Growth Of AuNRs Research Articles

Revisiting El-Sayed Synthesis: Bayesian Optimization for Revealing New Insights during the Growth of Gold Nanorods.

In diverse fields, machine learning (ML) has sparked transformative changes, primarily driven by the wealth of big data. However, an alternative approach seeks to mine insights from "precious data", offering the possibility to reveal missed knowledge and escape potential knowledge traps. In this context, Bayesian optimization (BO) protocols have emerged as crucial tools for optimizing the synthesis and discovery of a broad spectrum of compounds including nanoparticles. In our work, we aimed to go beyond the commonly explored experimental conditions and showcase a workflow capable of unearthing fresh insights, even in well-studied research domains. The growth of AuNRs is a nonequilibrium process that remains poorly understood despite the presence of well-established seeded growth protocols. Traditional research aimed at understanding the mechanism of AuNR growth has primarily relied on altering one reaction condition at a time. While these studies are undeniably valuable, they often fail to capture the synergies between different reaction conditions, thus constraining the depth of insights they can offer. In the present study, we exploit BO, to identify diverse experimental conditions yielding AuNRs with similar spectroscopic characteristics. Notably, we identify viable and accelerated synthesis conditions involving elevated temperatures (36-40 °C) as well as high ascorbic acid concentrations. More importantly, we note that ascorbic acid and temperature can modulate each other's undesirable influences on the growth of AuNRs. Finally, by harnessing the power of interpretable ML algorithms, complemented by our deep chemical understanding, we revisited the established hierarchical relationships among reaction conditions that impact the El-Sayed-based growth of AuNRs.

Surfactant Layers on Gold Nanorods.

ConspectusGold nanorods (Au NRs) are an exceptionally promising tool in nanotechnology due to three key factors: (i) their strong interaction with electromagnetic radiation, stemming from their plasmonic nature, (ii) the ease with which the resonance frequency of their longitudinal plasmon mode can be tuned from the visible to the near-infrared region of the electromagnetic spectrum based on their aspect ratio, and (iii) their simple and cost-effective preparation through seed-mediated chemical growth. In this synthetic method, surfactants play a critical role in controlling the size, shape, and colloidal stability of Au NRs. For example, surfactants can stabilize specific crystallographic facets during the formation of Au NRs, leading to the formation of NRs with specific morphologies.The process of surfactant adsorption onto the NR surface may result in various assemblies of surfactant molecules, such as spherical micelles, elongated micelles, or bilayers. Again, the assembly mode is critical toward determining the further availability of the Au NR surface to the surrounding medium. Despite its importance and a great deal of research effort, the interaction between Au NPs and surfactants remains insufficiently understood, because the assembly process is influenced by numerous factors, including the chemical nature of the surfactant, the surface morphology of Au NPs, and solution parameters. Therefore, gaining a more comprehensive understanding of these interactions is essential to unlock the full potential of the seed-mediated growth method and the applications of plasmonic NPs. A plethora of characterization techniques have been applied to reach such an understanding, but many open questions remain.In this Account, we review the current knowledge on the interactions between surfactants and Au NRs. We briefly introduce the state-of-the-art methods for synthesizing Au NRs and highlight the crucial role of cationic surfactants during this process. The self-assembly and organization of surfactants on the Au NR surface is then discussed to better understand their role in seed-mediated growth. Subsequently, we provide examples and elucidate how chemical additives can be used to modulate micellar assemblies, in turn allowing for a finer control over the growth of Au NRs, including chiral NRs. Next, we review the main experimental characterization and computational modeling techniques that have been applied to shed light on the arrangement of surfactants on Au NRs and summarize the advantages and disadvantages for each technique. The Account ends with a "Conclusions and Outlook" section, outlining promising future research directions and developments that we consider are still required, mostly related to the application of electron microscopy in liquid and in 3D. Finally, we remark on the potential of exploiting machine learning techniques to predict synthetic routes for NPs with predefined structures and properties.

Investigating Growth of Gold Nanorods by Simultaneous Small‐Angle X‐Ray and Neutron Scattering

Increased usage of gold nanorods (AuNRs) in various biosensing and medical applications requires tight size and morphology control. This is often achieved by tuning the aggregation behavior of the stabilizing ligand cetrimonium bromide (CTAB). Because the role of CTAB during AuNR growth is still a matter of debate, simultaneous small‐angle X‐ray and neutron scattering experiments (SAXS/SANS) and measurements are performed. The SAXS/SANS measurements have enabled an instantaneous correlation between the size of evolving AuNR and the nanostructure of guiding CTAB moieties. Upon modifying the aggregation behavior of CTAB micelles by adding hexanol or pentanol as inert additives in the precursor solution, a marked change in reaction kinetics is observed. Alcohol‐modified CTAB nanostructures have improved AuNR size uniformity compared to those prepared in alcohol‐free CTAB solutions, which are attributed to different growth modes. The change in reaction kinetics is linked to a changed stabilization mechanism of reactants and nascent AuNR facilitated by CTAB micelles.

Effect of reducing agents on the synthesis of anisotropic gold nanoparticles

The seed-mediated method is a general procedure for the synthesis of gold nanorods (Au NRs), and reducing agents such as ascorbic acid (AA) and hydroquinone (HQ) are widely used for the growth process. Further, they are mild reducing agents; however, when AA is used, controlling the size of Au NRs with a higher aspect ratio (localized surface plasmon resonance (LSPR) peak, λLmax > 900 nm) is challenging because it results in a faster growth rate of Au NRs. In contrast, when HQ is used, Au NRs with a higher aspect ratio can be synthesized as it slows down the growth rate of the Au NRs and greatly enhanced the λLmax. However, the increase in λLmax is still needs not satisfactory due to the limited enhancement in the aspect ratio of Au NRs due to utilization of single reducing agent. The growth kinetics of the Au NRs can be modulated by controlling the reducing power of the reducing agents. In such scenario, judicious use of two reducing agents such as AA and HQ simultaneously can help us to design Au NRs of higher aspect ratio in a controlled manner due to the optimum growth rate resulting from the combined effect of both the reducing agents. In this study, we investigated the effect of the two reducing agents by controlling the volume ratios. When the growth solution contains both the reducing agents, the growth of Au NRs is first initiated by the fast reduction of Au3+ to Au+ due to stronger reducing power of the AA and when the AA in the growth solution is completely utilized, further growth of the Au NRs continues as a result of the HQ thereby resulting to high aspect ratio Au NRs. Consequently, the LSPR peak (λLmax > 1275 nm) can be tuned by controlling the volume ratios of the reducing agents.

Development of Indirect Competitive ELISA and Visualized Multicolor ELISA Based on Gold Nanorods Growth for the Determination of Zearalenone.

In this study, a zearalenone (ZEN) hapten was designed and prepared against the mycotoxin ZEN, and the original coating ZEN-ovalbumin (ZEN-OVA) was prepared by conjugation with OVA. Based on the gold nanorods (AuNRs) of uniform size and stable properties synthesized by the seed-mediated method, the indirect competitive enzyme-linked immunosorbent assay (ic-ELISA) and the AuNRs growth-based multicolor ELISA for detecting ZEN toxin were further established. Under the optimal experimental conditions, the coating amount of ZEN-OVA: 0.025 μg/well, antibody (Ab) dilution factor: 32,000 times, blocking solution: 0.5% skimmed milk powder, enzyme-labeled secondary Ab diluted 10,000 times, and a pH of the PBS buffer at 7.4, the sensitivity (IC50) of the established ic-ELISA for ZEN detection reached 0.85 ± 0.04 μg/L, and the limit of detection (IC15) reached 0.22 ± 0.08 μg/L. In the multicolor ELISA based on the growth of AuNRs, as the content of ZEN increased, the mixed solution exhibited a significant color change from brownish red to colorless. ZEN concentration as low as 0.1 μg/L can be detected by the naked eye (brown red to dark gray). This study provided an effective analysis strategy for the rapid screening and accurate monitoring of the ZEN contaminant in foods.

Citrate-Stabilized Gold Nanorods-Directed Osteogenic Differentiation of Multiple Cells.

ObjectiveGold nanorods (AuNRs) show great potential for versatile biomedical applications, such as stem cell therapy and bone tissue engineering. However, as an indispensable shape-directing agent for the growth of AuNRs, cetyltrimethylammonium bromide (CTAB) is not optimal for biological studies because it forms a cytotoxic bilayer on the AuNR surface, which interferes with the interactions with biological cells.MethodsCitrate-stabilized AuNRs with various aspect-ratios (Cit-NRI, Cit-NRII, and Cit-NRIII) were prepared by the combination of end-selective etching and poly(sodium 4-styrenesulfonate)-assisted ligand exchange method. Their effects on osteogenic differentiation of the pre-osteoblastic cell line (MC3T3-E1), rat bone marrow mesenchymal stem cells (rBMSCs), and human periodontal ligament progenitor cells (PDLPs) have been investigated. Potential signaling pathway of citrate-stabilized AuNRs-induced osteogenic effects was also investigated.ResultsThe experimental results showed that citrate-stabilized AuNRs have superior biocompatibility and undergo aspect-ratio-dependent osteogenic differentiation via expression of osteogenic marker genes, alkaline phosphatase (ALP) activity and formation of mineralized nodule. Furthermore, Wnt/β-catenin signaling pathway might provide a potential explanation for the citrate-stabilized AuNRs-mediated osteogenic differentiation.ConclusionThese findings revealed that citrate-stabilized AuNRs with great biocompatibility could regulate the osteogenic differentiation of multiple cell types through Wnt/β-catenin signaling pathway, which promote innovative AuNRs in the field of tissue engineering and other biomedical applications.

Optimized Au NRs for efficient SERS and SERRS performances with molecular and longitudinal surface plasmon resonance

Chemically stable and biocompatible gold nanorods (Au NRs) are an excellent building block for plasmonic-based applications, including surface-enhanced Raman spectroscopy (SERS). However, the quest for controlling the aspect ratio (AR) for desirable application needs an in-depth understanding of the synthesis procedure. In this article, the seed-mediated growth of Au NRs with a controlled AR is reported. Influencing reagents, including the seed concentration, are varied individually to unfurl the impact of them on AR. A subsequent optimized protocol is developed to achieve a fine-tuning in the longitudinal surface plasmonic resonance (LSPR) of Au NRs with a narrow distribution of NRs and minimal by-products. The effect of resonance of LSPR peaks closely tallying both 785 and 532 nm with laser excitations are studied for SERS applications using rhodamine 6G (R6G) dye. Furthermore, the molecular resonance of R6G analyte is achieved successfully with a 532 nm excitation laser to accomplish as high of 10−12 M, thanks to the suitable ARs and the surface-enhanced resonance Raman scatterings (SERRS) phenomenon. The enhancement factor is calculated to be 5 × 109, which allows Raman intensity mapping for a trace amount of R6G, demonstrating the potential utility of Au NRs for applications.

Synthesis of Gold Nanorods Using Poly(vinylpyrrolidone) of Different Molecular Weights as an Additive

AbstractThe use of poly(vinylpyrrolidone) (PVP) of different molecular weights (5‐360 kDa) during the synthesis of gold nanorods (AuNRs) via seedless and seed‐mediated approaches is reported. For both syntheses, the LSPR band can be tuned from 700 to 1050 nm by modifying the molecular weight of PVP in a time dependent addition of polymer. Moreover, the growth of AuNRs in 100 mM cetyltrimethylammonium bromide (CTAB) is accelerated as the molecular weight of PVP increases from 5 to 360 kDa for the seedless approach. In the case of AuNRs synthesized by the seed‐mediated approach, the aspect ratio decreases from 7.41 to 3.72 as the molecular weight of PVP increases to 55 kDa. For both protocols, high molecular weight of PVP reduces the shape yield despite of producing smaller AuNRs. Therefore, the incorporation of small amounts of PVP during the growth stage can be utilized for the preparation of anisotropic nanostructures to tune their optical properties and improve their shape yield.

New Aspects of the Gold Nanorod Formation Mechanism via Seed-Mediated Methods Revealed by Molecular Dynamics Simulations.

New aspects of the formation and growth mechanism of gold nanorods (AuNRs) during seed-mediated colloidal synthesis are revealed from the results of molecular dynamics simulation. The model systems consist of cetyltrimethylammonium bromide (CTAB) units adsorbed on low-index [Au(110), Au(100), and Au(111)] and high-index [Au(250)] gold surfaces. The CTAB units are adsorbed as adjacent cylindrical micelles when the relative number of adsorbed bromide ions is small. At later AuNR growth stages, the number of bromide ions increases as the [AuBr2]- species pass through the channels between the adsorbed micelles on the gold surface. Thus, the mature AuNRs have a high concentration of bromide ions at their surface, which appears to change the organization of the CTAB units on the particle surface from adsorbed micelles to a compact CTAB bilayer.

Distinct Bimodal Roles of Aromatic Molecules in Controlling Gold Nanorod Growth for Biosensing

New aromatic molecule–seed particle interactions are examined and exploited to control and guide seed‐mediated gold nanorod (Au NR) growth. This new approach enables better understanding of how small molecules impact the synthesis of metallic nanostructures, catalyzing their use in various biomedical applications, such as plasmonic biosensing. Experimental studies and theoretical molecular simulations using a library of aromatic molecules, making use of the chemical versatility of the molecules with varied spatial arrangements of electron‐donating/withdrawing groups, charge, and Au‐binding propensity, are performed. Au NR growth is regulated by two principal mechanisms, producing either a red or blue shift in the longitudinal localized surface plasmon resonance (LLSPR) peaks. Aromatic molecules with high redox potentials produce an increase in NR aspect ratio and red shift of LLSPR peaks. In contrast, molecules that strongly bind gold surfaces result in blue shifts, demonstrating a strong correlation between their binding energy and blue shifts produced. Through enzymatic conversion of selected molecules, 4‐aminophenylphosphate to 4‐aminophenol, opposing growth mechanisms at opposite extremes of target concentration are obtained, and a chemical pathway for performing plasmonic enzyme‐linked immunosorbent assays is established. This unlocks new strategies for tailoring substrate design and enzymatic mechanisms for controlling plasmonic response to target molecules in biosensing applications.

Experimental and theoretical studies on the role of silver in gold nanorods growth

Gold nanorods (AuNRs) have attracted high attention because of their multifunctions and potential applications in optical, electronic, catalytic and biomedical areas. This study demonstrates a key role of silver (Ag) atoms/clusters, experimentally and theoretically, in the formation and growth of AuNRs. It was found that the addition of silver salt (silver nitrate) can preferably deposit on certain Au crystalline {100} and/or {110} facets to affect the stacking of Au atoms when form and grow to AuNRs in the reported reaction system, resulting in slower atomic stacking on these two {100} and {110} facets but regular growth on the {111} facets. If no use of silver salt(s), gold nanospheres rather than nanorods were obtained in such a reaction system. It was found, by theoretical simulations (molecular dynamic method, MD), that Ag atoms can be oxidized to Ag+ ions by AuCl4 − ions and exist in a short lifetime, which finally diffuses out from the Au crystal structure. The findings would be useful for better understanding the role of Ag in the formation and growth of AuNRs with crystal facet control, which will be beneficial for catalytic and gas sensing applications that often require highly exposed crystalline facets.

Anisotropic Overgrowth of Palladium on Gold Nanorods in the Presence of Salicylic Acid Family Additives

We explored the use of salicylic acid (SA) and its derivatives 5-formylsalicylic acid (FSA) and 5-sulfosalicylic acid (SSA) as organic additives to cetyltrimethylammonium bromide (CTAB) in synthesizing gold nanorods (AuNRs) followed by palladium (Pd) capping at the ends of AuNRs. In the AuNR synthesis step, SA family additives in the presence of low concentration of CTAB (50 mM) serve as both the prereducing agent and the cofactor in nanorod growth. At an optimum additive/CTAB ratio (0.1–0.2), AuNRs grow to the longest length. At low additive concentrations, the gold seeds do not grow. At high concentrations, the longitudinal growth of AuNRs is disrupted because the excessive additive disturbs the ligand structure, leading to more isotropic growth. In the Pd overgrowth step, Pd starts to grow from both ends for AuNRs synthesized at optimum additive/CTAB ratios. Feeding more Pd grows the particles into a core–shell structure, possibly because there lacks a tight ligand layer on Pd that favors the longitudinal growth. For AuNRs synthesized at high additive/CTAB ratios, Pd growth loses preference, showing randomized Pd nucleation on AuNR surface. Finally, the palladium-end-capped–AuNRs’ catalytic activity was tested using the resazurin reduction reaction. This study shows a new way to produce controllable deposition of Pd on AuNRs.

Optimizing Seed Aging for Single Crystal Gold Nanorod Growth: The Critical Role of Gold Nanocluster Crystal Structure

Controlled synthesis of single crystal gold nanorods (Au NRs) with desired dimensions, narrow polydispersity, and minimal byproducts depends critically on the state of the seed solution. Herein, we clarify the growth of cetyltrimethylammonium bromide stabilized Au seeds and their impact on conventional seed-mediated growth of Au NRs. UV–vis spectroscopy, TEM microscopy, and small-angle X-ray scattering reveal that during aging of the seed solution, constituents evolve from solubilized Au-salt precursors (Au[III]) to Au nanoclusters (Aun) to multitwinned Au nanocrystals. The most consistent single crystal Au NR growth, with minimal byproducts, occurs when the seed solution contains the maximum concentration of small (<1 nm) nanoclusters (n < 55, 1 min < tage < 10 min at T = 25 °C). This point can be identified spectroscopically between 300 and 480 nm. Additionally, the optimal clusters coincide approximately with a relative shift in structural equilibrium of closed-shell Au nanoclusters from predominately ...

Signal-Amplified Near-Infrared Ratiometric Electrochemiluminescence Aptasensor Based on Multiple Quenching and Enhancement Effect of Graphene/Gold Nanorods/G-Quadruplex.

Dual-signaling ratiometric electrochemiluminescence (ECL) technology has attracted particular attention in analytical science due to its precise measurement to normalize variation in environmental changes. Creating new mated ECL report units with two emitting states and improving the detection sensitivity are major challenges for ratiometric ECL measurement. Here, we fabricate an ultrasensitive near-infrared ratiometric ECL aptasensor based on a dual-potential signal amplification strategy triggered by the quencher/enhancer [graphene/hemin/gold nanorods/G-quadruplex-hemin (rGO-H-AuNRs-G4H) composite]. The composite was initially prepared through three consecutive steps: the π-π stacking interaction between hemin and graphene, in-site growth of AuNRs, and surface ligand exchange. Dual ECL quenching of quantum dots (QDs) and multiple signal enhancement of luminol can be achieved simultaneously by the fabrication of the sandwich "thrombin aptamer I (TBA1)-TB-TBA2 (rGO-H-AuNRs-G4H)" mode: (i) the formation of three-dimensional G-quadruplex between aptamer and thrombin not only shortens the distance between the donor (QDs) and receptor (rGO-H and AuNRs) to trigger electrochemiluminescence energy transfer but also provides the place for intercalating hemin; (ii) the hemin intercalated into G4 structure and hemin connected onto rGO together with AuNRs/rGO nanomaterials can achieve the multiple peroxidase-like catalysis of H2O2 to greatly enhance the ECL of luminol. The ratiometric ECL aptasensor self-calibrated by the internal reference (luminol or QDs) exhibits ultrasensitive and accurate analytical performance toward thrombin (TB) with a linear detection range from 100 ng/mL to 0.5 pg/mL and a detection limit of 4.2 fg/mL [defined as signal-to-noise ratio (S/N) = 3].

Wet Chemical Synthesis of Soluble Gold Nanogaps

A central challenge in molecular electronics is to create electrode pairs separated by only a few nanometers that can accommodate a single molecule of interest to be optically or electrically characterized while residing in the gap. Current techniques for nanogap fabrication are largely based on top-down approaches and often rely on subsequent deposition of molecules into the nanogap. In such an approach, the molecule may bridge the gap differently with each experiment due to variations at the metal-molecule interface. Conversely, chemists can readily synthesize gold nanorods (AuNRs) in aqueous solution. Through controlled end-to-end assembly of the AuNRs into dimers or chains, facilitated via target molecules, they can be used as electrical contacts. In this way, the preparation of AuNR-molecule-AuNR junctions by wet chemical methods may afford a large number of identical devices with little variation in the interface between molecule and electrode (AuNR). In this Account, we highlight recent progress in using chemically synthesized AuNRs as building blocks for molecular electronic applications. We outline the general synthesis and properties of AuNRs and describe the aqueous growth of dimeric AuNR structures from an insulating molecule linked to AuNR precursors (gold seeds). Conjugated, electronically active molecules are typically not soluble under the conditions required for the bottom-up growth of AuNRs. Therefore, we present a strategy that utilizes host-guest chemistry in order to make such π-systems compatible with the AuNR growth procedure. In order to electrically characterize the AuNR-molecule-AuNR constructs, we must transfer them onto a substrate and contact external electrodes. We discuss the implications of using electron-beam lithography for making this contact. In addition, we introduce a novel fabrication approach in which we can grow AuNR nanogap electrodes in situ on prepatterned substrates, thus circumventing post-processing steps that potentially damage the nanogap environment. Due to the inherent optical properties of AuNRs, electromagnetic field enhancement in the nanogaps lets us spectroscopically characterize the molecules via surface-enhanced Raman scattering. We discuss the incorporation of oligopeptides functionalized with acetylene units having uniquely identifiable vibrational modes. This acetylene moiety allows chemical reactions to be performed in the gaps via click chemistry, and the oligopeptide linking platform opens for integration of larger biological components.

Growth Mechanism of Gold Nanorods

Gold nanorods (Au NRs) are the archetype of a nanoantenna, enabling the directional capture, routing, and concentration of electromagnetic fields at the nanoscale. Solution-based synthesis methods afford advantages relative to top-down fabrication but are challenged by insufficient precision of structure, presence of byproducts, limited tunability of architecture, and device integration. This is due in part to an inadequate understanding of the early stages of Au NR growth. Here, using phase transfer via ligand exchange with mono-thiolated polystyrene, we experimentally demonstrate the complete evolution of seed-mediated Au NR growth in hexadecyltrimethylammonium bromide (CTAB) solution. Au NR size and shape progress from slender spherocylinders at short reaction times to rods with a dumbbell profile, flattened end facets, and octagonal prismatic structures at later stages. These evolve from a single mechanism and reflect the majority of reported Au NR morphologies, albeit reflecting different stages. Add...

The Early Life of Gold Nanorods: Temporal Separation of Anisotropic and Isotropic Growth Modes

Gold nanorods (AuNRs) are a particularly interesting class of nanomaterials because their dimensions and size-dependent optical properties make them ideally suited for many applications. AuNRs are typically synthesized using seeded growth approaches, in which a small spherical gold nanoparticle seed grows anisotropically into a rod-shaped particle. Using AuNRs themselves as seeds for the growth of other anisotropic shapes has been demonstrated but is relatively little-explored. In this study, we show that AuNRs grown using a common method (silver-assisted seeded growth) cannot be used as seeds in the synthesis of higher aspect ratio AuNRs. Instead, the seed AuNRs grow isotropically, providing a new synthetic approach to precisely tune the absolute dimensions of the final AuNRs. We furthermore show that the dimensions of the AuNRs are determined by the reaction conditions at very early times (<10 min), and that perturbing the growth solution beyond these times has little influence on the final AuNR properties. The observation of these behaviors may be relevant to ongoing investigations of AuNR growth mechanisms.

The fate of silver ions in the photochemical synthesis of gold nanorods: an Extended X-ray Absorption Fine Structure Analysis

Water-soluble gold nanorods (Au NRs) were synthesized using a silver-ion mediated photochemical route under UV irradiation. Extended X-ray Absorption Fine Structure (EXAFS) measurements on the Ag K-edge were performed on samples obtained at different Ag/Au ratios and at increasing irradiation times in order to investigate the fate of silver ions during the growth of Au NRs. EXAFS measurements allowed to probe the chemical state and the local environment of silver in the final product. Experimental data suggest that Ag atoms are placed on top of the Au particles as metallic Ag(0), while no significant contribution to the EXAFS spectra comes from AgBr or other Ag(+) based species. The reported results strongly support the deposition of Ag(0) islands on the (110) surfaces of the Au particles, thus driving the anisotropic growth via the (111) surfaces.