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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.

This paper reports on the generation, properties, and spatial variability of the graded layer in functionally graded concrete (FGC) made using 20, 35, and 50% ground granulated blast furnace slag (GGBFS) as partial replacement of ordinary Portland cement (OPC). Two different layers of concrete, one being OPC based normal concrete and the other being GGBFS blended concrete were used to prepare the FGC specimens. The control concrete specimens were made with a single layer OPC or GGBFS concrete. Excluding the control concrete samples, three types of double-layered cube samples of 150 mm thick were prepared in various combinations of the thickness of constituent layers. These double-layered combinations were 25 mm + 125 mm, 75 mm + 75 mm, and 125 mm + 25 mm thick containing OPC concrete and GGBFS blended concrete respectively. The properties like compressive strength, the interfacial bond between two constituent layers, modulus of elasticity, micro-structure, and graded layer were examined. The formation, thickness, and properties of the graded layer at the interface of constituent layers were evaluated using elastic equations and microstructural studies like scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS). The investigation was conducted by applying the load parallel and perpendicular to the interface plane between constituent layers. The results showed that the properties of concrete improved in FGC compared to control. Formation of graded layer added value to the FGC. Among the specimens of various thickness combinations, the samples with 75 mm OPC concrete and 75 mm GGBFS concrete showed the best results when the load was applied parallel to the graded layer. Finally, environmental benefit in terms of embodied CO2, energy and cost benefit of the different mix proportion concrete are analysed. Further the effectiveness of FGC is also reported which has huge potential to be used in concrete structure elements.

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.

Functionalization of single-walled carbon nanotubes (SWCNT) with polyethylene glycol (PEG) is among the most promising strategies to avoid SWCNT aggregation in aqueous media, improving its interactions with biological systems. However, the best molecular PEG weight and functionalization strategy remain under investigation. In this work we assessed the toxicological effects of SWCNT functionalized with PEG at 600 Da in zebrafish embryos. Embryos were exposed to SWCNT at 0.01, 0.1 and 1 mg/L from 3 to 96 h post-fertilization (hpf). At the highest concentration, SWCNT led to toxic effects at several endpoints, including mortality, delayed hatching, malformations, reduced body length, increased ROS production and DNA damage. Even with these effects, SWCNT could not be detected within the bodily tissues of the larvae. Our results give evidence that the tested PEGylation approach was unsuitable to avoid SWCNT aggregation in aqueous media, and that SWCNT can induce toxicity even without being absorbed by the organism by obstructing the chorion pores.

During the heavy oil hydroprocessing, a decrease in catalytic activity with time-on-stream (TOS), is due to the metal and carbon deposition on the catalysts. In this investigation, spent catalysts were obtained from the Maya heavy crude hydrotreating unit, as the processing conditions were close to the industrial practice. The catalysts were unloaded after considerable activity decrease, considering the initial activity as base activity. The spent catalysts were characterized by pore size distribution, SEM-EDS, TEM and 13C solid state NMR. Results indicate that catalysts were deactivated mainly due to the deposition of metal and carbon. The sources of deactivation were identified along with the location of foreign species by analyzing the deposited species on the spent catalysts. The nature of the coke and its compositions were derived from 13C CP/MAS and CP/MAS with dipolar dephasing NMR experiments. The wide range of analysis of spent catalysts specify that the catalyst pores were plugged during the heavy oil processing. The deactivation of catalysts were not only due to the carbon deposition but also due to the deposited metal sulfide (VxSy, NixSy) over the existing (CoMoS) active sites. It appear from the results that considerable amount of deactivation is irreversible and non-regeneratable (i.e., metal deposition). Hence catalyst deactivation during heavy oil hydrotreating (HDT) is a function of metal and carbon deposition during time-on-stream. The metal deposition on spent catalysts, e.g. vanadium is on the surface, while Ni distributed deeper into the pore of the catalysts. The removal of Ni and V showed different behavior, which was attributed to an oxygen atom presence to vanadium and its influence on the vanadium porphyrin structure.

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.

Raman spectroscopy is widely used to investigate the structure and property of the molecules from their vibrational transitions and may allow for the diagnosis of cancer in a fast, objective, and nondestructive manner. This experimental study aims to propose the use of the 1064-nm wavelength laser in a Raman spectroscopy and to evaluate its discrimination capability in prostate cancer diagnosis. Seventy-four spectra from patients who underwent radical prostatectomy were evaluated. The acquired signals were filtered, normalized, and corrected for possible oscillations in the laser intensity and fluorescence effects. Wilcoxon tests revealed significant differences between the benign and malign samples associated with the deformation vibration characteristic of nucleic acids, proteins, and lipids. A classifier based on support vector machines was able to predict the Gleason scores of the samples with 95% of accuracy, opening a perspective for the use of the 1064-nm excitatory wavelength in prostatic cancer diagnosis.

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.