Gil Nonato Santos

The influence of nanostructured materials on biointerfacial interactions

Control over biointerfacial interactions in vitro and in vivo is the key to many biomedical applications: from cell culture and diagnostic tools to drug delivery, biomaterials and regenerative medicine. The increasing use of nanostructured materials is placing a greater demand on improving our understanding of how these new materials influence biointerfacial interactions, including protein adsorption and subsequent cellular responses. A range of nanoscale material properties influence these interactions, and material toxicity. The ability to manipulate both material nanochemistry and nanotopography remains challenging in its own right, however, a more in-depth knowledge of the subsequent biological responses to these new materials must occur simultaneously if they are ever to be affective in the clinic. We highlight some of the key technologies used for fabrication of nanostructured materials, examine how nanostructured materials influence the behavior of proteins and cells at surfaces and provide details of important analytical techniques used in this context.

Theoretical investigation on single-wall carbon nanotubes doped with nitrogen, pyridine-like nitrogen defects, and transition metal atoms

This study addresses the inherent difficulty in synthesizing single-walled carbon nanotubes (SWCNTs) with uniform chirality and well-defined electronic properties through the introduction of dopants, topological defects, and intercalation of metals. Depending on the desired application, one can modify the electronic and magnetic properties of SWCNTs through an appropriate introduction of imperfections. This scheme broadens the application areas of SWCNTs. Under this motivation, we present our ongoing investigations of the following models: (i) (10, 0) and (5, 5) SWCNT doped with nitrogen (CNxNT), (ii) (10, 0) and (5, 5) SWCNT with pyridine-like defects (3NV-CNxNT), (iii) (10, 0) SWCNT with porphyrine-like defects (4ND-CNxNT). Models (ii) and (iii) were chemically functionalized with 14 transition metals (TMs): Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pd, Ag, Pt and Au. Using the spin-unrestricted density functional theory (DFT), stable configurations, deformations, formation and binding energies, the effects of the doping concentration of nitrogen, pyridine-like and porphyrine-like defects on the electronic properties were all examined. Results reveal that the electronic properties of SWCNTs show strong dependence on the concentration and configuration of nitrogen impurities, its defects, and the TMs adsorbed.

Theoretical Investigation on the Solubilization in Water of Functionalized Single-Wall Carbon Nanotubes

An important technique to increase the solubility and reactivity of carbon nanotube is through functionalization. In this study, the effects of functionalization of some single-walled carbon nanotubes (SWCNTs) were investigated with the aid of density functional theory. The SWCNT model used in the study consists of a finite, (5, 0) zigzag nanotube segment containing 60 C atoms with hydrogen atoms added to the dangling bonds of the perimeter carbons. There are three water-dispersible SWCNTs used in this study that were functionalized with (a) formic acid, as a model of carboxylic acid, (b) isophthalic acid, as a model aromatic dicarboxylic acid, and (c) benzenesulfonic acid, as a model aromatic sulfonic acid. Binding energies of the organic radicals to the nanotubes are calculated, as well as the HOMO-LUMO gaps and dipole moments of both nanotubes and functionalized nanotubes. Binding was found out to be thermodynamically favorable. The functionalization increases the electrical dipole moments and results in an enhancement in the solubility of the nanotubes in water manifested through favorable changes in the free energies of solvation. This should lower the toxicity of nanotubes and improve their biocompatibility.

Scandium and Titanium Containing Single-Walled Carbon Nanotubes for Hydrogen Storage: a Thermodynamic and First Principle Calculation

The generalized gradient approximation (GGA) to density functional theory (DFT) calculations indicate that the highly localized states derived from the defects of nitrogen doped carbon nanotube with divacancy (4ND-CNxNT) contribute to strong Sc and Ti bindings, which prevent metal aggregation. Comparison of the H2 adsorption capability of Sc over Ti-decorated 4ND-CNxNT shows that Ti cannot be used for reversible H2 storage due to its inherent high adsorption energy. The Sc/4ND-CNxNT possesses favorable adsorption and consecutive adsorption energy at the local-density approximation (LDA) and GGA level. Molecular dynamics (MD) study confirmed that the interaction between molecular hydrogen and 4ND-CNxNT decorated with scandium is indeed favorable. Simulations indicate that the total amount of adsorption is directly related to the operating temperature and pressure. The number of absorbed hydrogen molecules almost logarithmically increases as the pressure increases at a given temperature. The total excess adsorption of hydrogen on the (Sc/4ND)10-CNxNT arrays at 300 K is within the range set by the department of energy (DOE) with a value of at least 5.85 wt%.

Graphene-titanium dioxide nanocomposite based hypoxanthine sensor for assessment of meat freshness

We report on the fabrication of a graphene/titanium dioxide nanocomposite (TiO2-G) and its use as an effective electrode material in an amperometric hypoxanthine (Hx) sensor for meat freshness evaluation. The nanocomposite was characterized by TEM, XRD, FTIR, XPS, TGA, BET, and CV using the redox couples [Fe(CN)6]-3/-4 and [Ru(NH3)6]+3/+2 respectively. The TiO2/G nanocomposite offered a favorable microenvironment for direct electrochemistry of xanthine oxidase (XOD). The fabricated Nafion/XOD/TiO2-G/GCE sensor exhibited excellent electro catalytic activity towards Hx with linear range of 20μM to 512μM, limit of detection of 9.5μM, and sensitivity of 4.1nA/μM. In addition, the biosensor also demonstrated strong anti-interference properties in the presence of uric acid (UA), ascorbic acid (AA) and glucose. Minimal interference of xanthine (Xn) was observed at ~7%. Moreover, the biosensor showed good repeatability (4.3% RSD) and reproducibility (3.8% RSD). The reported biosensor was tested towards the detection of Hx in pork tenderloins stored at room temperature for seven days. There was a good correlation (r=0.9795) between biosensor response and measurements obtained by a standard enzymatic colorimetric method. The TiO2-G nanocomposite is therefore an effective electrode material to be used in electrochemical biosensors to assess the freshness of meat.

Adsorption of Mercury(II) Chloride and Carbon Dioxide on Graphene/Calcium Oxide (0 0 1)

In this work, recent progress on graphene/metal oxide composites as advanced materials for and capture was investigated. Density Functional Theory calculations were used to understand the effects of temperature on the adsorption ability of and water vapor on adsorption on CaO (001) with reinforced carbon-based nanostructures using B3LYP functional. Understanding the mechanism by which mercury and adsorb on graphene/CaO (g-CaO) is crucial to the design and fabrication of effective capture technologies. The results obtained from the optimized geometries and frequencies of the proposed cluster site structures predicted that with respect to molecular binding the system possesses unusually large ( sorbent) and ( sorbent) uptake capacities. The and were found to be stable on the surface as a result of the topology and a strong interaction with the g-CaO system; these results strongly suggest the potential of CaO-doped carbon materials for and capture applications, the functional gives reliable answers compared to available experimental data.

Nitrogen substitution and vacancy mediated scandium metal adsorption on carbon nanotubes

First-principle calculation reveals that N containing carbon nanotubes (CNTs) can support the functionalization of transition metals such as Sc on the CNT surface. For N-substituted CNTs without a vacancy, the enhanced adsorption results from large electron affinity difference of the N adjacent to C atom. In this case, the N atom activates nearby C atom and enhances its interaction with the Sc metal on the CNT surface. Meanwhile, the formation of a vacancy in CNTs causes local reconstruction of the surface near the vacancy site. Simulation and analysis show that vacancy mediated N substitution is a more favored scheme for Sc functionalization on the surface of CNTs that suppresses the clustering of Sc. The enhanced Sc adsorption in N-doped CNTs with mono- and di-vacancy defects was attributed to strong hybridization between the Scandium d orbital and nitrogen p orbital. The results explain theoretically the mechanism of enhanced functionalization of metals on N doped CNTs and suggests that Sc functionalized nitrogen doped CNTs with vacancies is an excellent candidate for the adsorption of small molecules.

Hydrogen Adsorption on Nearly Zigzag-Edged Nanoribbons: A Density Functional Theory Study

The realistic shapes of N doped graphene nanoribbons (GNRs) can be realized by considering nearly zigzag-edged (NZE) imperfections and pyridine defects (3NV). The paper focuses on NZE-GNRs with 3NV that is populated by Scandium abbreviated as Sc/NZE-3NVGNRs. Systematic calculations have clarified roles of the nano-shapes of NZE-3NVGNRs in its formation, energetics, stability and electron states functionalized with Sc using density functional theory (DFT) formalisms. According to DFT calculations, the magnitude of the spin that is attributed to the rise of magnetic order is closely linked to the altered shape of the ribbon edges. Also, calculations show that the stability of Sc functionalization at the 3NV and NZE site is thermodynamically stable and is dictated by a strong binding energy (BE). The magnitude of the BE is enhanced when the zigzag edge is short or the ribbon width is narrow, suggesting a reduced clustering of Sc atoms over the Sc-doped NZE-3NVGNRs. Results also show that as the length of the zigzag edge in Sc/NZE-3NVGNRs increases it creates considerable distortion on the appearance of the structure. Finally, the Sc/NZE-3NVGNRs as a potential candidate for hydrogen storage was evaluated and it was found that it could adsorb multiple hydrogen molecules.

Magnetic-Field-Enhanced Morphology of Tin Oxide Nanomaterials for Gas Sensing Applications

We studied the effect of an external magnetic field (up to 0.31 T) on the growth of SnO2 nanowires fabricated using the horizontal vapor phase growth (HPVG) technique. The morphology of the nanowires was characterized by using scanning electron microscopy (SEM), and the chemical composition was characterized by energy dispersive X-ray (EDX) analysis. We found that the length of nanowires was significantly enhanced by the application of EMF. The aspect ratio, as well as the density of the fabricated nanowires, increased with increasing magnetic field intensity. Although the physics behind the morphology enhancement of the nanowires under magnetic field is still being investigated, nevertheless, we demonstrated that the magnetic field could be used as a key parameter to control the morphology of tin oxide nanomaterials grown via HPVG technique. The magnetically enhanced nanowires were used in the development of a gas sensor and were found to be sensitive to hydrogen sulfide gas and the headspace gas emitted by spoiling meat.

Primary education in Vietnam and pupil online engagement

This paper focuses on exploring the disparities in social awareness and use of the Internet between urban and rural school children in the North of Vietnam. Design/methodology/approach: A total of 525 pupils, aged 9 to 11 years old, randomly selected from 7 urban and rural schools, who are Internet users, participated in the study and consented to responding to a questionnaire adapted from an equivalent European Union (EU) study. A comparative statistical analysis of the responses was then carried out, using IBM SPSS v21, which consisted of a descriptive analysis, an identification of personal self-development opportunities, as well as issues related to pupils’ digital prowess and knowledge of Internet use, and Internet safety, including parental engagement in their offspring’s online activities. Findings: The study highlights the fact that children from both the urban and rural regions of the North of Vietnam mostly access to the Internet from home, but with more children in the urbanized areas accessing it at school than their rural counterparts. Although children from the rural areas scored lower on all the Internet indicators, such as digital access and online personal experience and awareness, there was no disparity in awareness of Internet risks between the two sub-samples. It is noteworthy that there was no statistically significant gender difference towards online activities that support self-development. In relation to safe Internet usage, children are likely to seek advice from their parents, rather than through teachers or friends. However, they are not yet provided with an effective safety net while exposing themselves to the digital world. Originality/value: Although the Vietnamese national curriculum on the Computer Science subject does not explicitly cover the use of the Internet and its related aspects, the majority of children who took part in this study claimed to have used the Internet in their learning activities. This emphasises the urgent need for the MoE and educators in the country to not only improve ICT facilities in schools, but also to revise the Computer Science curriculum in order to (a) provide a supportive environment for learning development and (b) collectively advocate the dynamics of Internet use in order to ensure safe access and use by the children.