Optical actuation of inorganic/organic interfaces: comparing peptide-azobenzene ligand reconfiguration on gold and silver nanoparticles

YesPhotoresponsive molecules that incorporate peptides capable of material-specific recognition provide a basis for biomolecule-mediated control of the nucleation, growth, organization, and activation of hybrid inorganic/organic nanostructures. These hybrid molecules interact with the inorganic surface through multiple noncovalent interactions which allow reconfiguration in response to optical stimuli. Here, we quantify the binding of azobenzene-peptide conjugates that exhibit optically triggered cis-trans isomerization on Ag surfaces and compare to their behavior on Au. These results demonstrate differences in binding and switching behavior between the Au and Ag surfaces. These molecules can also produce and stabilize Au and Ag nanoparticles in aqueous media where the biointerface can be reproducibly and reversibly switched by optically triggered azobenzene isomerization. Comparisons of switching rates and reversibility on the nanoparticles reveal differences that depend upon whether the azobenzene is attached at the peptide N- or C-terminus, its isomerization state, and the nanoparticle composition. Our integrated experimental and computational investigation shows that the number of ligand anchor sites strongly influences the nanoparticle size. As predicted by our molecular simulations, weaker contact between the hybrid biomolecules and the Ag surface, with fewer anchor residues compared with Au, gives rise to differences in switching kinetics on Ag versus Au. Our findings provide a pathway toward achieving new remotely actuatable nanomaterials for multiple applications from a single system, which remains difficult to achieve using conventional approaches.Air Office of Scientific Research, grant number FA9550-12-1-0226

Comparative study of materials-binding peptide interactions with gold and silver surfaces and nanostructures: A thermodynamic basis for biological selectivity of inorganic materials

NoControllable 3D assembly of multicomponent inorganic nanomaterials by precisely positioning two or more types of nanoparticles to modulate their interactions and achieve multifunctionality remains a major challenge. The diverse chemical and structural features of biomolecules can generate the compositionally specific organic/inorganic interactions needed to create such assemblies. Toward this aim, we studied the materials-specific binding of peptides selected based upon affinity for Ag (AgBP1 and AgBP2) and Au (AuBP1 and AuBP2) surfaces, combining experimental binding measurements, advanced molecular simulation, and nanomaterial synthesis. This reveals, for the first time, different modes of binding on the chemically similar Au and Ag surfaces. Molecular simulations showed flatter configurations on Au and a greater variety of 3D adsorbed conformations on Ag, reflecting primarily enthalpically driven binding on Au and entropically driven binding on Ag. This may arise from differences in the interfacial solvent structure. On Au, direct interaction of peptide residues with the metal surface is dominant, while on Ag, solvent-mediated interactions are more important. Experimentally, AgBP1 is found to be selective for Ag over Au, while the other sequences have strong and comparable affinities for both surfaces, despite differences in binding modes. Finally, we show for the first time the impact of these differences on peptide mediated synthesis of nanoparticles, leading to significant variation in particle morphology, size, and aggregation state. Because the degree of contact with the metal surface affects the peptide’s ability to cap the nanoparticles and thereby control growth and aggregation, the peptides with the least direct contact (AgBP1 and AgBP2 on Ag) produced relatively polydispersed and aggregated nanoparticles. Overall, we show that thermodynamically different binding modes at metallic interfaces can enable selective binding on very similar inorganic surfaces and can provide control over nanoparticle nucleation and growth. This supports the promise of bionanocombinatoric approaches that rely upon materials recognition.Air Office of Scientific Research grant number FA9550-12-1-022

Synthesis by Hydrothermal Treatment of ZnO-Based Varistors Doped with Rare Earth Oxides and Their Characterization by Impedance Spectroscopy

ZnO-based ceramic varistors have shown excellent electrical and dielectric properties due to their characteristics microstructures represented by the arrangement of their grains and grain boundaries that allow the absorption and flow of energy when subjected to an electrical surge. Their properties and characteristics depend on their chemical compositions and processing routes. Typical processing routes involve several stages of grinding and precalcination—which are time consuming processes. Because of this, this study proposes a simpler and cheaper alternative route for processing ceramic varistors. The alternative process proposed is the mixing of the precursor oxides by means of a hydrothermal treatment. The characteristics and properties of the synthesized ceramic varistors were evaluated by means of scanning electron microscopy, X-ray diffraction and impedance spectroscopy, considering the effect of the addition of rare earth oxides (La2O3, CeO2 and Nd2O3). The results showed that the mixing of the oxides through hydrothermal treatment produces ceramic varistors with characteristics and properties similar to those obtained by other processing routes. Furthermore, it was observed that the addition of rare earth oxides affects the characteristics and properties of the ceramic varistor depending on the type of rare earth oxide added, its concentration and ionic radius

Effect of Noble Metal Addition on the Disorder Dynamics of Ni3Al by Means of Monte Carlo Simulation

In this work, the effect of the addition of noble metals on the order–order disorder process of the L12 structure corresponding to the intermetallic Ni3Al is analyzed. Stoichiometric, nonstoichiometric, and quasi-binary compositions doped with noble metals such as Ag, Au, Pd, and Pt (1 at%) were analyzed. It was observed that depending on the composition, there is a modification in the activation energies calculated from the two time constants that characterize the disorder process. The statistic of atomic jumps was typified based on the configuration of the window to be crossed and, with this, it was identified that the origin of the negative activation energy of the long disorder process is due to an increase in the corresponding energy of the AlAl-Ni jump through unnatural windows