From Multi- to Single-Hollow Trimetallic Nanocrystals by Ultrafast Heating.

Metal nanocrystals (NCs) display unique physicochemical features that are highly dependent on nanoparticle dimensions, anisotropy, structure, and composition. The development of synthesis methodologies that allow us to tune such parameters finely emerges as crucial for the application of metal NCs in catalysis, optical materials, or biomedicine. Here, we describe a synthetic methodology to fabricate hollow multimetallic heterostructures using a combination of seed-mediated growth routes and femtosecond-pulsed laser irradiation.

A Nanoparticle-Based Model System for the Study of Heterogeneous Nucleation Phenomena.

Heterogeneous nucleation processes are involved in many important phenomena in nature, including devastating human diseases caused by amyloid structures or the harmful frost formed on fruits. However, understanding them is challenging due to the difficulties of characterizing the initial stages of the process occurring at the interface between the nucleation medium and the substrate surfaces. This work implements a model system based on gold nanoparticles to investigate the effect of particle surface chemistry and substrate properties on heterogeneous nucleation processes.

Chiral Seeded Growth of Gold Nanorods Into Fourfold Twisted Nanoparticles with Plasmonic Optical Activity.

A robust and reproducible methodology to prepare stable inorganic nanoparticles with chiral morphology may hold the key to the practical utilization of these materials. An optimized chiral growth method to prepare fourfold twisted gold nanorods is described herein, where the amino acid cysteine is used as a dissymmetry inducer. Four tilted ridges are found to develop on the surface of single-crystal nanorods upon repeated reduction of HAuCl , in the presence of cysteine as the chiral inducer and ascorbic acid as a reducing agent.

How a Facet of a Nanocrystal Is Formed: The Concept of the Symmetry Based Kinematic Theory.

Conventional nanocrystal (NC) growth mechanisms have overwhelmingly focused on the final exposed facets to explain shape evolution. However, how the final facets are formed from the initial nuclei or seeds, has not been specifically interrogated. In this concept paper, we would like to concentrate on this specific topic, and introduce the symmetry based kinematic theory (SBKT) to explain the formation and evolution of crystal facets.

Self-Assembly of Colloidal Nanocrystals into 3D Binary Mesocrystals.

Biominerals are unique materials found in many living organisms that often display outstanding functionalities attributed to their mesocrystalline structure. Mesocrystals are nanocrystal superstructures with mutual crystallographic alignment of the building units. One could thus imagine these optimized evolutionary systems as archetypes to fabricate advanced materials.

Tuneable helices of plasmonic nanoparticles using liquid crystal templates: molecular dynamics investigation of an unusual odd-even effect in liquid crystalline dimers.

Liquid crystalline (LC) dimers formed helical nanofilaments depending on the parity of the alkyl linker, revealing an unusual odd-even effect. Molecular dynamics simulations were used to investigate the observed tendency. Elongation of the linker translates to an increase of the pitch of the helices, which allows achieving tuneable helical assemblies of Au nanoparticles doped to the LC matrix.

Influence of anisotropy on heterogeneous nucleation of gold nanorod assemblies.

In this study, we analysed for the first time heterogeneous nucleation with anisotropic nanoparticles as a model system for non-spherical building units on the nanoscale. Gold nanorods were synthesised and assembled to investigate the phenomenon of heterogeneous nucleation. To determine the influence of the particle shape on heterogeneous nucleation, we utilised gold nanorods with varying aspect ratios, ranging from 3.

A Symmetry-Based Kinematic Theory for Nanocrystal Morphology Design.

The growth of crystalline nanoparticles (NPs) generally involves three processes: nucleation, growth, and shape evolution. Among them, the shape evolution is less understood, despite the importance of morphology for NP properties. Here, we propose a symmetry-based kinematic theory (SBKT) based on classical growth theories to illustrate the process.

STEM Tomography of Au Helical Assemblies.

Composite, helical nanostructures formed using cooperative interactions of liquid crystals and Au nanoparticles were studied using a scanning transmission electron microscopy (STEM) mode. The investigated helical assemblies exhibit long-range hierarchical order across length scales, as a result of the crystallization (freezing) directed growth mechanism of nanoparticle-coated twisted nanoribbons and their ability to form organized bundles. Here, STEM methods were used to reproduce the 3D structure of the Au nanoparticle double helix.

Simple Determination of Gold Nanocrystal Dimensions by Analytical Ultracentrifugation via Surface Ligand-Solvent Density Matching.

Analytical ultracentrifugation (AUC) is a powerful technique to observe colloidal nanocrystals (NCs) directly in solution and obtain critical information about their physical-chemical properties. Nevertheless, a more comprehensive implementation of AUC for the characterisation of such a class of crystalline colloids has been traditionally impaired by the requirement of having a priori knowledge of the complex, multilayered structure formed by NC in solution. This includes the nature (density and mass) of the surface ligands (SLs) that provide NC colloidal stability and the shell of solvent molecules formed on it.

Insights into colloidal nanoparticle-protein corona interactions for nanomedicine applications.

Colloidal nanoparticles (NPs) have attracted significant attention due to their unique physicochemical properties suitable for diagnosing and treating different human diseases. Nevertheless, the successful implementation of NPs in medicine demands a proper understanding of their interactions with the different proteins found in biological fluids. Once introduced into the body, NPs are covered by a protein corona (PC) that determines the biological behavior of the NPs.

Synthesis of nickel hexacyanoferrate nanocubes with tuneable dimensions temperature-controlled Ni-citrate complexation.

The citrate-assisted growth of nickel hexacyanoferrate (NiHCF) nanocubes was investigated. Control over the complexation of Ni2+ ions with citrate at different temperatures enabled fine tuning of the nanocrystal (NC) dimensions and their self-assembly into mesocrystals. Our results introduce new concepts towards the synthesis of NiHCF NCs, potentially applicable to other members of the Prussian blue analogues family.

SANS study of mixed cholesteric cellulose nanocrystal - gold nanorod suspensions.

Self-assembly of cellulose nanocrystals (CNCs) doped with anisotropic gold nanorods (AuNRs) was studied by small-angle neutron scattering. Correlation distances and structured domains were analysed to determine the influence of CNC and AuNR concentration on structuring. The transfer of the nematic structure of CNCs to AuNRs is explained in terms of an entropy-driven evolution from an isotropic to a cholesteric phase, with small nematic domains already present in the "isotropic" phase in equilibrium with the chiral nematic phase.

3D Characterization and Plasmon Mapping of Gold Nanorods Welded by Femtosecond Laser Irradiation.

Ultrafast laser irradiation can induce morphological and structural changes in plasmonic nanoparticles. Gold nanorods (Au NRs), in particular, can be welded together upon irradiation with femtosecond laser pulses, leading to dimers and trimers through the formation of necks between individual nanorods. We used electron tomography to determine the 3D (atomic) structure at such necks for representative welding geometries and to characterize the induced defects.

Micelle-directed chiral seeded growth on anisotropic gold nanocrystals.

Surfactant-assisted seeded growth of metal nanoparticles (NPs) can be engineered to produce anisotropic gold nanocrystals with high chiroptical activity through the templating effect of chiral micelles formed in the presence of dissymmetric cosurfactants. Mixed micelles adsorb on gold nanorods, forming quasihelical patterns that direct seeded growth into NPs with pronounced morphological and optical handedness. Sharp chiral wrinkles lead to chiral plasmon modes with high dissymmetry factors (~0.

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.

Microscopic Analysis of Heterogeneous Nucleation of Nanoparticle Superstructures.

Nucleation phenomena play an important role in our world, and understanding them is of major interest. However, we lack analytical methods with the sufficient temporal and spatial resolution to analyze nucleation processes. In this work we used CTAB-stabilized gold nanocubes as a model system for nucleation, meaning the nanoparticles act like ions or atoms and built up larger superstructures comparable to normal nucleation phenomena.

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.

Intercellular Trafficking of Gold Nanostars in Uveal Melanoma Cells for Plasmonic Photothermal Therapy.

Efficient plasmonic photothermal therapies (PPTTs) using non-harmful pulse laser irradiation at the near-infrared (NIR) are a highly sought goal in nanomedicine. These therapies rely on the use of plasmonic nanostructures to kill cancer cells while minimizing the applied laser power density. Cancer cells have an unsettled capacity to uptake, retain, release, and re-uptake gold nanoparticles, thus offering enormous versatility for research.

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.

Shaping Liquid Crystals with Gold Nanoparticles: Helical Assemblies with Tunable and Hierarchical Structures Via Thin-Film Cooperative Interactions.

The availability of helical assemblies of plasmonic nanoparticles with precisely controlled and tunable structures can play a key role in the future development of chiral plasmonics and metamaterials. Here, a strategy to efficiently yield helical structures based on the cooperative interactions of liquid crystals and gold nanoparticles in thin films is developed. These nanocomposites exhibit exceptional long-range hierarchical order across length scales, which results from the growth mechanism of nanoparticle-coated twisted nanoribbons and their ability to form organized bundles.

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.