Noncovalent Interactions of Tiopronin-Protected Gold Nanoparticles with DNA: Two Methods to Quantify Free Energy of Binding

The binding of gold nanoparticles capped with N-(2-mercaptopropionyl)glycine (Au@tiopronin) with double-stranded DNA has been investigated and quantified in terms of free energies by using two different approaches. The first approach follows the DNA conformational changes induced by gold nanoparticles using the CD technique. The second methodology consists in the use of pyrene-1-carboxaldehyde as a fluorescent probe. This second procedure implies the determination of the “true” free energy of binding of the probe with DNA, after corrections through solubility measurements. Working at different salt concentrations, the nonelectrostatic and electrostatic components of the binding free energy have been separated. The results obtained revealed that the binding is of nonelectrostatic character, fundamentally. The procedure used in this work could be extended to quantify the binding affinity of other AuNPs/DNA systems

Electrochemiluminescence of the [Ru(bpy)₃]²⁺ Complex: The Coreactant Effect of PAMAM Dendrimers in an Aqueous Medium

Electrogenerated chemiluminescence (ECL) from aqueous solutions of tris­(2,2′-bipyridine)­ruthenium­(II), [Ru­(bpy)₃]²⁺, in the presence of PAMAM G1.5 and G4.5 dendrimers, was observed without the addition of coreactants. The ECL efficiency, Φ_ECL, was enhanced with the addition of increasing amounts of G1.5 dendrimer. Indeed, the ECL efficiency for the [Ru­(bpy)₃]²⁺/G1.5 dendrimer became about 10 times higher than that for the [Ru­(bpy)₃]²⁺/ oxalate anion system. However, the ECL efficiency in the presence of the G4.5 dendrimer was smaller than that for the G1.5 dendrimer at concentrations similar to those for G1.5 with identical medium conditions. Besides, the addition of NaCl at a given concentration of G1.5 dendrimer decreased the ECL efficiency. The results of Φ_ECL were interpreted by taking into account the coreactant effect and the electrostatic (long-range and short-range) interactions between the ruthenium­(II) complex and the electric field of the dendrimer surface. Standard formal potentials of the [Ru­(bpy)₃]^3+/2+ couple in the presence of G1.5 and G4.5 dendrimers were also determined

Solvent Effects on the Kinetics of the Interaction of 1-Pyrenecarboxaldehyde with Calf Thymus DNA

The kinetics of the interaction of a fluorescent probe, 1-pyrenecarboxaldehyde, with calf thymus DNA has been studied in different water/alcohol mixtures (ethanol, 2-propanol, and ter-butanol) at 25 degrees C, by using the stopped flow technique. The kinetic curves are biexponential and reveal the presence of two processes whose rates differ by about I order of magnitude on the time scale. The dependence of the reciprocal fast relaxation time on the DNA concentration is linear, whereas the concentration dependence of the reciprocal slow relaxation time tends to a plateau at high DNA concentrations. The simplest mechanism consistent with the kinetic results involves a simple two-step series mechanism reaction scheme. The first step corresponds to the formation of a precursor complex, (DNA/PA, while the second one corresponds to full intercalation of the pyrene dye between the DNA base pairs. The values of the rate constants of both steps decrease as water activity decreases. The results have been discussed in terms of solvation of the species and changes in the viscosity of the solution

Design of highly stabilized nanocomposite inks based on biodegradable polymer-matrix and gold nanoparticles for Inkjet Printing

Nowadays there is a worldwide growing interest in the Inkjet Printing technology owing to its potentially high levels of geometrical complexity, personalization and resolution. There is also social concern about usage, disposal and accumulation of plastic materials. In this work, it is shown that sugar-based biodegradable polyurethane polymers exhibit outstanding properties as polymer-matrix for gold nanoparticles composites. These materials could reach exceptional stabilization levels, and demonstrated potential as novel robust inks for Inkjet based Printing. Furthermore, a physical comparison among different polymers is discussed based on stability and printability experiments to search for the best ink candidate. The University of Seville logo was printed by employing those inks, and the presence of gold was confirmed by ToF-SIMS. This approach has the potential to open new routes and applications for fabrication of enhanced biomedical nanometallic-sensors using stabilized AuNP

The fluorophore 4',6-diamidino-2-phenylindole (DAPI) induces DNA folding in long double-stranded DNA

DAPI (4’,6-diamidino-2-phenylindole) is a widely used fluorescent dye, whose complicated binding features to DNAs and RNAs have been the object of debates and are still not fully understood. In this study, different approaches were employed, including binding equilibrium measurements (spectrofluorometry), melting experiments (spectrophotometry), viscometric measurements, and circular dichroism and T-jump kinetic analyses; all data concur in shedding light on the complex mechanistic aspects of the binding mode of DAPI to natural DNA. Conditions are found that induce the mode of the DAPI/DNA interaction to change from groove binding to intercalation. Moreover, it is observed, for the first time, that DAPI is able to induce the formation of a rather compact polymer–dye adduct under particular conditions. The results suggest that this form is a folded or coiled DNA structure stabilized by DAPI dye bridges