Controlled pDNA Release in Gemini Cationic Lipoplexes by Femtosecond Laser Irradiation of Gold Nanostars.

The design of nanovectors able to overcome biological barriers is one of the main challenges in biomedicine. Gemini cationic lipids are considered potential candidates for gene therapy due to their high biocompatibility and capacity to condense nucleic acids safely in the form of lipoplexes. However, this approach presents difficulties regarding genetic unpacking and, therefore, control over this process becomes crucial to ensure successful transfection. In this work, gemini cationic lipoplexes were prepared in the presence of plasmonic gold nanostars (AuNSs) to afford a nanovector that efficiently releases plasmid DNA (pDNA) upon irradiation with near-infrared femtosecond laser pulses. A critical AuNSs concentration of 50 pM and optimized laser power density of 400 mW led to successful pDNA release, whose efficiency could be further improved by increasing the irradiation time. Agarose gel electrophoresis was used to confirm pDNA release. UV-Vis-NIR spectroscopy and transmission electron microscopy studies were performed to monitor changes in the morphology of the AuNSs and lipoplexes after irradiation. From a physicochemical point of view, this study demonstrates that the use of AuNSs combined with gemini cationic lipoplexes allows control over pDNA release under ultrafast laser irradiation.

Hollow Gold Nanoparticles Produced by Femtosecond Laser Irradiation.

Metallic hollow nanoparticles exhibit interesting optical properties that can be controlled by geometrical parameters. Irradiation with femtosecond laser pulses has emerged recently as a valuable tool for reshaping and size modification of plasmonic metal nanoparticles, thereby enabling the synthesis of nanostructures with unique morphologies. In this Letter, we use classical molecular dynamics simulations to investigate the solid-to-hollow conversion of gold nanoparticles upon femtosecond laser irradiation. Here, we suggest an efficient method for producing hollow nanoparticles under certain specific conditions, namely that the particles should be heated to a maximum temperature between 2500 and 3500 K, followed by a fast quenching to room temperature, with cooling rates lower than 120 ps. Therefore, we describe the experimental conditions for efficiently producing hollow nanoparticles, opening a broad range of possibilities for applications in key areas, such as energy storage and catalysis.

Au@Ag Core-Shell Nanorods Support Plasmonic Fano Resonances.

In this work, we investigated experimentally and theoretically the plasmonic Fano resonances (FRs) exhibited by core-shell nanorods composed of a gold core and a silver shell (Au@Ag NRs). The colloidal synthesis of these Au@Ag NRs produces nanostructures with rich plasmonic features, of which two different FRs are particularly interesting. The FR with spectral location at higher energies (3.7 eV) originates from the interaction between a plasmonic mode of the nanoparticle and the interband transitions of Au. In contrast, the tunable FR at lower energies (2.92-2.75 eV) is ascribed to the interaction between the dominant transversal LSPR mode of the Ag shell and the transversal plasmon mode of the Au@Ag nanostructure. The unique symmetrical morphology and FRs of these Au@Ag NRs make them promising candidates for plasmonic sensors and metamaterials components.

Formation of Hollow Gold Nanocrystals by Nanosecond Laser Irradiation.

The irradiation of spherical gold nanoparticles (AuNPs) with nanosecond laser pulses induces shape transformations yielding nanocrystals with an inner cavity. The concentration of the stabilizing surfactant, the use of moderate pulse fluences, and the size of the irradiated AuNPs determine the efficiency of the process and the nature of the void. Hollow nanocrystals are obtained when molecules from the surrounding medium (e.g., water and organic matter derived from the surfactant) are trapped during laser pulse irradiation. These experimental observations suggest the existence of a subtle balance between the heating and cooling processes experienced by the nanocrystals, which induce their expansion and subsequent recrystallization keeping exogenous matter inside. The described approach provides valuable insight into the mechanism of interaction of a pulsed nanosecond laser with AuNPs, along with interesting prospects for the development of hollow plasmonic nanoparticles with potential applications related to gas and liquid storage at the nanoscale.

On the Large Near-Field Enhancement on Nanocolumnar Gold Substrates.

One of the most important and distinctive features of plasmonic nanostructures is their ability to confine large electromagnetic fields on nanometric volumes; i.e., the so-called hot spots. The generation, control and characterization of the hot spots are fundamental for several applications, like surface-enhanced spectroscopies. In this work, we characterize the near-field distribution and enhancement of nanostructured gold thin films fabricated by glancing angle deposition magnetron sputtering. These films are composed of columnar nanostructures with high roughness and high density of inter-columnar gaps, where the electromagnetic radiation can be confined, generating hot spots. As expected, the hot spots are localized in the gaps between adjacent nanocolumns and we use scattering-type scanning near-field optical microscopy to image their distribution over the surface of the samples. The experimental results are compared with finite-difference time-domain simulations, finding an excellent agreement between them. The spectral dependence of the field-enhancement is also studied with the simulations, together with surface-enhanced Raman spectroscopy at different excitation wavelengths in the visible-NIR range, proving a broad-band response of the substrates. These findings may result in interesting applications in the field of surface-enhanced optical spectroscopies or sensing.

Disconnecting Symmetry Breaking from Seeded Growth for the Reproducible Synthesis of High Quality Gold Nanorods.

One of the major difficulties hindering the widespread application of colloidal anisotropic plasmonic nanoparticles is the limited robustness and reproducibility of multistep synthetic methods. We demonstrate herein that the reproducibility and reliability of colloidal gold nanorod (AuNR) synthesis can be greatly improved by disconnecting the symmetry-breaking event from the seeded growth process. We have used a modified silver-assisted seeded growth method in the presence of the surfactant hexadecyltrimethylammonium bromide and n-decanol as a co-surfactant to prepare small AuNRs in high yield, which were then used as seeds for the growth of high quality AuNR colloids. Whereas the use of n-decanol provides a more-rigid micellar system, the growth on anisotropic seeds avoids sources of irreproducibility during the symmetry breaking step, yielding uniform AuNR colloids with narrow plasmon bands, ranging from 600 to 1270 nm, and allowing the fine-tuning of the final dimensions. This method provides a robust route for the preparation of high quality AuNR colloids with tunable morphology, size, and optical response in a reproducible and scalable manner.

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.

Femtosecond laser reshaping yields gold nanorods with ultranarrow surface plasmon resonances.

The irradiation of gold nanorod colloids with a femtosecond laser can be tuned to induce controlled nanorod reshaping, yielding colloids with exceptionally narrow localized surface plasmon resonance bands. The process relies on a regime characterized by a gentle multishot reduction of the aspect ratio, whereas the rod shape and volume are barely affected. Successful reshaping can only occur within a narrow window of the heat dissipation rate: Low cooling rates lead to drastic morphological changes, and fast cooling has nearly no effect. Hence, a delicate balance must be achieved between irradiation fluence and surface density of the surfactant on the nanorods. This perfection process is appealing because it provides a simple, fast, reproducible, and scalable route toward gold nanorods with an optical response of exceptional quality, near the theoretical limit.

Near- and Far-Field Optical Response of Eccentric Nanoshells.

We study the optical response of eccentric nanoshells (i.e., spherical nanoparticles with an eccentric spherical inclusion) in the near and the far field through finite-difference time-domain simulations. Plasmon hybridization theory is used to explain the obtained results. The eccentricity generates a far-field optical spectrum with various plasmon peaks. The number, position, and width of the peaks depend on the core offset. Near-field enhancements in the surroundings of these structures are significantly larger than those obtained for equivalent concentric nanoshells and, more importantly, they are almost independent of the illumination conditions. This opens up the door for using eccentric nanoshells in applications requiring intense near-field enhancements.