Exploiting Localized Surface Binding Effects to Enhance the Catalytic Reactivity of Peptide-Capped Nanoparticles

Abstract

Peptide-based methods represent new approaches to selectively produce nanostructures with potentially important functionality. Unfortunately, biocombinatorial methods can only select peptides with target affinity and not for the properties of the final material. In this work, we present evidence to demonstrate that materials-directing peptides can be controllably modified to substantially enhance particle functionality without significantly altering nanostructural morphology. To this end, modification of selected residues to vary the site-specific binding strength and biological recognition can be employed to increase the catalytic efficiency of peptide-capped Pd nanoparticles. These results represent a step toward the de novo design of materials-directing peptides that control nanoparticle structure/function relationships.

The disclosure of mesoscale behaviour of a 3d-SMM monolayer on Au(111) through a multilevel approach

“…1), for each of the adsorbed Fe 4 Ph molecules. As already shown in previous studies, 9 the direction of the magnetization vector in the Fe 4 family is approximately perpendicular to the plane formed by the four iron atoms. Two distributions of θ were calculated (see Fig.…”

“…The other peaks, whose slightly broader shapes reveal a thermal contribution, present a regular recurrence, which maps a hexagonal lattice. As already observed in the single Fe 4 Ph molecule, no particular contact has been found between the Au(111) and Fe 4 Ph monolayer lattices, ruling out any surface imprinting effects on the symmetry of the Fe 4 Ph monolayer. Such a result is of extreme importance since the presence of a sort of "crystallographic" symmetry represents a prerequisite for 2D engineering and the exploitation of system properties of relevance for technological applications.…”

“…To account for the metallic character of the surface, a smearing of the occupation numbers of the molecular orbitals with a Fermi-Dirac distribution with a temperature of 1500 K was considered. All the simulation cells present four layers of gold with the bottom layer kept fixed to mimic the bulk and only one Fe 4 Ph molecule in it. Their dimensions and symmetry are chosen depending on the MM/MD results obtained for the FM and HM scenarios as discussed in details in the following sections.…”

“…Indeed, the realization of nanodevices by innovative structures with new or ad hoc intrinsic properties can enable breakthroughs in fundamental science and technological applications. [1][2][3] One of the possible ways to achieve smallness and novel properties at the same time is represented by the deposition of molecular systems with peculiar properties (catalytic, 4 magnetic 5 and conduction 6 ) on different surfaces.…”

Prediction of Specific Biomolecule Adsorption on Silica Surfaces as a Function of pH and Particle Size

“…9,19,20 However, limitations of current laboratory instrumentation pose difficulties to answer questions related to silica biomineralization and specific molecular recognition at the scale of 1 to 100 nm while complementary guidance from simulations can be very helpful. 9,18,[21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36] Studies by biopanning and molecular simulation with the polymer consistent force field (PCFF) extended to silica recently identified a range of contributions to specific adsorption of 4 peptides on amorphous silica particles. 9,10,26 These contributions include ion pairing between positively charged groups in the peptides and siloxide groups on the silica surface accompanied by neutralization of the ζ-potential, hydrogen bonds, van-der-Waals interactions with the surface, and conformation effects.…”