Spectrophotometric analysis of stability of gold nanoparticles during catalytic reduction of 4-nitrophenol.

Spectrophotometric monitoring of 4-nitrophenol (4-NP) reduction by sodium borohydride (NaBH4) using gold nanoparticles (GNPs) as a catalyst has been extensively studied, but the stability of GNPs in terms of change in the surface plasmon resonance (SPR) at different temperatures has not been explored. In the present investigation, our aim was to evaluate the SPR stability of GNPs as a catalyst during the reduction of 4-NP at different elevated temperatures (i.e. 30-60 °C) and sodium borohydride concentrations. Sensitivity of this degradation process toward concentration of GNPs at a range of temperatures is also evaluated. The spectrophotometric results reveal that up to 45 °C, 12 ± 1.5 nm catalyst has a consistent optical density (OD) during the entire 4-NP reduction process, which is related to the surface integrity of catalyst atoms. As the temperature approached 50 °C, the OD gradually decreased and showed a blue shift as the reaction proceeded, which could be related to a decrease in particle size or surface dissolution of gold atoms. The present study may find application in the design of catalysts for the reduction of organic pollutants in industrial wastewater at a range of temperatures.

Investigating the scavenging of reactive oxygen species by antioxidants via theoretical and experimental methods.

Reactive oxygen (hydroxyl OH, hydroperoxyl OOH) species are highly unstable to be studied experimentally under normal conditions. The present study reports the antioxidant potential of the vitamins namely ascorbic acid, riboflavin and nicotinic acid against these reactive oxygen species (ROS) using the predictive power of Density Functional Theory (DFT) (B3LYP with 6311G basis set) calculations. The order of reactivity of aforementioned vitamins was assessed by determining the bond dissociation enthalpy (BDE) of the OH bond, which is the controlling factor, if hydrogen atom transfer (HAT) mechanism is considered. Transition state calculations were also carried out to determine the reaction barrier for the radical scavenging reaction of vitamins by calculating the forward and the backward activation energies using the same level of theory as mentioned above. The theoretical methodology was first validated by taking a model stable free radical, 2, 2-diphenyl-1, picrylhydrazyl radical (DPPH) and applying the proposed approach followed by the experimental studies using UV-visible spectroscopy and cyclic voltammetry. The close agreement between the theoretical prediction and experimental observations proved the authenticity of theoretical approach.

Interaction of gold nanoparticles with free radicals and their role in enhancing the scavenging activity of ascorbic acid.

The present study investigates the interaction of citrate stabilized gold nanoparticles (12±1.5nm) (GNPs) with free radicals; 1,1-diphenyl-2-picrylhydrazyl (DPPH) stable and electrochemically generated superoxide, O2(-). Different experiments were designed to understand the interaction between GNPs and DPPH by employing cyclic voltammetry, UV-vis spectroscopy and computational chemistry using 6-311G basis set. The increase in heterogeneous rate constant, ksh, of DPPH upon addition of GNPs pointed towards possible complex formation, DPPH-GNPs which were further explained by a model assuming surface adsorption of DPPH on GNPs. Further, the model was validated by studying interaction of GNPs with a biologically important free radical, O2(-). Exciting result in terms of disappearance of anodic peak after GNPs addition confirmed that gold nanoparticles interacted with stable as well as unstable free radicals. Also, the stoichiometry of the most stable complex GNP-DPPH was determined from UV-vis spectroscopy by applying Job's method. The GNP-DPPH complex was found to be active with 46.0% reduction of the IC50 value of standard antioxidant, ascorbic acid (AA), indicating its role in enhancing antioxidant activity. Hence, this study presents a simple and potential approach to enhance the efficiency of natural antioxidants without modifying their structure, or involving the complex functionalization of GNPs with antioxidants.

Negotiation of intracellular membrane barriers by TAT-modified gold nanoparticles.

This paper contributes to the debate on how nanosized objects negotiate membrane barriers inside biological cells. The uptake of peptide-modified gold nanoparticles by HeLa cells has been quantified using atomic emission spectroscopy. The TAT peptide from the HIV virus was singled out as a particularly effective promoter of cellular uptake. The evolution of the intracellular distribution of TAT-modified gold nanoparticles with time has been studied in detail by TEM and systematic image analysis. An unusual trend of particles disappearing from the cytosol and the nucleus and accumulating massively in vesicular bodies was observed. Subsequent release of the particles, both by membrane rupture and by direct transfer across the membrane boundary, was frequently found. Ultimately, near total clearing of particles from the cells occurred. This work provides support for the hypothesis that cell-penetrating peptides can enable small objects to negotiate membrane barriers also in the absence of dedicated transport mechanisms.

Charge transfer complexes of picolines with sigma- and pi-acceptors.

In the present study CT complexes of 2-, 3- and 4-Picolines with (DDQ) 2, 3-dichloro-5, 6-dicyano parabenzoquinone (pi-acceptor) and (I2) Iodine (sigma-acceptor) have been investigated spectrophotometrically in three different solvents (CCl4, CHCl3 and CH2Cl2) at six different temperatures. The formation constants of the CT complexes were determined by the Benesi-Hildebrand equation. The thermodynamic parameters were calculated by Van(')t Hoff equation. The DeltaH degrees , DeltaG degrees and DeltaS degrees values are all negative implying that the formation of studied complexes is exothermic in nature.