Graphene oxide-silver nanoparticle hybrid material: an integrated nanosafety study in zebrafish embryos.

This work reports an integrated nanosafety study including the synthesis and characterization of the graphene oxide-silver nanoparticle hybrid material (GO-AgNPs) and its nano-ecotoxicity evaluation in the zebrafish embryo model. The influences of natural organic matter (NOM) and a chorion embryo membrane were considered in this study, looking towards more environmentally realistic scenarios and standardized nanotoxicity testing. The nanohybrid was successfully synthesized using the NaBH4 aqueous method, and AgNPs (~ 5.8 nm) were evenly distributed over the GO surface. GO-AgNPs showed a dose-response acute toxicity: the LC50 was 1.5 mg L-1 for chorionated embryos. The removal of chorion, however, increased this toxic effect by 50%. Furthermore, the presence of NOM mitigated mortality, and LC50 for GO-AgNPs changed respectively from 2.3 to 1.2 mg L-1 for chorionated and de-chorionated embryos. Raman spectroscopy confirmed the ingestion of GO by embryos; but without displaying acute toxicity up to 100 mg L-1, indicating that the silver drove toxicity down. Additionally, it was observed that silver nanoparticle dissolution has a minimal effect on these observed toxicity results. Finally, understanding the influence of chorion membranes and NOM is a critical step towards the standardization of testing for zebrafish embryo toxicity in safety assessments and regulatory issues.

Development of an Impression Material with Antimicrobial Properties for Dental Application.

PURPOSE: To evaluate the antimicrobial activity and physico-mechanical properties of an irreversible hydrocolloid in which nanostructured silver vanadate decorated with silver nanoparticles (AgVO3 ) was added at various concentrations (0% - control, 2.5%, 5%, and 10% by weight). MATERIALS AND METHODS: The agar diffusion method (n = 10) was used to evaluate the inhibitory effect on the following species: Streptococcus mutans, Staphyloccocus aureus, Pseudomonas aeruginosa, Escherichia coli, and Candida albicans. The gelation time, flow capacity and plastic deformation were verified (n = 10). The data were analyzed using the Kruskal-Wallis test followed by the Dunn post-test, or via one-way ANOVA with multiple comparisons with a Bonferroni adjustment depending on the distribution (α = 0.05). RESULTS: All percentages of the nanomaterial were able to promote the antimicrobial activity of a hydrocolloid, with the formation of an inhibition zone (p < 0.05). In general, there was a dose-dependent effect on antimicrobial activity: higher concentrations of the nanomaterial promoted greater action except in the cases of P. aeruginosa (p < 0.001; F = 51.74) and S. aureus (p < 0.001), where the highest inhibition was for the 2.5% group. No difference was found in the gelation time when the control was compared with the groups with AgVO3 (p > 0.05). The difference was between the 5% and 10% groups (p = 0.007), and the latter promoted an increase in time. The flow capacity of the hydrocolloid with 5% of AgVO3 was significantly lower when compared with the control (p = 0.034). The AgVO3 influenced the plastic deformation (p < 0.001) in such a way that concentrations of 5% (p = 0.010) and 10% (p < 0.001) promoted an increase in this property when compared with the control. CONCLUSIONS: AgVO3 can be incorporated into an irreversible hydrocolloid as an antimicrobial agent without promoting adverse effects on physical-mechanical properties when used in concentrations of 2.5%.

In vitro study of the antibacterial properties and impact strength of dental acrylic resins modified with a nanomaterial.

STATEMENT OF PROBLEM: The accumulation of bacteria on the surface of dental prostheses can lead to systemic disease. PURPOSE: The purpose of this in vitro study was to evaluate the growth of Staphylococcus aureus and Pseudomonas aeruginosa on the surface of autopolymerizing (AP) and heat-polymerizing (HP) acrylic resins incorporated with nanostructured silver vanadate (ß-AgVO3) and its impact strength. MATERIAL AND METHODS: For each resin, 216 circular specimens (9 × 2 mm) were prepared for microbiologic analysis and 60 rectangular specimens (65 × 10 × 3.3 mm) for mechanical analysis, according to the percentage of ß-AgVO3: 0%, control group; 0.5%; 1%; 2.5%; 5%; and 10%. After a biofilm had formed, the metabolic activity of the bacteria was measured using the XTT reduction assay (2,3-bis-(2-methoxy-4-nitro-5-sulfophenyl)-2H-tetrazolium-5-carboxanilide) (n=8), and the number of viable cells was determined by counting colony forming units per milliliter (CFU/mL) (n=8). Confocal laser scanning microscopy (CLSM) was used to complement the analyses (n=2). The mechanical behavior was evaluated by impact strength assays (n=10). Data were analyzed by 2-way ANOVA, followed by the Tukey honestly significant difference (HSD) post hoc test (α=.05). RESULTS: The addition of 5% and 10% ß-AgVO3 significantly decreased the metabolic activity of P. aeruginosa for both resins (P<.05). The HP resin promoted a greater reduction in metabolic activity than the AP resin (P<.05). No difference was found in the metabolic activity of S. aureus according to the XTT (P>.05). The number of CFU/mL for S. aureus and P. aeruginosa decreased significantly when 5% and 10% ß-AgVO3 were added (P<.001). These concentrations significantly reduced the impact strength of the resins (P<.001) because the system was weakened by the presence of clusters of ß-AgVO3. CONCLUSION: The addition of ß-AgVO3 can provide acrylic resins with antibacterial activity but reduces their impact strength. More efficient addition methods should be investigated.

Ecotoxicological effects of carbofuran and oxidised multiwalled carbon nanotubes on the freshwater fish Nile tilapia: nanotubes enhance pesticide ecotoxicity.

The interactions of carbon nanotubes with pesticides, such as carbofuran, classical contaminants (e.g., pesticides, polyaromatic hydrocarbons, heavy metals, and dyes) and emerging contaminants, including endocrine disruptors, are critical components of the environmental risks of this important class of carbon-based nanomaterials. In this work, we studied the modulation of acute carbofuran toxicity to the freshwater fish Nile tilapia (Oreochromis niloticus) by nitric acid treated multiwalled carbon nanotubes, termed HNO3-MWCNT. Nitric acid oxidation is a common chemical method employed for the purification, functionalisation and aqueous dispersion of carbon nanotubes. HNO3-MWCNT were not toxic to Nile tilapia at concentrations ranging from 0.1 to 3.0 mg/L for exposure times of up to 96 h. After 24, 48, 72 and 96 h, the LC50 values of carbofuran were 4.0, 3.2, 3.0 and 2.4 mg/mL, respectively. To evaluate the influence of carbofuran-nanotube interactions on ecotoxicity, we exposed the Nile tilapia to different concentrations of carbofuran mixed together with a non-toxic concentration of HNO3-MWCNT (1.0 mg/L). After 24, 48, 72, and 96 h of exposure, the LC50 values of carbofuran plus nanotubes were 3.7, 1.6, 0.7 and 0.5 mg/L, respectively. These results demonstrate that HNO3-MWCNT potentiate the acute toxicity of carbofuran, leading to a more than five-fold increase in the LC50 values. Furthermore, the exposure of Nile tilapia to carbofuran plus nanotubes led to decreases in both oxygen consumption and swimming capacity compared to the control. These findings indicate that carbon nanotubes could act as pesticide carriers affecting fish survival, metabolism and behaviour.

Nanotoxicity of graphene and graphene oxide.

Graphene and its derivatives are promising candidates for important biomedical applications because of their versatility. The prospective use of graphene-based materials in a biological context requires a detailed comprehension of the toxicity of these materials. Moreover, due to the expanding applications of nanotechnology, human and environmental exposures to graphene-based nanomaterials are likely to increase in the future. Because of the potential risk factors associated with the manufacture and use of graphene-related materials, the number of nanotoxicological studies of these compounds has been increasing rapidly in the past decade. These studies have researched the effects of the nanostructural/biological interactions on different organizational levels of the living system, from biomolecules to animals. This review discusses recent results based on in vitro and in vivo cytotoxicity and genotoxicity studies of graphene-related materials and critically examines the methodologies employed to evaluate their toxicities. The environmental impact from the manipulation and application of graphene materials is also reported and discussed. Finally, this review presents mechanistic aspects of graphene toxicity in biological systems. More detailed studies aiming to investigate the toxicity of graphene-based materials and to properly associate the biological phenomenon with their chemical, structural, and morphological variations that result from several synthetic and processing possibilities are needed. Knowledge about graphene-based materials could ensure the safe application of this versatile material. Consequently, the focus of this review is to provide a source of inspiration for new nanotoxicological approaches for graphene-based materials.

Biogenic antimicrobial silver nanoparticles produced by fungi.

Aspergillus tubingensis and Bionectria ochroleuca showed excellent extracellular ability to synthesize silver nanoparticles (Ag NP), spherical in shape and 35 ± 10 nm in size. Ag NP were characterized by transmission electron microscopy, X-ray diffraction analysis, and photon correlation spectroscopy for particle size and zeta potential. Proteins present in the fungal filtrate and in Ag NP dispersion were analyzed by electrophoresis (sodium dodecyl sulfate polyacrylamide gel electrophoresis). Ag NP showed pronounced antifungal activity against Candida sp, frequently occurring in hospital infections, with minimal inhibitory concentration in the range of 0.11-1.75 µg/mL. Regarding antibacterial activity, nanoparticles produced by A. tubingensis were more effective compared to the other fungus, inhibiting 98.0 % of Pseudomonas. aeruginosa growth at 0.28 µg/mL. A. tubingensis synthesized Ag NP with surprisingly high and positive surface potential, differing greatly from all known fungi. These data open the possibility of obtaining biogenic Ag NP with positive surface potential and new applications.

Nanostructured silver vanadate as a promising antibacterial additive to water-based paints.

In this article, we report the use of nanostructured silver vanadate as a promising antibacterial additive to water-based paints that has potential for applications in bathrooms, kitchens, and hospital environments. This hybrid nanomaterial was prepared by a simple and fast precipitation reaction involving silver nitrate and ammonium vanadate, dismissing the hydrothermal treatment. The preparation involved using Ag vanadate nanowires (ß-AgVO(3)) with diameters ranging from 20 to 60 nm and decorated with silver (Ag) nanoparticles (NPs) with diameters ranging from 5 to 40 nm. Results of antibacterial tests show that this hybrid material has a promising antibacterial activity against several types of bacteria strains, such as methicillin-resistant Staphylococcus aureas (MRSA), Enterococcus faecalis, Escherichia coli, and Salmonella enterica Typhimurium. The evaluated material exhibits antibacterial activity 30 times larger than that of Oxacillin. In addition, this nanomaterial was tested as an antibacterial additive to water-based paints, and formulations with 1% show a 4-mm inhibition zone against a MRSA strain.

Co-exposure of carbon nanotubes with carbofuran pesticide affects metabolic rate in Palaemon pandaliformis (shrimp).

Palaemon pandalirformis (shrimp) is a species widely distributed in the Brazilian coastal region and with an important economic role. In addition, this organism is considered an indicator of environmental pollution in estuaries; however, its physiological responses to toxic environmental pollutants, including pesticides and nanomaterials, are not well known, mainly, the effects of co-exposure. Thus, the purpose of this study was to evaluate the ecotoxicological effects of co-exposure between oxidized multiwalled carbon nanotubes (HNO3-MWCNT) and carbofuran pesticide on the routine metabolism of P. pandalirformis. The shrimps were exposed to different concentrations of HNO3-MWCNT (0; 10; 100; 500; 1000 µg L-1), carbofuran (0; 0.1; 1.0; 5.0; 10 µg L-1) and to co-exposure with 100 µg L-1 of HNO3-MWCNT + carbofuran (0; 0.1; 1.0; 5.0; 10 µg L-1), to evaluate the effects on metabolic rate (O2 consumption) and excretion of ammonia (NH4+NH3). Our results showed that the shrimps exposed to HNO3-MWCNT (10 µg L-1) increased the metabolic rate by 292% and the excretion of ammonia by 275%; those exposed to carbofuran (10 µg L-1) increased their metabolic rate by 162% and the excretion of ammonia by 425%; and with the co-exposure of HNO3-MWCNT + carbofuran there was also an increase in the metabolic rate by 317% and an excretion of ammonia by 433% when compared to control. These findings provides useful information toward better understanding the physiological responses of shrimps after combined exposure to nanomaterials and pesticides in aquatic environments.

Surface chemistry in the process of coating mesoporous SiO2 onto carbon nanotubes driven by the formation of Si-O-C bonds.

The deposition of mesoporous silica (SiO(2)) on carbon nanotubes (CNTs) has opened up a wide range of assembling possibilities by exploiting the sidewall of CNTs and organosilane chemistry. The resulting systems may be suitable for applications in catalysis, energy conversion, environmental chemistry, and nanomedicine. However, to promote the condensation of silicon monomers on the nanotube without producing segregated particles, (OR)(4-x)SiO(x)(x-) units must undergo nucleophilic substitution by groups localized on the CNT sidewall during the transesterification reaction. In order to achieve this preferential attachment, we have deposited silica on oxidized carbon nanotubes (single-walled and multiwalled) in a sol-gel process that also involved the use of a soft template (cetyltrimethylammonium bromide, CTAB). In contrast to the simple approach normally used to describe the attachment of inorganic compounds on CNTs, SiO(2) nucleation on the tube is a result of nucleophilic attack mainly by hydroxyl radicals, localized in a very complex surface chemical environment, where various oxygenated groups are covalently bonded to the sidewall and carboxylated carbonaceous fragments (CCFs) are adsorbed on the tubes. Si-O-C covalent bond formation in the SiO(2)-CNT hybrids was observed even after removal of the CCFs with sodium hydroxide. By adding CTAB, and increasing the temperature, time, and initial amount of the catalyst (NH(4)OH) in the synthesis, the SiO(2) coating morphology could be changed from one of nanoparticles to mesoporous shells. Concomitantly, pore ordering was achieved by increasing the amount of CTAB. Furthermore, preferential attachment on the sidewall results mostly in CNTs with uncapped ends, having sites (carboxylic acids) that can be used for further localized reactions.

Cytotoxic and genotoxic effects in human gingival fibroblast and ions release of endodontic sealers incorporated with nanostructured silver vanadate.

The cytotoxic and genotoxic effects of commercial endodontic sealers (AH Plus, Sealer 26 and Endomethasone N) incorporated with nanostructured silver vanadate decorated with silver nanoparticles (AgVO3 - at concentrations 2.5, 5, and 10%) on human gingival fibroblast (HGF), and the silver (Ag+ ) and vanadium (V4+ /V5+ ) ions release were evaluated. Cytotoxicity, cell death, and genotoxicity tests were carried out with extract samples of 24-hr and 7-days. The release of Ag+ and V4+ /V5+ was evaluated. Cytotoxicity in HGF was caused by AH Plus (AP) with 5 and 10% of AgVO3 (83.84 and 67.49% cell viability, respectively) with 24-hr extract (p < 0.05), as well as all concentrations of AP with 7-days extract (p < 0.05 -AP 0% = 73.17%; AP 2.5% = 75.07%; AP 5% = 70.62%; AP 10% = 68.46% cell viability). The commercial sealers Sealer 26 (S26) and Endomethasone N (EN) were cytotoxic (p < 0.05 - S26 0% = 34.81%; EN 0% = 20.99% cell viability with 7-days extract). AP 10% with 7-days extract induced 32% apoptotic cells in HGF (p < 0.05). Genotoxic effect was not observed. The AP groups released more Ag+ , while S26 and EN released more V4+ /V5+ in 24 hr. The Ag+ can be cytotoxic. In conclusion, the cytotoxicity caused to HGF can be attributed by the commercial sealers and enhanced by incorporation of AgVO3 , was not observed genotoxic effect, and apoptosis was induced only by AH Plus 10% 7-days extract. Ag+ can influence cell viability.

Recent Advances in Immunosafety and Nanoinformatics of Two-Dimensional Materials Applied to Nano-imaging.

Two-dimensional (2D) materials have emerged as an important class of nanomaterials for technological innovation due to their remarkable physicochemical properties, including sheet-like morphology and minimal thickness, high surface area, tuneable chemical composition, and surface functionalization. These materials are being proposed for new applications in energy, health, and the environment; these are all strategic society sectors toward sustainable development. Specifically, 2D materials for nano-imaging have shown exciting opportunities in in vitro and in vivo models, providing novel molecular imaging techniques such as computed tomography, magnetic resonance imaging, fluorescence and luminescence optical imaging and others. Therefore, given the growing interest in 2D materials, it is mandatory to evaluate their impact on the immune system in a broader sense, because it is responsible for detecting and eliminating foreign agents in living organisms. This mini-review presents an overview on the frontier of research involving 2D materials applications, nano-imaging and their immunosafety aspects. Finally, we highlight the importance of nanoinformatics approaches and computational modeling for a deeper understanding of the links between nanomaterial physicochemical properties and biological responses (immunotoxicity/biocompatibility) towards enabling immunosafety-by-design 2D materials.

Understanding the driving forces of camptothecin interactions on the surface of nanocomposites based on graphene oxide decorated with silica nanoparticles.

Camptothecin (CPT) is a potent antitumor drug frequently used in studies of drug delivery systems. The poor water solubility and unfavourable pharmacokinetic conditions of CPT and the development of nanomaterials such as mesoporous silica nanoparticles (MSNs), graphene oxide (GO) and a new family of GO decorated with MSNs (GO-MSNs) motivated the present work, which sought to solve these challenges. In this context, release assays showed rapid and prolonged release, respectively, by silica and GO/GO-MSN nanomaterials; release was faster at pH 7.4 and slower at pH 5.0 in all situations. In particular, GO-MSNs presented an important advantage compared to GO due to their slower drug release at pH 7.4 (physiological conditions in blood; slowest release is expected under these conditions) and faster drug delivery at pH 5.0 (acidic conditions in endosomes of cancer cells; fastest release is expected under these conditions). The results, therefore, present the GO-MSN nanomaterial as a potential candidate for antitumor applications. The main drug-nanocarrier chemical interactions (London forces, hydrogen bonds, and electrostatic and dipole-dipole interactions) are also exhaustively described in order to understand the observed differences in drug delivery properties among these nanomaterials and to comprehend the influence of pH on concomitant and dynamic interactions.

Influence of AgVO3 incorporation on antimicrobial properties, hardness, roughness and adhesion of a soft denture liner.

The objective of this in vitro study was to investigate the effect of nanostructured silver vanadate decorated with silver nanoparticles (AgVO3) on antimicrobial activity, hardness, roughness, and adhesion of a soft denture liner. The antimicrobial efficacy of the Trusoft (Boswoth) liner incorporated with different concentrations of AgVO3 against Enterococcus faecalis, Pseudomonas aeruginosa, Candida albicans, and Staphyloccocus aureus (n = 5) was evaluated by the agar diffusion method. Roughness, hardness, and adhesion properties were also evaluated. The data were analyzed by analysis of variance (ANOVA) and Tukey's multiple comparison test with significance at the p < 0.05 level. At concentrations of 1 and 2.5%, AgVO3 incorporation was effective only against E. faecalis, and at 5 and 10%, against E. faecalis, P. aeruginosa, and C. albicans. None of the concentrations was effective against S. aureus. A decrease in hardness was found for the 1, 2.5, and 10% AgVO3 concentrations (p < 0.001) and at 5%, hardness was not affected. None of the concentrations affected the roughness of the material. A significant increase in tensile values was observed between the liner and heat-curing acrylic resin for 2.5% (p < 0.001) and 10% (p = 0.042) concentrations. AgVO3 incorporation to a soft denture liner promoted antimicrobial activity against E. faecalis, P. aeruginosa, and C. albicans without affecting roughness, maintaining the hardness properties recommended for soft and extra soft liners, and improving the adhesion between the liner and the acrylic resin used for dentures.

Biological effects of oxidized carbon nanomaterials (1D versus 2D) on Spodoptera frugiperda: Material dimensionality influences on the insect development, performance and nutritional physiology.

In this work, we developed an integrative experimental design to investigate the long-term effects of two important classes of carbon nanomaterials with different dimensionalities (i.e., 1D oxidized multiwalled carbon nanotube, ox-MWCNT, and 2D graphene oxide, GO) on the development of the generalist insect Spodoptera frugiperda (Lepidoptera: Noctuidae). Insects are exciting in vivo biological models for investigating the impact of nanomaterials on nanobio-ecological interactions. S. frugiperda larvae were reared from egg hatching to pupation on diets containing ox-MWCNT and GO at different concentrations (0, 10, 100 and 1000 µg g-1 of dry mass of diet). Several aspects of larval and adult performance were measured under controlled conditions. The effects of the carbon nanomaterial (CNM)-containing diets on the nutritional physiology and digestive enzymatic activities of S. frugiperda larvae were also evaluated. The results showed that the type and concentration of CNMs in the diet negatively affected the reproductive parameters and the digestive and metabolic efficiency of S. frugiperda. The diet containing the highest concentration of GO significantly reduced the fecundity and fertility of S. frugiperda compared to the effects of other treatments. S. frugiperda larvae showed decreased efficiency of food conversion into biomass and maximal approximate digestibility when fed diets containing GO at higher concentrations. However, quantitative differences in digestive enzyme activities were not observed between all treatments. These findings highlighted the critical influence of CNM dimensionality on the general performance and nutritional physiology of the moth. This work contributes to the safety evaluation and future applications of CNMs in agri-environmental nanotechnology.

Covalent functionalization of graphene oxide with d-mannose: evaluating the hemolytic effect and protein corona formation.

In this work, graphene oxide (GO) was covalently functionalized with d-mannose (man-GO) using mannosylated ethylenediamine. XPS (C1s and N1s) confirmed the functionalization of GO through the binding energies at 288.2 eV and 399.8 eV, respectively, which are attributed to the amide bond. ATR-FTIR spectroscopy showed an increase in the amine bond intensity, at 1625 cm-1 (stretching C[double bond, length as m-dash]O), after the functionalization step. Furthermore, the man-GO toxicity to human red blood cells (hemolysis) and its nanobiointeractions with human plasma proteins (hard corona formation) were evaluated. The mannosylation of GO drastically reduced its toxicity to red blood cells. SDS-PAGE analysis showed that the mannosylation process of GO also drastically reduced the amount of the proteins in the hard corona. Additionally, proteomics analysis by LC-MS/MS revealed 109 proteins in the composition of the man-GO hard corona. Finally, this work contributes to future biomedical applications of graphene-based materials functionalized with active biomolecules.

Pressure-induced phase transition and fracture in α-MoO3 nanoribbons.

MoO3 nanoribbons were studied under different pressure conditions ranging from 0 to 21GPa at room temperature. The effect of the applied pressure on the spectroscopic and morphologic properties of the MoO3 nanoribbons was investigated by means of Raman spectroscopy and scanning electron microscopy techniques. The pressure dependent Raman spectra of the MoO3 nanoribbons indicate that a structural phase transition occurs at 5GPa from the orthorhombic α-MoO3 phase (Pbnm) to the monoclinic MoO3-II phase (P21/m), which remains stable up to 21GPa. Such phase transformation occurs at considerably lower pressure than the critical pressure for α-MoO3 microcrystals (12GPa). We suggested that the applanate morphology combined with the presence of crystalline defects in the sample play an important role in the phase transition of the MoO3 nanoribbons. Frequencies and linewidths of the Raman bands as a function of pressure also suggest a pressure-induced morphological change and the decreasing of the nanocrystal size. The observed spectroscopic changes are supported by electron microscopy images, which clearly show a pressure-induced morphologic change in MoO3 nanoribbons.

Microwave-assisted synthesis of palladium nanoparticles intercalated nitrogen doped reduced graphene oxide and their electrocatalytic activity for direct-ethanol fuel cells.

Palladium nanoparticles decorated reduced graphene oxide (Pd-rGO) and palladium nanoparticles intercalated inside nitrogen doped reduced graphene oxide (Pd-NrGO) hybrids have been synthesized by applying a very simple, fast and economic route using microwave-assisted in-situ reduction and exfoliation method. The Pd-NrGO hybrids materials show good activity as catalyst for ethanol electro oxidation for direct ethanol fuel cells (DEFCs) as compared to Pd-rGO hybrids. The enhanced direct ethanol fuel cell can serve as alternative to fossil fuels because it is renewable and environmentally-friendly with a high energy conversion efficiency and low pollutant emission. As proof of concept, the electrocatalytic activity of Pd-NrGO hybrid material was accessed by cyclic voltammetry in presence of ethanol to evaluate its applicability in direct-ethanol fuel cells (DEFCs). The Pd-NrGO catalyst presented higher electro active surface area (∼6.3 m2 g-1) for ethanol electro-oxidation when compared to Pd-rGO hybrids (∼3.7 m2 g-1). Despite the smaller catalytic activity of Pd-NrGO, which was attributed to the lower exfoliation rate of this material in relation to the Pd-rGO, Pd-NrGO showed to be very promising and its catalytic activity can be further improved by tuning the synthesis parameters to increase the exfoliation rate.

Antimicrobial textiles: Biogenic silver nanoparticles against Candida and Xanthomonas.

This paper introduces cotton fibers impregnated with biogenic silver nanoparticles (AgNPs), synthesized from a Fusarium oxysporum fungal filtrate (FF) solution, and open up the possibility for their use in medical environment and agriculture clothing as means to avoid microbial spreading. After thorough AgNPs characterization, regarding their physical, chemical and biochemical properties, Minimum Inhibitory Concentrations (MIC) against some human and orange tree pathogens were determined. We report the strong AgNPs activity against Candida parapsilosis and Xanthomonas axonopodis pv. citri (Xac) that was morphologically characterized, pointing to strong AgNPs effects on microorganisms' membranes. Cotton fibers were then impregnated with AgNPs suspension and these maintained strong antimicrobial activity even after repeated mechanical washing cycles (up to 10). Reported data might point to an application for biogenic AgNPs as potent agrochemicals, as well as, to their application in textiles for antiseptic clothing for medical and agronomic applications.

Coating carbon nanotubes with humic acid using an eco-friendly mechanochemical method: Application for Cu(II) ions removal from water and aquatic ecotoxicity.

In this work, industrial grade multi-walled carbon nanotubes (MWCNT) were coated with humic acid (HA) for the first time by means of a milling process, which can be considered an eco-friendly mechanochemical method to prepare materials and composites. The HA-MWCNT hybrid material was characterized by atomic force microscopy (AFM), scanning electron microscopies (SEM and STEM), X-ray photoelectron spectroscopy (XPS), termogravimetric analysis (TGA), and Raman spectroscopy. STEM and AFM images demonstrated that the MWCNTs were efficiently coated by the humic acid, thus leading to an increase of 20% in the oxygen content at the nanotube surface as observed by the XPS data. After the milling process, the carbon nanotubes were shortened as unveiled by SEM images and the values of ID/IG intensity ratio increased due to shortening of the nanotubes and increasing in the number defects at the graphitic structure of carbon nanotubes walls. The analysis of TGA data showed that the quantity of the organic matter of HA on the nanotube surface was 25%. The HA coating was responsible to favor the dispersion of MWCNTs in ultrapure water (i.e. -42mV, zeta-potential value) and to improve their capacity for copper removal. HA-MWCNTs hybrid material adsorbed 2.5 times more Cu(II) ions than oxidized MWCNTs with HNO3, thus evidencing that it is a very efficient adsorbent material for removing copper ions from reconstituted water. The HA-MWCNTs hybrid material did not show acute ecotoxicity to the tested aquatic model organisms (Hydra attenuata, Daphnia magna, and Danio rerio embryos) up to the highest concentration evaluated (10mgL-1). The results allowed concluding that the mechanochemical method is effective to coat carbon nanotubes with humic acid, thus generating a functional hybrid material with low aquatic toxicity and great potential to be applied in environmental nanotechnologies such as the removal of heavy metal ions from water.

Optical sensor for sulfur dioxide determination in wines.

A method for the determination of free and total sulfur dioxide in wines, based on the use of an optical sensor that employs a dichlorobis(diphenylphosphino)methane dipalladium I complex [Pd(2)(dppm)(2)Cl(2)] immobilized in a PVC membrane plasticized with o-nitrophenyloctylether (o-NPOE) is described. A sensing membrane [4.2% Pd(2)(dppm)(2)Cl(2), 20.8% PVC, and 75% o-NPOE] was adapted to the tip of a bifurcated optical fiber bundle to perform reflectance measurements at 550 nm. The detection system consisted of two cells (40 mL), which hold the sample solution (plus reagents) and the optical sensor, respectively. For the determination of free SO(2), a wine sample was mixed with H(2)SO(4) solution in the sample cell, into which N(2) was bubbled, providing mixing of the solutions and conducting the SO(2) formed toward the detection cell. For determination of total SO(2), a KOH solution was mixed with the wine in the sample cell. Afterward, an H(2)SO(4) solution was added to the cell, and then N(2) was bubbled to conclude the measurement. Linear responses up to 50 and 150 mg L(-1) were obtained for free and total SO(2), with detection limits of 0.37 and 0.70 mg L(-1), respectively. The repeatability of the method was evaluated by carrying out 10 measurements using a single wine sample, providing relative standard deviation values of 2.2 and 2.5% for free and total SO(2), respectively. The sensing membrane prepared from 10 muL of the cocktail solution lasted for 80 measurements, whereas those prepared from 200 muL can be used for 250 measurements. The method was applied to free and total SO(2) determination in wines, and the results did not show significant difference from those obtained with the Ripper reference method at a confidence level of 95%.