The stable dispersion of graphene flakes in an aqueous medium is highly desirable for the development of materials based on this two-dimensional carbon structure, but current production protocols that make use of a number of surfactants typically suffer from limitations regarding graphene concentration or the amount of surfactant required to colloidally stabilize the sheets. Here, we demonstrate that an innocuous and readily available derivative of vitamin B2, namely the sodium salt of flavin mononucleotide (FMNS), is a highly efficient dispersant in the preparation of aqueous dispersions of defect-free, few-layer graphene flakes. Most notably, graphene concentrations in water as high as ∼50 mg mL(-1) using low amounts of FMNS (FMNS/graphene mass ratios of about 0.04) could be attained, which facilitated the formation of free-standing graphene films displaying high electrical conductivity (∼52000 S m(-1)) without the need of carrying out thermal annealing or other types of post-treatment. The excellent performance of FMNS as a graphene dispersant could be attributed to the combined effect of strong adsorption on the sheets through the isoalloxazine moiety of the molecule and efficient colloidal stabilization provided by its negatively charged phosphate group. The FMNS-stabilized graphene sheets could be decorated with nanoparticles of several noble metals (Ag, Pd, and Pt), and the resulting hybrids exhibited a high catalytic activity in the reduction of nitroarenes and electroreduction of oxygen. Overall, the present results should expedite the processing and implementation of graphene in, e.g., conductive inks, composites, and hybrid materials with practical utility in a wide range of applications.
Voltammetric enzyme genosensors on streptavidin-modified screen-printed carbon electrodes (SPCEs) for the detection of virulence nucleic acid determinants of pneumolysin and autolysin genes, exclusively present on the genome of the human pathogen Streptococcus pneumoniae, were described. Alkaline phosphatase (AP) and 3-indoxyl phosphate were used as the enzymatic label and substrate, respectively. The oligonucleotide probes were immobilized on electrochemically pretreated SPCEs through the streptavidin/biotin reaction. The adsorption of streptavidin was performed by deposition of a drop of a streptavidin solution overnight at 4 degrees C on the surface of the SPCEs. After the hybridization reaction with FITC-labeled complementary targets, the enzyme is captured using an anti-FITC antibody conjugated to AP. In nonstringent experimental conditions, these genosensors can detect 0.49 fmol of 20-mer oligonucleotide target and discriminate between a complementary oligo and an oligo with a three-base mismatch. In the presence of 25% formamide in the hybridization buffer, a single-base mismatch on the oligonucleotide target can be detected.
Enzyme immunoassays (EIAs) are currently the predominant analytical technique for the quantitative determination of a broad variety of analytes in clinical, medical, biotechnological, and environmental significance. Although the most common detection methods for EIAs are based on spectroscopic measurements, electrochemical techniques, due to their high sensitivity, selectivity, simplicity and low cost, have emerged as a very attractive alternative to carry out the detection step in this kind of assays. The intention of this review is to cover the progress and development in integrating electrochemical detection methods with EIAs, over the past five years.
The exfoliation and colloidal stabilization of layered transition metal dichalcogenides (TMDs) in an aqueous medium using functional biomolecules as dispersing agents have a number of potential benefits toward the production and practical use of the corresponding two-dimensional materials, but such a strategy has so far remained underexplored. Here, we report that DNA and RNA nucleotides are highly efficient dispersants in the preparation of stable aqueous suspensions of MoS and other TMD nanosheets at significant concentrations (up to 5-10 mg mL). Unlike the case of common surfactants, for which adsorption on 2D materials is generally based on weak dispersive forces, the exceptional colloidal stability of the TMD flakes was shown to rely on the presence of relatively strong, specific interactions of Lewis acid-base type between the DNA/RNA nucleotide molecules and the flakes. Moreover, the nucleotide-stabilized MoS nanosheets were shown to be efficient catalysts in the reduction of nitroarenes (4-nitrophenol and 4-nitroaniline), thus constituting an attractive alternative to the use of expensive heterogeneous catalysts based on noble metals, and exhibited an electrocatalytic activity toward the hydrogen evolution reaction that was not impaired by the possible presence of nucleotide molecules adsorbed on their active sites. The biocompatibility of these materials was also demonstrated on the basis of cell proliferation and viability assays. Overall, the present work opens new vistas on the colloidal stabilization of 2D materials based on specific interactions that could be useful toward different practical applications.
Sixteen phenolic compounds, 14 of which naturally occurring, were compared to the synthetic 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) and violuric acid (VA) in terms of their ability to act as mediators/enhancers in: (1) laccase oxidation of veratryl alcohol as a lignin model compound, and (2) electrochemical oxidation of kraft and flax lignins. HPLC analysis revealed that the syringyl-type phenols methyl syringate and acetosyringone were the most efficient natural enhancers in the laccase oxidation of veratryl alcohol. Both compounds, though far from the performance of ABTS were able to generate veratraldehyde in amount similar to that obtained with VA. By contrast, the best performing phenolic enhancers for the electrochemical oxidation of lignins were sinapinaldehyde, vanillin, acetovanillone, and syringic acid. Catalytic efficiencies close to those achieved with ABTS and VA were calculated for these phenolic compounds.
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