Reshaping, Fragmentation, and Assembly of Gold Nanoparticles Assisted by Pulse Lasers

ConspectusThe vast majority of the outstanding applications of metal nanoparticles (NPs) developed during the last two decades have arisen from their unique optical properties. Within this context, rational synthesis and assembly of gold NPs have been the main research focus, aiming at the design of nanoplasmonic devices with tailored optical functionalities. The progress made in this field is thus to be ascribed to the understanding of the origin of the interaction between light and such gold nanostructures, the dynamics of which have been thoroughly investigated with significant contributions from short and ultrashort pulse laser technologies.We focus this Account on the potential of pulse lasers to provide new fundamental insights into the electron dynamics involved in the interaction of light with the free conduction electrons of Au NPs, that is, localized surface plasmon resonances (LSPRs). The excitation of LSPRs with a femtosecond pulse laser is followed by thermalization of the Au NP electrons and the subsequent relaxation of the nanocrystal lattice and the surrounding environment, which generally results in surface melting. By contrast, nanosecond irradiation usually induces AuNP fragmentation and uncontrolled melting due to overlapping excitation and relaxation phenomena. These concepts have been exploited toward the preparation of highly monodisperse gold nanospheres via pulse laser irradiation of polyhedral nanocrystal colloids, or in the fabrication of nanostructures with “written-in” optical properties. The applicability of pulsed coherent light has been extended toward the direct synthesis and manipulation of Au NPs. Through ablation of a gold target in a liquid with pulse lasers, spherical Au NPs can be synthesized with no need of stabilizing ligands, which is a great advantage in terms of reducing toxicity, rendering these NPs particularly suitable for medical applications. In addition, femtosecond laser irradiation has been proven a unique tool for the controlled welding of plasmonic gold nanostructures by electromagnetic field enhancement at the hot spots of assembled Au NPs. The combination of such nanostructures with pulse lasers promises significant chemical and biochemical advances, including the structural determination of organic reaction intermediates, the investigation of phase transitions in inorganic nanomaterials at mild reaction conditions, or the efficient photothermal destruction of cancer cells avoiding damage of surrounding tissue

Cooperative Self-Assembly Transfer from Hierarchical Supramolecular Polymers to Gold Nanoparticles

The transfer of information encoded by molecular subcomponents is a key phenomenon that regulates the biological inheritance in living organisms, yet there is a lack of understanding of related transfer mechanisms at the supramolecular level in artificial multicomponent systems. Our contribution to tackle this challenge has focused on the design of a thiolated π-conjugated linking unit, whose hierarchical, cooperative self-assembly in nonpolar media can be efficiently transferred from the molecular to the nanoscopic level, thereby enabling the reversible self-assembly of gold nanoparticle (AuNP) clusters. The transfer of supramolecular information by the linking π-system can only take place when a specific cooperative nucleation-elongation mechanism is operative, whereas low-ordered noncooperative assemblies formed below a critical concentration do not suffice to extend the order to the AuNP level. To the best of our knowledge, our approach has allowed for the first time a deep analysis of the hierarchy levels and thermodynamics involved in the self-assembly of AuNPs

Remote Control by π‑Conjugation of the Emissive Properties of Fischer Carbene-BODIPY Dyads

The synthesis, structure, and complete characterization of mono- and bimetallic dyads joining Fischer carbene complexes and BODIPY chromophores are reported. In these organometallic species, the Fischer carbene complex is attached to the BODIPY moiety through a <i>p</i>-aminophenyl group linked at the C8 carbon atom of the BODIPY core. The photophysical properties, namely the corresponding UV/vis absorption and emission spectra of these new metal–carbene complexes, are analyzed and discussed. It is found that whereas the absorption of the considered dyads strongly resembles that of the parent 4-anilinyl-substituted BODIPY, the fluorescence emission is significantly reduced in these species, very likely as a result of a Förster-type energy transfer mechanism. At variance, the replacement of the pentacarbonyl-metal(0) fragment by a carbonyl group leads to high fluorescence emission intensity. In addition, the emissive properties of the BODIPY core in these organometallic dyads can be tuned by remote groups by means of π-conjugation, as supported by density functional theory calculations

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-EO₁-16 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-EO₁-16. 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

Using Inclusion Complexes with Cyclodextrins To Explore the Aggregation Behavior of a Ruthenium Metallosurfactant

The aggregation behavior of a chiral metallosurfactant, bis­(2,2′-bipyridine)­(4,4′-ditridecyl-2,2′-bipyridine)­ruthenium­(II) dichloride (Ru₂⁴C₁₃), synthesized as a racemic mixture was characterized by small-angle neutron scattering, light scattering, NMR, and electronic spectroscopies. The analysis of the SANS data indicates that micelles are prolate ellipsoids over the range of concentrations studied, with a relatively low aggregation number, and the micellization takes place gradually with increasing concentration. The presence of cyclodextrins (β-CD and γ-CD) induces the breakup of the micelles and helps to establish that micellization occurs at a very slow exchange rate compared to the NMR time scale. The open structure of this metallosurfactant enables the formation of very stable complexes of 3:1 stoichiometry, in which one CD threads one of the hydrocarbon tails and two CDs the other, in close contact with the polar head. The complex formed with β-CD, more stable than the one formed with the wider γ-CD, is capable of resolving the Δ and Λ enantiomers at high CD/surfactant molar ratios. The chiral recognition is possible due to the very specific interactions taking place when the β-CD coversvia its secondary rimpart of the diimine moiety connected to the hydrophobic tails. A SANS model comprising a binary mixture of hard spheres (complex + micelles) was successfully used to study quantitatively the effect of the CDs on the aggregation of the surfactant

Intracellular pH-Induced Tip-to-Tip Assembly of Gold Nanorods for Enhanced Plasmonic Photothermal Therapy

The search for efficient plasmonic photothermal therapies using nonharmful pulse laser irradiation at the near-infrared (NIR) is fundamental for biomedical cancer research. Therefore, the development of novel assembled plasmonic gold nanostructures with the aim of reducing the applied laser power density to a minimum through hot-spot-mediated cell photothermolysis is an ongoing challenge. We demonstrate that gold nanorods (Au NRs) functionalized at their tips with a pH-sensitive ligand assemble into oligomers within cell lysosomes through hydrogen-bonding attractive interactions. The unique intracellular features of the plasmonic oligomers allow us to significantly reduce the femtosecond laser power density and Au NR dose while still achieving excellent cell killing rates. The formation of gold tip-to-tip oligomers with longitudinal localized surface plasmon resonance bands at the NIR, obtained from low-aspect-ratio Au NRs close in resonance with 800 nm Ti:sapphire 90 fs laser pulses, was found to be the key parameter for realizing the enhanced plasmonic photothermal therapy

Large-Scale Plasmonic Pyramidal Supercrystals via Templated Self-Assembly of Monodisperse Gold Nanospheres

Three-dimensional supercrystals of plasmonic nanoparticles are a novel class of materials with exciting applications in technologies such as light harvesting or metamaterials. However, their realization relies on extraordinarily regular colloidal building blocks and accurate self-assembly methods. We present here a simple and up-scalable protocol for the synthesis of smooth gold nanospheres with high monodispersity in size and sphericity. The synthesis involves rapid growth up to the desired size and subsequent removal of surface roughness via an efficient etching step, so that nanospheres with diameters ranging between 10 and 110 nm can be obtained in large quantities. Upon functionalization with thiolated polyethylene glycol and low surfactant concentration, Au nanospheres were employed as building blocks to produce uniform arrays of micron-sized 3D pyramidal supercrystals over large areas, by means of a template-assisted approach. Focused ion beam cutting and SEM characterization revealed a face-centered cubic lattice within individual pyramidal supercrystals

Femtosecond Laser-Controlled Tip-to-Tip Assembly and Welding of Gold Nanorods

Directed assembly of gold nanorods through the use of dithiolated molecular linkers is one of the most efficient methodologies for the morphologically controlled tip-to-tip assembly of this type of anisotropic nanocrystals. However, in a direct analogy to molecular polymerization synthesis, this process is characterized by difficulties in chain-growth control over nanoparticle oligomers. In particular, it is nearly impossible to favor the formation of one type of oligomer, making the methodology hard to use for actual applications in nanoplasmonics. We propose here a light-controlled synthetic procedure that allows obtaining selected plasmonic oligomers in high yield and with reaction times in the scale of minutes by irradiation with low fluence near-infrared (NIR) femtosecond laser pulses. Selective inhibition of the formation of gold nanorod <i>n</i>-mers (trimers) with a longitudinal localized surface plasmon in resonance with a 800 nm Ti:sapphire laser, allowed efficient trapping of the (<i>n</i> – 1)-mers (dimers) by hot spot mediated photothermal decomposition of the interparticle molecular linkers. Laser irradiation at higher energies produced near-field enhancement at the interparticle gaps, which is large enough to melt gold nanorod tips, offering a new pathway toward tip-to-tip welding of gold nanorod oligomers with a plasmonic response at the NIR. Thorough optical and electron microscopy characterization indicates that plasmonic oligomers can be selectively trapped and welded, which has been analyzed in terms of a model that predicts with reasonable accuracy the relative concentrations of the main plasmonic species

Au@Ag Nanoparticles: Halides Stabilize {100} Facets

Seed-mediated growth is the most efficient methodology to control the size and shape of colloidal metal nanoparticles. In this process, the final nanocrystal shape is defined by the crystalline structure of the initial seed as well as by the presence of ligands and other additives that help to stabilize certain crystallographic facets. We analyze here the growth mechanism in aqueous solution of silver shells on presynthesized gold nanoparticles displaying various well-defined crystalline structures and morphologies. A thorough three-dimensional electron microscopy characterization of the morphology and internal structure of the resulting core–shell nanocrystals indicates that {100} facets are preferred for the outer silver shell, regardless of the morphology and crystallinity of the gold cores. These results are in agreement with theoretical analysis based on the relative surface energies of the exposed facets in the presence of halide ions