exposure to FLG through a diet for four weeks. Transmission electron microscopy and dynamic light scattering measurements showed a distribution of lateral sheet sizes between 100 and 2000 nm with the average length and width of 800 and 400 nm, respectively. Oxidative stress parameters were analyzed, indicating that FLG exposure led to an increase in the concentration of reactive oxygen species, modulated the activity of antioxidant enzymes such as glutamate cysteine ligase and glutathione-S-transferase, and reduced glutathione levels and total antioxidant capacity. However, the observed modulations were not sufficient to avoid lipid and DNA damage in both gill and hepatopancreas tissues. Furthermore, graphene exposure resulted in morphological changes in hepatopancreas tissues. These results demonstrate that exposure to FLG through the diet induces alterations in the redox state of cells, leading to a subsequent oxidative stress situation. It is therefore clear that nanomaterials presenting these physico-chemical characteristics may be harmful to aquatic biota.

Two different types of multi walled carbon nanotubes (MWCNT) were introduced in a calcium aluminate refractory castable used in steelmaking process. The first MWCNT was purchased from Cheap Tubes (USA), a hydroxyl (-OH) functionalized, outer diameter of 50-80 nm, length of 10-20 μm, and, the second one was supplied by Nanocyl (Belgium), not functionalized, outer diameter of 9.5 nm, and length of 1.5 μm. Both types of MWCNT were incorporated into the dry castable mixture before water addition. The workability and properties of the final product, such as apparent density, apparent porosity and hot modulus of rupture were evaluated. The nanocarbons were characterized by SEM, TEM, TGA and Raman spectroscopy. In both cases, the incorporation of MWCNT had a negative effect on the rheology of wet castables, decreasing their workability. No significant improvements on mechanical properties of the castables were observed with the incorporation until MWCNT concentration reached 0.15 % (m/m), except for the increase of hot modulus of rupture observed for Cheap Tubes MWCNT introduction.

Anaplasmosis is one of the most prevalent tick-borne diseases of cattle caused by Anaplasma marginale. MSP1a surface protein has been shown to be involved in eliciting immunity to infected cattle. Carbon nanotubes (CNTs) has been increasingly highlighted due to their needle like structure, which contain multiple attachment sites for biomolecules and may interact with or cross biological membranes, increasing antigen availability to immune system. Here, we have successfully designed a nanocomplex of a synthetic peptide noncovalently attached to multiwalled CNT (MWCNT). Peptide comprising the core motif of the MSP1a was efficiently adsorb onto the nanoparticle surface. The MWCNT-Am1 nanocomplex exhibited high stability and good dispersibility and in vivo immunization showed high levels of IgG1 and IgG2a, followed by increased expression of pro-inflammatory and anti-inflammatory cytokines. This is a proof-of-concept of a nanovaccine that was able to generate a strong immune response compared to the common antigen-adjuvant vaccine without the nanoparticles.

Carbon nanomaterials (CNM), such as graphene oxide (GO), have been the focus of study in several areas of science mostly due to their physical-chemical properties. However, data concerning the potential toxic effects of these CNM in bivalves are still scarce. When present in the aquatic systems, the combination with other contaminants, as well as pH environmental variations, can influence the behavior of these nanomaterials and, consequently, their toxicity. Thus, the main goal of this study was to evaluate the effect of exposure of clam Ruditapes philippinarum to GO when acting alone and in the combination with copper (Cu), under two pH levels (control 7.8 and 7.3). A 28-day exposure was performed and metabolism and oxidative stress-related parameters were evaluated. The effects caused by GO and Cu exposures, either isolated or co-exposed, showed a direct and dependent relationship with the pH in which the organisms were exposed. In clams maintained at control pH (7.8), Cu and GO + Cu treatments showed lower lipid peroxidation (LPO) and lower electron transport system (ETS) activity, respectively. In clams maintained at low pH, glutathione-S-transferases (GSTs) activities were increased in Cu and Cu + GO treatments, whereas reduced glutathione (GSH) levels were increased in Cu treatment and ETS activity was higher in GO + Cu. Thus, it can be observed that clams responses to Cu and GO were strongly modulated by pH in terms of their defense system and energy production, although this does not result into higher LPO levels.

Xerogeis de carbono (CXs) sao materiais constituidos por uma estrutura tridimensional formada por esferas nanometricas interligadas e poros interconectados. Diversos trabalhos apresentam os CXs como suporte para utilizacao em catalise. A principal vantagem destes suportes e que suas propriedades fisicas e quimicas superficiais podem ser adaptadas as exigencias cataliticas. Neste trabalho, compositos CX/TiO2 foram sintetizados em etapa unica, por polimerizacao/condensacao sol-gel de solucao formaldeido e resorcinol, com simultânea adicao de nanoparticulas de TiO2 ou Ti(IV), seguido de secagem e tratamento termico. Os compositos foram caracterizados por analise termogravimetrica (TG), difratometria de raios X (DRX), microscopia eletronica de varredura (MEV), espectroscopia Raman e isotermas de adsorcao de nitrogenio (N2) com determinacao de area superficial (BET) e volume de poros (Vp). Os resultados mostraram a presenca de uma mistura das fases anatase e rutilo do TiO2 nos compostos obtidos. Atraves das imagens de MEV verificou-se grande homogeneidade na distribuicao das particulas de TiO2 no suporte de CX. As propriedades fotocataliticas dos compositos foram investigadas para fotodegradacao de azul de metileno (AM). A cinetica de degradacao de azul de metileno ajustou-se ao modelo de pseudo primeira ordem. Observou-se um efeito sinergico entre os solidos, com um aumento da atividade fotocatalitica nos compositos de CX/TiO2, em relacao ao TiO2. Palavras-chave: carbono xerogel, fotocatalise, oxido de titânio.

The use of carbon nanomaterials (CNMs) is growing in different technological fields, raising concern on their potential impacts on the environment. Given its diverse nanothenological applications, graphene oxide (GO) stands out among the most widely used CNMs. Its hydrophilic capacity enables it to remain stable in suspension in water allowing that GO can be accessible for accumulation by aquatic organisms through ingestion, filtration and superficial dermal contact when present in aquatic ecosystems. Considering that the effects induced to aquatic organisms may depend on environment characteristics, such as temperature, salinity, water pH as well as the presence/absence of sediment, the present study aimed to investigate the influence of sediment on the impacts caused by GO exposure. For this, oxidative stress parameters were measured in the clam Ruditapes philippinarum, exposed to different GO concentrations (0.01, 0.1 and 1 mg/L), in the presence and absence of sediment, for a 28-days experimental period. The results here presented showed that regardless the presence or absence of sediment, most of the biochemical parameters considered were altered when clams were exposed to the highest concentration. The present findings further revealed that in the presence of sediment, clams mostly invested in non-enzymatic defenses (such as reduced glutathione, GSH), while animals exposed to GO in the absence of sediment favored their enzymatic antioxidant defense capacity (catalase, CAT and superoxide dismutase, SOD). This study highlights the relevance of environmental variations as key factors influencing organisms' responses to pollutants.

Single-wall carbon nanotubes functionalized with polyethylene glycol (SWCNT-PEG) are promising materials for biomedical applications such as diagnostic devices and controlled drug-release systems. However, several questions about their toxicological profile remain unanswered. Thus, the aim of this study was to investigate the action of SWCNT-PEG in Danio rerio zebrafish embryos at the molecular, physiological and morphological levels. The SWCNT used in this study were synthesized by the high-pressure carbon monoxide process, purified and then functionalized with distearoyl phosphatidylethanolamine block copolymer-PEG (molecular weight 2 kDa). The characterization process was carried out with low-resolution transmission electron microscopy, thermogravimetric analysis and Raman spectroscopy. Individual zebrafish embryos were exposed to the SWCNT-PEG. Toxic effects occurred only at the highest concentration tested (1 ppm) and included high mortality rates, delayed hatching and decreased total larval length. For all the concentrations tested, the alkaline comet assay revealed no genotoxicity, and Raman spectroscopy measurements on the histological slices revealed no intracellular nanotubes. The results shown here demonstrate that SWCNT-PEG has low toxicity in zebrafish embryos, but more studies are needed to understand what mechanisms are involved. However, the presence of residual metals is possibly among the primary mechanisms responsible for the toxic effects observed, because the purification process was not able to remove all metal contamination, as demonstrated by the thermogravimetric analysis. More attention must be given to the toxicity of these nanomaterials before they are used in biomedical applications. Copyright © 2016 John Wiley & Sons, Ltd.

The influence of extensive purification on oxidized multiwalled carbon nanotube surface composition was studied through the characterization and differentiation of the actual surface submitted to three oxidation methods: microwave-assisted acid oxidation, hydrogen peroxide reflux, and Fenton reaction. The oxidized samples were purified by a multi-step procedure including the sequential use of basic reflux and dispersion in dimethylformamide (DMF). The results showed a significant increase in the amount of oxidation debris with hydrogen peroxide and Fenton reaction times longer than 8 h and strong surface characteristic modification. With regard to sample purification, basic reflux led to a reduction in oxygenated group concentration of only 10% in the samples treated by acid oxidation. On the other hand, the subsequent use of DMF led to a further decrease in concentration of 39%, proving to be a more efficient method for the removal of oxidation debris.

Arsenic (As) is one of the most widespread contaminants; it is found in almost every environment. Its toxic effects on living organisms have been studied for decades, but the interaction of this metalloid with other contaminants is still relatively unknown, mainly whether this interaction occurs with emerging contaminants such as nanomaterials. To examine this relationship, the marine shrimp Litopenaeus vannamei was exposed for 48 h to As, graphene oxide (GO; two different concentrations) or a combination of both, and gills, hepatopancreas and muscle tissues were sampled. Glutathione S-transferase (GST)-omega gene expression and activity were assessed. As accumulation and speciation (metabolisation capacity) were also examined. Finally, a molecular docking simulation was performed to verify the possible interaction between the nanomaterial and GST-omega. The main finding was that GO modulated the As toxic effect: it decreased GST-omega activity, a consequence related to altered As accumulation and metabolism. Besides, the molecular docking simulation confirmed the capacity of GO to interact with the enzyme structure, which also can be related to the decreased GST-omega activity and subsequently to the altered As accumulation and metabolisation pattern.

Multi-layer graphene (MLG) sheets were obtained by exfoliation of natural graphite flakes in chloroform. Dispersions with concentration up to 19 mg/mL were prepared. Statistical measurements of MLG sheet sizes by transmission electron microscopy showed average width and length of ~340 nm and 860 nm, respectively. MLG/chloroform dispersions were used to prepare poly(lactic acid) (PLA)/MLG composite fibrillar membranes by electrospinning. A homogeneous distribution of MLG into the fibers was observed by optical and scanning electron microscopies. The presence of MLG leads to the decrease in the diameter distribution of the fibers, which presented average diameter values below 500 nm. Isothermal kinetic crystallization of PLA showed to be influenced by the electrospinning process and the content of MLG sheets, which acts as nucleating agents.

Graphene has been shown to induce toxicity in mammals and marine crustaceans; however, information regarding oxidative stress in fish is scarce. The aim of this study was to evaluate the mechanism of graphene toxicity in different tissues of Danio rerio, considering different parameters of stress. Animals were injected intraperitoneally (i.p.) with 10 μL of suspensions containing different graphene concentrations (5 and 50 mg/L); the gills, intestine, muscle and brain were analysed 48 h later. There was no significant difference in the expression of the gclc (glutamate cysteine ligase catalytic subunit) and nrf2 (nuclear factor (erythroid-derived 2)-like 2) genes after exposure. In contrast, glutamate cysteine ligase (GCL) and glutathione-S-transferase (GST) activities were modulated and the glutathione (GSH) concentration was reduced in different tissues and at different concentrations. Lipid damage was observed in the gills. Histological analyses were performed to observe if the exposure could induce pathological damage in these tissues. The results showed pathological effects in all tissues, excluding the intestine, after exposure to both concentrations. Overall, these results indicate that graphene induces different grades of toxicological effects that are dependent on the analysed organ, with distinct pathological effects on some and oxidative effects on others. However, the brain and gills seem to be the primary target organs for graphene toxicity.

Carbon nanotubes (CNT) are promising materials for biomedical applications, especially in the field of neuroscience; therefore, it is essential to evaluate the neurotoxicity of these nanomaterials. The present work assessed the effects of single-walled CNT functionalized with polyethylene glycol (SWCNT-PEG) on the consolidation and retrieval of contextual fear memory in rats and on oxidative stress parameters in the hippocampus. SWCNT-PEG were dispersed in water at concentrations of 0.5, 1.0, and 2.1 mg/mL and infused into the rat hippocampus. The infusion was completed immediately after training and 30 min before testing of a contextual fear conditioning task, resulting in exposure times of 24 h and 30 min, respectively. The results showed that a short exposure to SWCNT-PEG impaired fear memory retrieval and caused lipid peroxidation in the hippocampus. This response was transient and overcome by the mobilization of antioxidant defenses at 24 h. These effects occurred at low and intermediate but not high concentration of SWCNT-PEG, suggesting that the observed biological response may be related to the concentration-dependent increase in particle size in SWCNT-PEG dispersions.

Exposure to ionizing radiation has been found to induce changes in poly(vinylidene fluoride) (PVDF) homopolymers. The high dose gamma irradiation process induces the formation of C=C and C=O bonds in its [CH2-CF2]n main chain. The irradiation also provokes crosslinking and chain scission. All these radio-induced defects lead to changes in the PVDF crystalline structure. As a consequence, it is common to observe a decrease in the melting temperature (TM) and melting latent heat (LM) and some changes in its ferroelectric features. We have investigated the possibility of preparing nanocomposites of PVDF with graphene oxide (GO) through the radio-induction of molecular bonds. In this work, we discuss how the gamma radiation interacts with the nanocomposite crystalline structure., {"references":["G. Botelho, S. Lanceros-Mendez, A.M. Gonçalves, V. Sencadas, J.G. Rocha, \"Relationship between processing conditions, defects and thermal degradation of poly(vinylidene fluoride) in the β-phase\" in Journal of Non-Crystalline Solids, vol. 354, 2008, pp.72-78.","M. Celina, T.R. Dargaville, R. A. Assink, J. W. Martín, \"Selection and optimization of piezoelectric polyvinylidene fluoride polymers for adaptive optics in space environments\" in High Performance Polymers, vol. 17, 2005, pp. 575-593.","R. D. Dreyer, S. Park, C. W. Bielawski, R. S. Ruoff, \"The chemistry of graphene oxide\" in Chemical Society Reviews, vol. 39, 2010, pp. 228-240.","C. Yu, D. Li, W. Wu, C. Luo, Y. Zhang, C. Pan, \"Mechanical property enhancement of PVDF/graphene composite based on a high-quality graphene\" in Journal Materials Science, vol. 49, 2014, pp. 8311-8316.","I. Boullier, S. Esnouf, A. L. Moël, \"Radiooxidation of fluoropolymers: identification of oxidation products\" in \"Journal of Polymer Science Part B Polymer Physics, vol. 41, 2003, pp. 1509 – 1517."]}

The production and use of graphene-based nanomaterials is rapidly increasing. However, few data are available regarding the toxicity of these nanomaterials in aquatic organisms. In the present study, the toxicity of few-layer graphene (FLG) (obtained by chemical exfoliation) was evaluated in different tissues of the shrimp

Raman spectra of octadecylamine (ODA) molecules covalently bound to the surface of single walled carbon nanotubes were obtained by varying the laser excitation energy from 1.92 to 3.81 eV. A strong dependence of the Raman intensity on the excitation energy was observed and, under specific conditions of resonance, the Raman signal from the amide linkage can become even stronger than the resonant Raman signal of the carbon nanotubes. This result is explained in terms of a chemical enhancement mechanism due to charge transfer between the ODA molecules and the nanotubes. The enhancement factor was up to 100 times higher than the value typically reported for the chemical Surface Enhanced Raman Scattering (SERS) effect. Our results show that carbon nanotubes may contribute to the still controversial understanding of the ‘chemical’ effects to the enhancement in SERS, extending the scope of application of this analytical tool in strategic areas such as biomedicine, catalysis and environmental analysis.

Suspensions of oleic acid with carbon nanotubes were prepared. Using a thermal lens experimental setup, the thermal diffusivity of oleic acid in presence of multi-walled carbon nanoparticles with different concentrations was measured. The results show that, the thermal diffusivity increases with the increase of nanotubes concentration, enhancing the thermal diffusivity in the solution. Modification in the thermal diffusivity as function of quantity of carbon nanotubes was investigated, for a constant volume of oleic acid 10 mL. The diffusivities were obtained by using the thermal lens spectrometry technique. The characteristic time constant of the transient thermal lens was obtained by fitting the theoretical expression to the experimental data.

Single-wall carbon nanotubes functionalized with polyethylene glycol (SWCNT-PEG) are promising materials for biomedical applications such as diagnostic devices and controlled drug-release systems. However, several questions about their toxicological profile remain unanswered. Thus, the aim of this study was to investigate the action of SWCNT-PEG in Danio rerio zebrafish embryos at the molecular, physiological and morphological levels. The SWCNT used in this study were synthesized by the high-pressure carbon monoxide process, purified and then functionalized with distearoyl phosphatidylethanolamine block copolymer-PEG (molecular weight 2 kDa). The characterization process was carried out with low-resolution transmission electron microscopy, thermogravimetric analysis and Raman spectroscopy. Individual zebrafish embryos were exposed to the SWCNT-PEG. Toxic effects occurred only at the highest concentration tested (1 ppm) and included high mortality rates, delayed hatching and decreased total larval length. For all the concentrations tested, the alkaline comet assay revealed no genotoxicity, and Raman spectroscopy measurements on the histological slices revealed no intracellular nanotubes. The results shown here demonstrate that SWCNT-PEG has low toxicity in zebrafish embryos, but more studies are needed to understand what mechanisms are involved. However, the presence of residual metals is possibly among the primary mechanisms responsible for the toxic effects observed, because the purification process was not able to remove all metal contamination, as demonstrated by the thermogravimetric analysis. More attention must be given to the toxicity of these nanomaterials before they are used in biomedical applications. Copyright © 2016 John WileySons, Ltd.

The combination of the properties of graphene oxide (OG) and PVDF homopolymer makes their combined composite materials as multifunctional systems with great potential. Knowledge of the molecular structure is essential for better use. In this work, the degradation of PVDF polymer exposed to gamma irradiation in oxygen atmosphere in high dose rate has been studied and compared to degradation of PVDF/OG composites. The samples were irradiated with a Co-60 source at constant dose rate, with doses ranging from 100 kGy to 1,000 kGy. In FTIR data shown that the formation of oxidation products was at the both samples with formation of carbonyl and hydroxyl groups amongst the most prevalent products in the pure PVDF samples. In the other hand, the composites samples exhibit less presence of degradation products with predominant formation of carbonyl groups, these results also seen in the UV-Vis analysis. The results show that the samples of composites may have greater resistance to the irradiation process, since they have less degradation products than pure PVDF samples seen by spectroscopic techniques.

The combination of multi–walled carbon nanotubes (MWCNTs) with polymers offers an attractive route to reinforce the macromolecular compounds as well as the introduction of new properties based on morphological modifications or electronic interactions between the two constituents. As they are only a few nanometers in dimension, it offers ultra-large interfacial area per volume between the nano-element and polymer matrix. Nevertheless, the use of MWCNTs as a rough material in different applications has been largely limited by their poor processability, insolubility, and infusibility. Studies concerning the nanofiller reinforced polymer composites are justified in an attempt to overcome these limitations. This work presents one preliminary study of MWCNTs dispersion into the PVDF homopolymer. For preparation, the composite components were diluted in n,n-dimethylacetamide (DMAc) with mechanical agitation assistance. After complete dilution, followed by slow evaporation of the solvent at 60°C, the samples were dried. Films of about 80 μm were obtained. FTIR and UV-Vis spectroscopic techniques were used to characterize the nanocomposites. The appearance of absorption bands in the FTIR spectra of nanofilled samples, when compared to the spectrum of pristine PVDF samples, are discussed and compared with the UV-Vis measurements.

This paper presents a novel TiO2-Graphene composite film one-step preparation method by electrochemical synthesis. The films were prepared on a Ti substrate by electrochemical deposition from a GO and Ti (IV) aqueous solution. For comparison, pure TiO2 on a Ti substrate was obtained by the same electrochemical method. The as-prepared samples were characterized by X-ray diffraction, scanning electron microscopy, Raman spectroscopy, photoluminescence and ultravioletevisible spectrophotometry. The photocatalytic properties of the films were investigated for the discoloration of Reactive Yellow 145 dye. The results showed that the TiO2-Graphene oxide composite film presented photocatalytic activity almost twice as high as that observed for the TiO2 film. In addition, the TiO2-Graphene oxide composite film presented better stability and recyclability, retaining its catalytic efficiency (z70%) even after 15 cycles. Published by Elsevier B.V.

In this work, it is demonstrated how a novel technique based on temperature-programmed chemical vapor deposition (TPCVD) can be used to investigate the synthesis of carbon nanotubes (CNTs) from methane on a classic catalyst FeMo(x)/MgO (x = 0.07, 0.35 and 1.00). TPCVD monitors carbon deposition by measuring H2 formed during CH4 decomposition and affords information on the different catalytic species, deactivation process, reaction kinetics and carbon yields. The obtained results showed for FeMgO catalyst a simple TPCVD peak related to the production of carbon beginning at 760 degrees C with maximum at 800 degrees C followed by a rapid deactivation resulting in a low carbon yield. The addition of Mo to Fe/MgO catalyst completely changes the TPCVD profile with the formation of a new catalytic species active at temperatures higher than 900 degrees C, which is stable and continuously decomposes CH4 to produce high carbon yields. Raman, TG/DTG, Mössbauer, SEM, TEM, XRD and TPR analyses suggested that this active catalytic phase is likely related to Fe-Mo and Fe-Mo-C phases active to produce single wall and mainly multiwall carbon nanotubes.

This chapter addresses the initial steps one has to give to explore the unique properties of carbon nanotubes in biomedical applications, which are their synthesis, purification and functionalization. We start with a brief description of the structure and properties, and we summarize the synthesis methods. The major issues are then addressed, which are purification and functionalization for bioapplications. We review the different methods, highlighting their advantages and disadvantages.

A new composite electrode is described for anodic stripping voltammetry determination of Pb(II) at trace level in aqueous solution. The electrode is based on the use of multiwalled carbon nanotubes and Amberlite IR-120. The anodic stripping voltammograms depend, to a large extent, on the composition of the modified electrode and the preconcentration conditions. Under optimum conditions, the anodic peak current at around −0.57 V is linearly related to the concentration of Pb(II) in the range from 9.6 × 10−8 to 1.7 × 10−6 mol L−1 (R = 0.998). The detection limit is 2.1 × 10−8 mol L−1, and the relative standard deviation (RSD) at 0.24 × 10−6 mol L−1 is 1.7% (n = 6). The modified electrode was applied to the determination of Pb(II) using the standard addition method; the results showed average relative recoveries of 95% for the samples analysed.

Single-wall carbon nanotubes dispersed in aqueous solutions of different surfactants are investigated by optical absorption and photoluminescence spectroscopies. The role played by the type of surfactant, surfactant concentration, and nanotube concentration on the efficiency of absorption and emission of light by the individualized nanotubes of different chiralities is discussed. By comparing the intensities of absorption and emission is possible to obtain the best nanotube and surfactant concentrations that optimize the light emission efficiency. Changes in the absorption and emission energies are observed and interpreted in terms of the variation of the environments screening on the exciton binding energies.

Multiwalled carbon nanotube/epoxy composites loaded with up to 0.5 wt % multiwalled carbon nanotubes were prepared and characterized. Infrared microscopy, scanning electron microscopy, thermogravimetry, differential scanning calorimetry, thermomechanical analysis, and electrical conductivity measurements of the composites were performed. Infrared microscopy and scanning electron microscopy images showed that the debundled nanotubes were well dispersed. The thermal expansion coefficients, before and after the glass transition, remained approximately constant with the addition of nanotubes, whereas the electrical conductivity at room temperature increased approximately 5 orders of magnitude. This result was attributed to the thermal expansion coefficients of the intertube gap on the carbon nanotube bundles, which were in the same range as that of the epoxy resin. Therefore, nanocomposites capable of electrostatic dissipation can be processed as neat epoxy materials with respect to the volume changes with temperature. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

Single-wall carbon nanotubes (SWCNT) have attracted great interest for applications in a variety of research areas, including electronics and functional materials. However, a good dispersion of these materials in polymer matrices is a demanding factor in order to obtain more homogeneous and less bundled films for constructing optoelectronic and electrochemical devices. In this report we describe a covalent modification with thiophene groups located at the edges and at defects in SWCNT to modify the interaction with the polymer matrix aiming at its application in solar cells. The modified SWCNT and its composites with poly(3-octylthiophene) were characterized by Raman, infrared, UV−vis, and luminescence spectroscopies and cyclic voltammetry. The best bulk heterojunction solar cell was obtained using 5 wt % of the modified carbon nanotube (SWCNT-THIOP) and shows open circuit voltage (VOC), short-circuit current (Isc), and efficiency (η) of 0.75 V, 9.5 μA cm-2, 0.184%, respectively.

Resonance Raman and photoluminescence excitation (PLE) spectroscopies are used to study the optical properties of different types of carbon nanostructures such as carbon nanotube, nanoribbons, nanographites and graphite edges. In the resonance Raman experiments of carbon nanotubes, the ( n , m ) assignment is obtained by comparing the experimental and theoretical diameter and chirality dependence of the optical transitions. The influence of the environment on the optical transitions of the nanotubes is also obtained in the Raman experiments. The PLE measurements in different samples of carbon nanotubes show both direct and phonon-assisted optical transitions, and the results give new evidences that the optical transitions in nanotubes have an excitonic character, which is very strong for the low energy transitions. We also analyze the Raman spectra of nanoribbons and nanographites, showing that this technique is an important tool for defect characterization in graphitic materials, and can be used to distinguish the atomic structure of the graphite edges.

A molecule with a π conjugated backbone built from aromatic thiophene and dialkoxyphenylene units and substituted imidazolium groups (TPO) is designed to obtain ultra-stable single walled carbon nanotube (SWCNT) dispersion in aqueous medium. The proposed mechanism of non-covalent interaction is accompanied by individualization of SWCNT and comprises of dominant nondisruptive π-π and cation-π interaction between them and the TPO conjugated oligomer. The individualization of SWCNT and dispersibility and stability of the ultra-stable suspensions were estimated using high resolution transmission electron microscopy, UV-Visible-NIR absorption spectroscopy, Raman spectroscopy, photoluminescence and zeta potential measurement. Nuclear magnetic resonance data provides direct evidence toward possible cation-π interaction.

Carbon nanotubes are promising nanomaterials for the diagnosis and treatment of brain disorders. However, the ability of these nanomaterials to cross cell membranes and interact with neural cells brings the need for the assessment of their potential adverse effects on the nervous system. This study aimed to investigate the biopersistence of single-walled carbon nanotubes functionalized with polyethylene glycol (SWCNT-PEG) directly infused into the rat hippocampus. Contextual fear conditioning, Y-maze and open field tasks were performed to evaluate the effects of SWCNT-PEG on memory and locomotor activity. The effects of SWCNT-PEG on oxidative stress and morphology of the hippocampus were assessed 1 and 7 days after infusion of the dispersions at 0.5, 1.0 and 2.1 mg/mL. Raman analysis of the hippocampal homogenates indicates the biopersistence of SWCNT-PEG in the hippocampus 7 days post-injection. The infusion of the dispersions had no effect on the acquisition or persistence of the contextual fear memory; likewise, the spatial recognition memory and locomotor activity were not affected by SWCNT-PEG. Histological examination revealed no remarkable morphological alterations after nanomaterial exposure. One day after the infusion, SWCNT-PEG dispersions at 0.5 and 1.0 mg/mL were able to decrease total antioxidant capacity without modifying the levels of reactive oxygen species or lipid hydroperoxides in the hippocampus. Moreover, SWCNT-PEG dispersions at all concentrations induced antioxidant defenses and reduced reactive oxygen species production in the hippocampus at 7 days post-injection. In this work, we found a time-dependent change in antioxidant defenses after the exposure to SWCNT-PEG. We hypothesized that the persistence of the nanomaterial in the tissue can induce an antioxidant response that might have provided resistance to an initial insult. Such antioxidant delayed response may constitute an adaptive response to the biopersistence of SWCNT-PEG in the hippocampus.

Made available in DSpace on 2015-10-21T20:15:10Z (GMT). No. of bitstreams: 0 Previous issue date: 2015-06-17. Added 1 bitstream(s) on 2015-10-22T09:48:16Z : No. of bitstreams: 1 WOS000356518200001.pdf: 803864 bytes, checksum: e41d7e36cd2e1f67d32a7945ba81b594 (MD5) Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Gold is a noble metal that, in comparison with silver and copper, has the advantage of corrosion resistance. Despite its high conductivity, chemical stability and biocompatibility, gold exhibits high plasticity, which limits its applications in some nanodevices. Here, we report an experimental and theoretical study on how to attain enhanced mechanical stability of gold nanotips. The gold tips were fabricated by chemical etching and further encapsulated with carbon nanocones via nanomanipulation. Atomic force microscopy experiments were carried out to test their mechanical stability. Molecular dynamics simulations show that the encapsulated nanocone changes the strain release mechanisms at the nanoscale by blocking gold atomic sliding, redistributing the strain along the whole nanostructure. The carbon nanocones are conducting and can induce magnetism, thus opening new avenues on the exploitation of transport, mechanical and magnetic properties of gold covered by sp(2) carbon at the nanoscale. Univ Fed Minas Gerais, ICEx, Dept Fis, BR-31270901 Belo Horizonte, MG, Brazil Penn State Univ, Mat Res Inst, University Pk, PA 16802 USA Univ Fed Minas Gerais, Ctr Microscopia, BR-30123970 Belo Horizonte, MG, Brazil Ctr Desenvolvimento Tecnol Nucl, BR-31270010 Belo Horizonte, MG, Brazil Univ Estadual Campinas, Inst Fis Gleb Wataghin, BR-13083970 Campinas, SP, Brazil Univ Estadual Paulista, UNESP, IGCE, Dept Fis, Rio Claro, SP 13506900, Brazil Univ Estadual Paulista, UNESP, IGCE, Dept Fis, Rio Claro, SP 13506900, Brazil FAPESP: 2013/08293-7 FAPESP: 2011/17253-3 FAPESP: 2013/09536-0

The thermal and morphological properties of PEO/copolyether electrolyte and carbon black composite have been studied. A copolyether poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminopropyl ether) was used at 20 wt.-% in relation to PEO in order the improve the carbon black dispersion through interaction with the amino end capped function. The polymer matrix presented semicrystalline structure and the addition of LiClO 4 and carbon black decreases significantly the crystallinity of the system. Sub-micrometric dispersion of carbon black was observed. The conductivity results as a function of temperature exhibited a typical VTF behaviour for the electrolyte. Almost constant conductivities of 2 × 10 -4 S cm -1 were observed for the composite with 5 wt.-% of carbon black, in the range of temperature between 35 and 95 °C, which indicates a significantly contribution of electronic conduction.

Wet chemical methods involving ultrasound and amide solvents were used to purify and separate large bundles of single-walled carbon nanotubes (SWNTs) into individual nanotubes that could then be transported to silicon or mica substrates. The SWNTs studied were produced by the arc-discharge process. Dry oxidation was used in an initial step to remove amorphous carbon. Subsequently, two acid purification schemes were investigated (HCl- and HNO(3)-reflux) to remove the metal growth catalyst (Ni-Y). Finally, ultrasonic dispersion of isolated tubes into either N,N-dimethylformamide (DMF) or N-methyl-2-pyrrolidone (NMP) was carried out. Raman scattering, atomic force microscopy (AFM), and electron microscopy were used to study the evolution of the products. Raman scattering was used to probe possible wall damage during the chemical processing. We found that both HCl and HNO(3) could be used to successfully remove the Ni-Y below approximately 1 wt %. However, the HNO(3)-reflux produced significant wall damage (that could be reversed by vacuum annealing at 1000 degrees C). In the dispersion step, both amide solvents (DMF and NMP) produced a high degree of isolated tubes in the final product, and no damage during this dispersion step was observed. HNO(3)-refluxed tubes were found to disperse the best into the amide solvents, perhaps because of significant wall functionalization. AFM was used to study the filament diameter and length distributions in the final product, and interesting differences in these distributions were observed, depending on the chemical processing route.