Sergio Gómez-Graña

Intense Optical Activity from Three‐Dimensional Chiral Ordering of Plasmonic Nanoantennas

Twisting nanoparticles: Plasmonic circular dichroism was experimentally obtained in chiral 3D organizations of gold nanorods obtained by self-assembly of the nanoantennas onto a fiber template with a twisted morphology. Numerical simulations based on coupled dipoles confirm the crucial role of gold nanorods in this intense circular dichroism

Atomic-scale determination of surface facets in gold nanorods

It is widely accepted that the physical properties of nanostructures depend on the type of surface facets. For Au nanorods, the surface facets have a major influence on crucial effects such as reactivity and ligand adsorption and there has been controversy regarding facet indexing. Aberration-corrected electron microscopy is the ideal technique to study the atomic structure of nanomaterials. However, these images correspond to two-dimensional (2D) projections of 3D nano-objects, leading to an incomplete characterization. Recently, much progress was achieved in the field of atomic-resolution electron tomography, but it is still far from being a routinely used technique. Here we propose a methodology to measure the 3D atomic structure of free-standing nanoparticles, which we apply to characterize the surface facets of Au nanorods. This methodology is applicable to a broad range of nanocrystals, leading to unique insights concerning the connection between the structure and properties of nanostructures.

Surfactant (Bi)Layers on Gold Nanorods

Gold nanorods in aqueous solution are generally surrounded by surfactants or capping agents. This is crucial for anisotropic growth during synthesis and for their final stability in solution. When CTAB is used, a bilayer has been evidenced from analytical methods even though no direct morphological characterization of the precise thickness and compactness has been reported. The type of surfactant layer is also relevant to understand the marked difference in further self-assembling properties of gold nanorods as experienced using 16-EO(1)-16 gemini surfactant instead of CTAB. To obtain a direct measure of the thickness of the surfactant layer on gold nanorods synthesized by the seeded growth method, we coupled TEM, SAXS, and SANS experiments for the two different cases, CTAB and gemini 16-EO(1)-16. Despite the strong residual signal from micelles in excess, it can be concluded that the thickness is imposed by the chain length of the surfactant and corresponds to a bilayer with partial interdigitation.

Three-Dimensional Elemental Mapping at the Atomic Scale in Bimetallic Nanocrystals

A thorough understanding of the three-dimensional (3D) atomic structure and composition of core-shell nanostructures is indispensable to obtain a deeper insight on their physical behavior. Such 3D information can be reconstructed from two-dimensional (2D) projection images using electron tomography. Recently, different electron tomography techniques have enabled the 3D characterization of a variety of nanostructures down to the atomic level. However, these methods have all focused on the investigation of nanomaterials containing only one type of chemical element. Here, we combine statistical parameter estimation theory with compressive sensing based tomography to determine the positions and atom type of each atom in heteronanostructures. The approach is applied here to investigate the interface in core-shell Au@Ag nanorods but it is of great interest in the investigation of a broad range of nanostructures.

Biogenic synthesis of metal nanoparticles using a biosurfactant extracted from corn and their antimicrobial properties

A new and promising biosurfactant extracted from corn steep liquor has been used for the green synthesis of gold and silver nanoparticles (NPs) in a one-step procedure induced by temperature. Most of the biosurfactants proposed in the literature are produced by pathogenic microorganisms; whereas the biosurfactant used in the current work was extracted from a liquid stream, fermented spontaneously by lactic acid bacteria, which are “generally recognized as safe” (GRAS) microorganisms. The reduction of a gold precursor in the presence of a biosurfactant gives rise to a mixture of nanospheres and nanoplates with distinct optical features. Moreover, the growth of nanoplates can be promoted by increasing the reaction temperature to 60 °C. In the case of silver, the biosurfactant just induces the formation of pseudo-spherical NPs. The biosurfactant plays a key role in the reduction of the metal precursor, as well as in the stabilization of the resulting NPs. Furthermore, the antimicrobial activity of the resulting silver colloids has been analyzed against Escherichia coli, Pseudomonas aeruginosa and Staphylococcus aureus. The biosurfactant stabilized NPs slightly increased the inhibition of E. coli in comparison with citrate stabilized Ag NPs. The use of this biosurfactant extracted from corn steep liquor for the synthesis of metal NPs contributes to enhancing the application of green technologies and increasing the utilization of clean, non-toxic and environmentally safe production processes. Therefore, it can help to reduce environmental impact, minimize waste and increase energy efficiency in the field of nanomaterials.

Supramolecular Control over the Interparticle Distance in Gold Nanoparticle Arrays by Cyclodextrin Polyrotaxanes

Amphiphilic nonionic ligands, synthesized with a fixed hydrophobic moiety formed by a thiolated alkyl chain and an aromatic ring, and with a hydrophilic tail composed of a variable number of oxyethylene units, were used to functionalize spherical gold nanoparticles (AuNPs) in water. Steady-state and time-resolved fluorescence measurements of the AuNPs in the presence of α-cyclodextrin (α-CD) revealed the formation of supramolecular complexes between the ligand and macrocycle at the surface of the nanocrystals. The addition of α-CD induced the formation of inclusion complexes with a high apparent binding constant that decreased with the increasing oxyethylene chain length. The formation of polyrotaxanes at the surface of AuNPs, in which many α-CDs are trapped as hosts on the long and linear ligands, was demonstrated by the formation of large and homogeneous arrays of self-assembled AuNPs with hexagonal close packing, where the interparticle distance increased with the length of the oxyethylene chain. The estimated number of α-CDs per polyrotaxane suggests a high rigidization of the ligand upon complexation, allowing for nearly perfect control of the interparticle distance in the arrays. This degree of supramolecular control was extended to arrays formed by AuNPs stabilized with polyethylene glycol and even to binary arrays. Electromagnetic simulations showed that the enhancement and distribution of the electric field can be finely controlled in these plasmonic arrays.