Fluorescent dual-mode sensor for the determination of graphene oxide and catechin in environmental or food field.

The novel fluorescent sensor is proposed in this work based on the competitive interactions between the known bioactive compounds, riboflavin and catechin, which act as guests, and graphene oxide (GO) material that acts as host. Specifically, this proposal is based on an indicator displacement assay which allows the detection of GO and catechin (fluorescence quenching of riboflavin signal by GO and increase in fluorescence by catechin on the GO-riboflavin system). Three GO structures with different lateral dimensions and thickness were synthesized and tested, being able to be the three differentiated depending on the attenuation capacity of the fluorescent signal that each one possesses. The environmental analytical control of GO is more and more important, being this method sensitive and selective in the presence of other potential interferent substances. On the other hand, the other sensing capacity of the sensor also allows the determination of catechin in food samples based on the formation of riboflavin-GO complex. It is a rapid, simple and non-expensive procedure. Thus, the same 2D nanomaterial (GO) is seen to play a double role in this sensing strategy (analyte and analytical tool for the determination of another compound).

Graphene Oxides (GOs) with Different Lateral Dimensions and Thicknesses Affect the Molecular Response in Chironomus riparius.

Graphene oxide (GO) materials possess physicochemical properties that facilitate their application in the industrial and medical sectors. The use of graphene may pose a threat to biota, especially aquatic life. In addition, the properties of nanomaterials can differentially affect cell and molecular responses. Therefore, it is essential to study and define the possible genotoxicity of GO materials to aquatic organisms and their ecosystems. In this study, we investigated the changes in the expression of 11 genes in the aquatic organism Chironomus riparius after 96 h of exposure to small GOs (sGO), large GOs (lGO) and monolayer GOs (mlGO) at 50, 500 and 3000 µg/L. Results showed that the different genes encoding heat shock proteins (hsp90, hsp70 and hsp27) were overexpressed after exposure to these nanomaterials. In addition, ATM and NLK-the genes involved in DNA repair mechanisms-were altered at the transcriptional level. DECAY, an apoptotic caspase, was only activated by larger size GO materials, mlGO and lGO. Finally, the gene encoding manganese superoxide dismutase (MnSOD) showed higher expression in the mlG O-treated larvae. The lGO and mlGO treatments indicated high mRNA levels of a developmental gene (FKBP39) and an endocrine pathway-related gene (DRONC). These two genes were only activated by the larger GO materials. The results indicate that larger and thicker GO nanomaterials alter the transcription of genes involved in cellular stress, oxidative stress, DNA damage, apoptosis, endocrine and development in C. riparius. This shows that various cellular processes are modified and affected, providing some of the first evidence for the action mechanisms of GOs in invertebrates. In short, the alterations produced by graphene materials should be further studied to evaluate their effect on the biota to show a more realistic scenario of what is happening at the molecular level.

Toxicological effects of three different types of highly pure graphene oxide in the midge Chironomus riparius.

Graphene oxide (GO) is a carbon nanomaterial used in electronics, biomedicine, environmental remediation and biotechnology. The production of graphene will increase in the upcoming years. The carbon nanoparticles (NPs) are released into the environment and accumulated in aquatic ecosystems. Information on the effects of GO in aquatic environments and its impact on organisms is still lacking. The aim of this study was to synthesise and characterise label-free GO with controlled lateral dimensions and thickness - small GO (sGO), large GO (lGO) and monolayer GO (mlGO) - and determine their impact on Chironomus riparius, a sentinel species in the freshwater ecosystem. Superoxide dismutase (SOD) and lipid peroxidation (LPO) was evaluated after exposures for 24 h and 96 h to 50, 500, and 3000 µg/L. GOs accumulated in the gut of C. riparius and disturbed its antioxidant metabolism. We suggest that all types of GO exposure can upregulate of SOD. Moreover, both lGO and mlGO treatments caused LPO damage in C. riparius in comparison to sGO, proving its favourable lateral size impact in this organism. Our results indicate that GOs could accumulate and induce significant oxidative stress on C. riparius. This work shows new information about the potential oxidative stress of these NMs in aquatic organisms.

Long-Term Performance of Nanomodified Coated Concrete Structures under Hostile Marine Climate Conditions.

Epoxy resin coatings are commonly used to protect concrete structures due to their excellent chemical corrosion resistance and strong adhesion capacity. However, these coatings are susceptible to damage by surface abrasion and long-term contact with marine climate conditions, deteriorating their appearance and performance. This study aims to optimize the performance of cement-based epoxy resin coatings, bisphenol-A and polyol, in aggressive environments by functionalizing the selected systems with different nanoparticles such as activated carbon, surface modified nanoclay, silica and zinc oxide. Nanomodified coatings were applied to concrete specimens and subjected to three weeks in a spray salt chamber and three weeks in a QUV chamber. They were found to present improved thermal resistance and curing degree after the weathering test. Their water permeability, adhesion, and abrasion resistance properties were evaluated before and after this test. The results showed that the nature of the nanocomposites determined their water permeability; the bare resin presented the worst result. Additionally, nanomodified composites with activated carbon and silica showed the best adherence and abrasion resistance properties, due to the effect of this aging test on their thermal stability and curing degree.

Evaluation of graphenic and graphitic materials on the adsorption of Triton X-100 from aqueous solution.

Presently, graphenic nanomaterials are being studied as candidates for wastewater pollutant removal. In this study, two graphite oxides produced from natural graphite with different grain sizes (325 and 10 mesh), their respective reduced graphene oxides and one reduced graphene oxide with nitrogen functional groups were synthesized and tested to remove a surfactant model substrate, Triton X-100, from an aqueous solution. Kinetic experiments were carried out and adjusted to pseudo-first order equation, pseudo-second order equation, Elovich, Chain-Clayton and intra-particle diffusion models. Reduced graphene oxides displayed an instantaneous adsorption due to their accessible and hydrophobic surfaces, while graphite oxides hindered the TX100 adsorption rate due to their highly superficial oxygen content. Results from the adsorption isotherms showed that the Sips model perfectly described the TX100 adsorption behavior of these materials. Higher adsorption capacities were developed with reduced graphene oxides, being maximum for the material produced from the lower graphite grain size (qe = 3.55·10-6 mol/m2), which could be explained by a higher surface area (600 m2/g), a lower amount of superficial oxygen (O/C = 0.04) and a more defected structure (ID/IG = 0.85). Additionally, three commercial high surface area graphites in the range of 100-500 m2/g were evaluated for comparison purposes. In this case, better adsorption results were obtained with a more graphitic material, HSAG100 (qe = 1.72·10-6 mol/m2). However, the best experimental results of this study were obtained using synthesized graphenic materials.

Utilization and reusability of hydroxyethyl cellulose alumina based aerogels for the removal of spilled oil.

Nowadays millions of oil tons are spilled into the environment causing important damage. Therefore, the development of new technologies and materials are needed to remediate this problem. In this study, hydroxyethyl cellulose alumina-based aerogels are synthesized by an environmentally friendly freeze-drying process to be used as sorbents for oil spills. It is demonstrated that the oil retention coefficient depends on the viscosity of the oil and the amount of hydroxyethyl cellulose contained in the aerogel, being 10% the optimal proportion. The aerogel synthetized with this content of hydroxyethyl cellulose displays the most favourable physicochemical and morphological properties to retain different oil spills, achieving 5.5 times its weight in comparison to its dry state. In addition, reusability experiments washing the aerogel with acetone or ethanol after the oil retention are carried out. Results show an improvement after a long washing of the sorbent with acetone, resulting in an oil weight gain of 38.7%.

Graphene oxide as a 2D platform for complexation and intracellular delivery of siRNA.

The development of efficient and safe nucleic acid delivery vectors remains an unmet need holding back translation of gene therapy approaches to the bedside. Graphene oxide (GO) could help bypass such bottlenecks, thanks to its large surface area, versatile chemistry and biocompatibility, which could overall enhance transfection efficiency while abolishing some of the limitations linked to the use of viral vectors. Here, we aimed to assess the capacity of bare GO, without any further surface modification, to complex a short double-stranded nucleic acid of biological relevance (siRNA) and mediate its intracellular delivery. GO formed stable complexes with siRNA at 10 : 1, 20 : 1 and 50 : 1 GO : siRNA mass ratios. Complexation was further corroborated by atomistic molecular dynamics simulations. GO : siRNA complexes were promptly internalized in a primary mouse cell culture, as early as 4 h after exposure. At this time point, intracellular siRNA levels were comparable to those provided by a lipid-based transfection reagent that achieved significant gene silencing. The time-lapse tracking of internalized GO and siRNA evidenced a sharp decrease of intracellular siRNA from 4 to 12 h, while GO was sequestered in large vesicles, which may explain the lack of biological effects (i.e. gene silencing) achieved by GO : siRNA complexes. This study underlines the potential of non-surface modified GO flakes to act as 2D siRNA delivery platforms, without the need for cationic functionalization, but warrants further vector optimization to allow the effective release of the nucleic acid and achieve efficient gene silencing.

Effects at molecular level of multi-walled carbon nanotubes (MWCNT) in Chironomus riparius (DIPTERA) aquatic larvae.

Nowadays, due to the physical, chemical, electrical, thermal and mechanical properties of carbon nanotubes (CNT), its have been currently incorporated into biomedical products and they are employed in drug delivery drug administration, biosensor design, microbial treatments, consumer products, and new products containing CNT are expected in the future. CNT are hydrophobic and have a tendency to accumulate in sediments if they are released into aquatic ecosystems. Vertebrate studies have revealed concerns about the toxicity of carbon nanotubes, but there is very limited data on the toxic effects in aquatic invertebrate species. The aim of the present study is to determine the effects of MWCNT in Chironomus riparius at the molecular level, understanding its mode of action and analyzing the suitability of this species to monitor and assess risk of nanomaterials in aquatic ecosystems. To evaluate possible toxic effects caused by carbon nanotube environmental dispersion with regard to aquatic compartment, we study the mRNA levels of several related genes with DNA repairing mechanisms, cell stress response, cell apoptosis and cytoskeleton by Real-Time PCR and proposed a freshwater invertebrate C. riparius, which is a reference organism in aquatic toxicology. The obtained results show a transcriptional alteration of some genes included in this study, indicating that different cell processes are affected and providing one the first evidences in the mechanisms of action of MWCNT in invertebrates. Moreover, this data reinforces the need for further studies to assess the environmental risk of nanomaterial to prevent future damage to aquatic ecosystems.