Large Gold Nanoparticles Research Articles

Light-enhanced catalytic activity of stable and large gold nanoparticles in homocoupling reactions.

Validating the direct photocatalytic activity of colloidal plasmonic nanoparticles is challenging due to their limited stability and needed support materials that can often contribute to the chemical reactions. Stable gold nanoparticles (AuNPs) with tunable sizes are prepared across porous polymer particles without any chemical bonds where the resulting composite particles exhibit intense surface plasmon resonances (SPRs) in the visible region. These composite particles are then tested as photocatalysts under a broadband solar-simulated light source to examine the contribution degree of photothermal heating and SPR coming from the incorporated AuNPs in the C-C bond forming homocoupling reaction. Generally, the thermal and photothermal heating are the main driving force to increase the reactivity of relatively smaller AuNPs (~ 44 nm in diameter) with a narrower SPR band. However, the SPR-induced catalytic activity is much greater for the composite particles containing larger AuNPs (~ 87 nm in diameter) with a broader SPR. As the polymer particle matrix does not influence the catalytic activity (e.g., inducing charge delocalization and/or separation), the unique SPR role of the colloidal AuNPs in the catalytic reaction is assessable under light irradiation. This study experimentally demonstrates the possibility of evaluating the direct contribution of SPRs to photocatalytic chemical reactions.

Size Segregation of Gold Nanoparticles into Bilayer-like Vesicular Assembly.

Size segregation of nanoparticles with different sizes into highly ordered, unique nanostructures is important for their practical applications. Herein, we demonstrate spontaneous self-assembly of the binary mixtures of small and large gold nanoparticles (GNPs; 5/15, 5/20, or 10/20 in diameter) in the presence of a tetra(ethylene glycol)-terminated octafluoro-4,4'-biphenol ligand, namely, TeOFBL, resulting in a size-segregated assembly. The outer single layer of large GNPs forming a gold nanoparticle vesicle (GNV) encapsulated the inner vesicle-like assembly composed of small GNPs, which is referred to as bilayer-like GNV and similar to the molecular bilayer structure of a liposome. The size segregation was driven by the solvophobic feature of the TeOFBLs on the surface of GNPs. A time-course study indicated that size segregation occurred instantaneously during the mixing stage of the self-organization process. The size-segregated precursors quickly fused with each other through the inner-inner and outer-outer layer fashion to form the bilayer-like GNV. This study provides a new approach to creating biomimetic bilayer capsules with different physical properties for potential applications such as surface-enhanced Raman scattering and drug delivery.

Nanoparticle Deep-Subwavelength Dynamics Empowered by Optical Meron-Antimeron Topology.

Optical meron is a type of nonplanar topological texture mainly observed in surface plasmon polaritons and highly symmetric points of photonic crystals in the reciprocal space. Here, we report Poynting-vector merons formed at the real space of a photonic crystal for a Γ-point illumination. Optical merons can be utilized for subwavelength-resolution manipulation of nanoparticles, resembling a topological Hall effect on electrons via magnetic merons. In particular, staggered merons and antimerons impose strong radiation pressure on large gold nanoparticles (AuNPs), while focused hot spots in antimerons generate dominant optical gradient forces on small AuNPs. Synergistically, differently sized AuNPs in a still environment can be trapped or orbit in opposite directions, mimicking a coupled galaxy system. They can also be separated with a 10 nm precision when applying a flow velocity of >1 mm/s. Our study unravels a novel way to exploit topological textures for optical manipulation with deep-subwavelength precision and switchable topology in a lossless environment.

Time Evolution of Ultrasmall Gold Nanoparticle-Protein Interactions.

To date, much effort has been devoted toward the study of protein corona formation onto large gold nanoparticles (GNPs). However, the protein corona concept breaks down for GNPs in the ultrasmall size regime (<3 nm), and, as a result, our understanding of ultrasmall GNP (usGNP)-protein interactions remains incomplete. Herein, we used anionic usGNPs and six different proteins as model systems to systematically investigate usGNP-protein interactions, with particular focus on the time evolution and long-term behavior of complex formation. The different proteins comprised chymotrypsin (Cht), trypsin (Try), thrombin (Thr), serum albumin (HSA), cytochrome c (Cyt c), and factor XII (FXII). We used a range of biochemical and biophysical methods to estimate binding affinities, determine the effects of usGNPs on protein structure and function, assess the reversibility of any protein structural and functional changes, and evaluate usGNP-protein complex stability. Among the main findings, we observed that prolonged (24 h)─but not short-term (10 min)─interactions between proteins and usGNPs permanently altered protein function, including enzyme activities (Try, Thr, and FXIIa), peroxidase-like activity (Cyt c), and ligand-binding properties (HSA). Remarkably, this occurred without any large-scale loss of the native global conformation, implying time-dependent effects of usGNPs on local protein conformation or dynamics. We also found that both short-(10 min) and long-term (24 h) interactions between proteins and usGNPs yielded short-lived complexes, i.e., there was no time-dependent "hardening" of the interactions at the binding interface as usually seen with large GNPs. The present study increases our fundamental understanding of nano-bio interactions in the ultrasmall size regime, which may assist the safe and effective translation of usGNPs into the clinic.

Ultrasensitive colorimetric detection of tetracyclines based on in-situ growth of gold nanoflowers.

A colorimetric method based on in-situ generation of gold nanoflowers for the detection of tetracyclines (TCs) was proposed. We found that gold nanoflowers could be formed in the HAuCl4-NH2OH redox reaction directly without the addition of small-sized gold nanoparticles (Au NPs) as seeds when an alkaline borax buffer solution was employed as the reaction medium. Interestingly, the shape and size of the generated gold nanoflowers were regulated with TC. Briefly, large flower-like gold nanoparticles were formed with a low concentration of TC while small spherical gold nanoparticles were generated with a high concentration of TC. The generated gold nanoflowers exhibited different surface plasmon absorption (SPR) properties. Thus, a simple and rapid colorimetric method was established for the detection of TC antibiotics. This method exhibited high sensitivity for the detection of TC, oxytetracycline (OTC), and doxycycline (DC) with detection limits of 2.23nM, 1.19nM, and 5.81nM, respectively. The proposed colorimetric method was applied to the determination of TC in both milk samples and water samples.

Highly Excretable Gold Supraclusters for Translatable In Vivo Raman Imaging of Tumors.

Raman spectroscopy provides excellent specificity for in vivo preclinical imaging through a readout of fingerprint-like spectra. To achieve sufficient sensitivity for in vivo Raman imaging, metallic gold nanoparticles larger than 10 nm were employed to amplify Raman signals via surface-enhanced Raman scattering (SERS). However, the inability to excrete such large gold nanoparticles has restricted the translation of Raman imaging. Here we present Raman-active metallic gold supraclusters that are biodegradable and excretable as nanoclusters. Although the small size of the gold nanocluster building blocks compromises the electromagnetic field enhancement effect, the supraclusters exhibit bright and prominent Raman scattering comparable to that of large gold nanoparticle-based SERS nanotags due to high loading of NIR-resonant Raman dyes and much suppressed fluorescence background by metallic supraclusters. The bright Raman scattering of the supraclusters was pH-responsive, and we successfully performed in vivo Raman imaging of acidic tumors in mice. Furthermore, in contrast to large gold nanoparticles that remain in the liver and spleen over 4 months, the supraclusters dissociated into small nanoclusters, and 73% of the administered dose to mice was excreted during the same period. The highly excretable Raman supraclusters demonstrated here offer great potential for clinical applications of in vivo Raman imaging.

Monte Carlo model for evaluation of concentration of gold nanoparticle clusters as predictor of effective dose in proton therapy of microscopic tumors

Radio-sensitization with gold nanoparticles (GNPs) is a relatively recent advancement of radiotherapy that is determined to increase radiation in the target tumor region. Monte Carlo (MC) simulation is a well-known method that has gained popularity by assisting in determining the effective dose in various tumors. Assessing the concentration of particles during proton therapy can provide the key to evaluating the efficiency of the performed treatment. Therefore, this study aimed to investigate the interconnection between the concentration of gold nanoparticle clusters and the dose enhancement in microscopic tumors by using the MC Model. A single cell tumor model with a size of 5 μm that was exposed to 100 MeV protons in a region resembling the human brain was investigated by using an MC simulation employing the Geant4 toolkit. With each nanoparticle having a diameter of 15 nm, a three-dimensional model of the random distribution of gold nanoparticle clusters was developed. Then, the dose enhancement for various concentrations of the GNPs accumulated around the tumor was estimated according to the dose enhancement factor (DEF), while the dose was concentrated on the surface of each GNP in the clusters. The results showed that the dose enhancement located at the Bragg-peak in the tumor region depended on the different concentrations of the GNPs. DEF values were found to be 1.016, 1.022, 1.026, 1.035, 1.013, 1.000, and 0.984 for the 1, 2, 3, 5, 10, 30, and 50 mg/ml concentration levels in water, respectively. The findings also revealed that large GNP clusters with high concentration levels yield larger DEFs than clusters with lower concentration levels, which may have an impact on radiation therapy. Specifically, at a concentration higher than 10 mg/ml, the estimated dose was significantly lower than those for a concentration of 5 mg/ml by about ∼100 mGy. As the benefit of the increased total dose must be balanced against the effect of the accumulation of nanoparticles, the current study detected dose reduction in regions that accumulate GNPs at high concentrations. As a result, the potential efficiency of the radiotherapeutic treatment can be reduced.

Encapsulation of gold nanoclusters by photo-initiated miniemulsion polymerization

Gold nanoclusters (AuNC) with a precise number of Au atoms feature unique properties for imaging applications, including size dependent photoluminescence, very high photostability, and large Stokes shift. However, their low colloidal stability often leads to aggregation and fusion into larger gold nanoparticles (AuNPs), hindering the wider use of AuNC. Here, we report the first successful encapsulation of NIR emitting AuNC in polymer nanoparticles (PNPs). The AuNC, with 25 gold atoms and stabilized by 6-mercaptohexanoic acid (MHA), were encapsulated in PNPs with ca. 50 nm in diameter, obtained by miniemulsion polymerization of butyl methacrylate (BMA) and varying amounts of methyl methacrylate (MMA). While thermo-initiation led to aggregation of AuNC into plasmonic (non-emissive) AuNPs, the use of photo-initiation effectively preserved the AuNC inside the PNPs. By encapsulating a large number of AuNC, we obtained PNPs with high brightness in the NIR, both by one- and two-photons excitation.

Ultrasensitive detection of SARS-CoV-2 nucleocapsid protein using large gold nanoparticle-enhanced surface plasmon resonance

The COVID-19 pandemic has created urgent demand for rapid detection of the SARS-CoV-2 coronavirus. Herein, we report highly sensitive detection of SARS-CoV-2 nucleocapsid protein (N protein) using nanoparticle-enhanced surface plasmon resonance (SPR) techniques. A crucial plasmonic role in significantly enhancing the limit of detection (LOD) is revealed for exceptionally large gold nanoparticles (AuNPs) with diameters of hundreds of nm. SPR enhanced by these large nanoparticles lowered the LOD of SARS-CoV-2 N protein to 85 fM, resulting in the highest SPR detection sensitivity ever obtained for SARS-CoV-2 N protein.

Synthesis of large and stable colloidal gold nanoparticles (AuNPs) by seeding-growth method

Colloidal gold nanoparticles (AuNPs) have been used in various applications, mainly in biomedical sciences for therapeutic and diagnostic purposes. These AuNPs can be conjugated with biomolecules and chemical substances due to their unique physical and chemical properties. The AuNPs are usually synthesized by a chemical method; namely Turkevich method or reduction method. However, this synthesis method is not suitable for synthesis of large AuNPs due to aggregation and instability of AuNPs suspension. Thus, the aim for this study is to evaluate the seeding-growth method for synthesis of large AuNPs. The seed of 15 nm AuNPs was initially produced using the citrate reduction method, then further grown to 40, 60, and 80 nm AuNPs using the mild reduction agent, hydroxylamine. Transmission electron microscopy (TEM), dynamic light scattering (DLS), and UV–vis- NIR spectroscopy were used to characterize the as-synthesized AuNPs. The narrow particle size distribution and low polydispersity index value (PDI) for all AuNPs revealed the presence of monodisperse AuNPs. The as-synthesized AuNPs are nearly spherical as shown by the degree of ellipticity (G) close to 1.00. This result showed no agglomeration of AuNPs in the colloidal suspension. The UV–vis-NIR spectra showed peaks shifted to a longer wavelength that confirmed increasing size of AuNPs. The synthesis of different sizes of AuNPs using the seeding-growth method was successful and stable with no aggregation and agglomeration.

A CRISPR-Cas12a integrated SERS nanoplatform with chimeric DNA/RNA hairpin guide for ultrasensitive nucleic acid detection.

Background: CRISPR-Cas12a has been integrated with nanomaterial-based optical techniques, such as surface-enhanced Raman scattering (SERS), to formulate a powerful amplification-free nucleic acid detection system. However, nanomaterials impose steric hindrance to limit the accessibility of CRISPR-Cas12a to the narrow gaps (SERS hot spots) among nanoparticles (NPs) for producing a significant change in signals after nucleic acid detection.Methods: To overcome this restriction, we specifically design chimeric DNA/RNA hairpins (displacers) that can be destabilized by activated CRISPR-Cas12a in the presence of target DNA, liberating excessive RNA that can disintegrate a core-satellite nanocluster via toehold-mediated strand displacement for orchestrating a promising “on-off” nucleic acid biosensor. The core-satellite nanocluster comprises a large gold nanoparticle (AuNP) core surrounded by small AuNPs with Raman tags via DNA hybridization as an ultrabright Raman reporter, and its disassembly leads to a drastic decrease of SERS intensity as signal readouts. We further introduce a magnetic core to the large AuNPs that can facilitate their separation from the disassembled nanostructures to suppress the background for improving detection sensitivity.Results: As a proof-of-concept study, our findings showed that the application of displacers was more effective in decreasing the SERS intensity of the system and attained a better limit of detection (LOD, 10 aM) than that by directly using activated CRISPR-Cas12a, with high selectivity and stability for nucleic acid detection. Introducing magnetic-responsive functionality to our system further improves the LOD to 1 aM.Conclusion: Our work not only offers a platform to sensitively and selectively probe nucleic acids without pre-amplification but also provides new insights into the design of the CRISPR-Cas12a/SERS integrated system to resolve the steric hindrance of nanomaterials for constructing biosensors.

Gold Nanoclusters: Imaging, Therapy, and Theranostic Roles in Biomedical Applications.

For the past two decades, atomic gold nanoclusters (AuNCs, ultrasmall clusters of several to 100 gold atoms, having a total diameter of <2 nm) have emerged as promising agents in the diagnosis and treatment of cancer. Owing to their small size, significant quantization occurs to their conduction band, which leads to emergent photonic properties and the disappearance of the plasmonic responses observed in larger gold nanoparticles. For example, AuNCs exhibit native luminescent properties, which have been well-explored in the literature. Using proteins, peptides, or other biomolecules as structural scaffolds or capping ligands, required for the stabilization of AuNCs, improves their biocompatibility, while retaining their distinct optical properties. This paved the way for the use of AuNCs in fluorescent bioimaging, which later developed into multimodal imaging combined with computer tomography and magnetic resonance imaging as examples. The development of AuNC-based systems for diagnostic applications in cancer treatment was then made possible by employing active or passive tumor targeting strategies. Finally, the potential therapeutic applications of AuNCs are extensive, having been used as light-activated and radiotherapy agents, as well as nanocarriers for chemotherapeutic drugs, which can be bound to the capping ligand or directly to the AuNCs via different mechanisms. In this review, we present an overview of the diverse biomedical applications of AuNCs in terms of cancer imaging, therapy, and combinations thereof, as well as highlighting some additional applications relevant to biomedical research.

TiO2/Au/TiO2 plasmonic photocatalyst with enhanced photocatalytic activity and stability under visible-light irradiation

Plasmonic photocatalysis, i.e., photocatalysis with activity under visible-light (vis) irradiation due to plasmonic feature of noble metals (NMs), has been intensively studied as promising method for solar energy conversion. Although various plasmonic photocatalysts have already been investigated, the vis activity is usually low, and thus should be improved for commercial application. Moreover, considering charge carriers’ mechanism, the stability of NMs during long-term irradiation should be also considered. Accordingly, this study has focused on the improvement of photocatalytic activity and stability of gold-modified titania photocatalysts under vis irradiation. Among a few proposed synthesis procedures, modified photodeposition method has resulted in the formation of TiO2/Au/TiO2 composites with high level of photoactivity. Large gold nanoparticles (NPs), formed on large rutile titania particles, are partially covered with fine anatase titania NPs, and thus the interface between titania and gold has been enlarged. Moreover, partial coverage of gold by fine titania NPs hinders gold aggregation, resulting in improved stability of these samples. Action spectrum of 2-propanol oxidation and numerical 3D-FDTD simulations of field distribution have indicated that the enhanced utilization of incident photons is responsible for high activity of TiO2/Au/TiO2 photocatalysts.

Effects of Gold Nanoparticles on the Stepping Trajectories of Kinesin.

A substantial increase in the temporal resolution of the stepping of dimeric molecular motors is possible by tracking the position of a large gold nanoparticle (GNP) attached to a labeled site on one of the heads. This technique was employed to measure the stepping trajectories of conventional kinesin (Kin1) using the time-dependent position of the GNP as a proxy. The trajectories revealed that the detached head always passes to the right of the head that is tightly bound to the microtubule (MT) during a step. In interpreting the results of such experiments, it is assumed that the GNP does not significantly alter the diffusive motion of the detached head. We used coarse-grained simulations of a system consisting of the MT-Kin1 complex with and without attached GNP to investigate how the stepping trajectories are affected. The two significant findings are: (1) The GNP does not faithfully track the position of the stepping head, and (2) the rightward bias is typically exaggerated by the GNP. Both these findings depend on the precise residue position to which the GNP is attached. Surprisingly, the stepping trajectories of kinesin are not significantly affected if, in addition to the GNP, a 1 μm diameter cargo is attached to the coiled coil. Our simulations suggest the effects of the large probe have to be considered when inferring the stepping mechanisms using GNP tracking experiments.

A Study on the Splitting of Large Gold Nanoparticles by Addition of Aqueous Ascorbic Acid

Control of the size and shape of nanoparticles significantly impacts the ability to control their physical and chemical properties. In this paper, we introduce a technique to split large nanoparticles into smaller ones. After the addition of ascorbic acid (AA), 50 nm-sized gold (Au) nanoparticles in the form of polycrystals were split into nanoparticles with sizes of 10 nm. We believe that AA plays a critical role in breaking down the Au particles. Additionally, this technique can be used to synthesize small AuPt bimetallic nanoparticles with a small amount of Pt on their surface showing that this reaction could help in the formation of a variety of small Au-based bimetallic nanoparticles.

Comparison of Single- and Mixed-Sized Gold Nanoparticles on Lateral Flow Assay for Albumin Detection.

The sensitivity and reproducibility of the lateral flow assay can be influenced by multiple factors, such as the size of gold nanoparticles (GNPs) employed. Here, we evaluated the analytical performance of single-sized and mixed-sized GNPs using a simple lateral flow assay (LFA) platform. This platform was used as a model assay to diagnose albumin levels and demonstrate the analytical performance of single-sized and mixed-sized GNPs in LFA tests. Two sizes of GNPs@anti-bovine serum albumin (BSA) conjugate proteins were mixed at different ratios. The unique optical properties of the GNPs induced a distinguishing color-shedding effect on the single- and mixed-sized GNPs@anti-BSA conjugates interacting with the target analyte BSA spotted on the test line. The use of mixed-sized GNPs@anti-BSA conjugates enhanced signal relative to the 20 nm GNPs, and provided superior stability compared with solely employing the large GNPs (50 nm). The proposed platform in this study could provide an efficient BSA detection mechanism that can be utilized as a model biomarker for confronting chronic kidney disease.

Single‐Atom Catalysis: Sustainable Synthesis of Bimetallic Single Atom Gold‐Based Catalysts with Enhanced Durability in Acetylene Hydrochlorination (Small 16/2021)

In article number 2004599, Javier Pérez-Ramírez and co-workers demonstrate that platinum chloride in aqueous solution promotes the dispersion of large gold nanoparticles on carbon carriers into single atoms, forming bimetallic single-atom catalysts with improved resistance against sintering at high temperatures and under the harsh reductive reaction conditions of vinyl chloride production via acetylene hydrochlorination.

One Pot Synthesis of Large Gold Nanoparticles with Triple Functional Ferrocene Ligands.

In biomedical, toxicological, and optoelectronic applications, the size of nanoparticles is one of the decisive factors. Therefore, synthesis of nanoparticles with controlled sizes is required. The current methods for synthesis of larger gold nanoparticles (GNPs, ~200 nm) are complex and tedious, producing nanoparticles with a lower yield and more irregular shapes. Using ferrocene as a primary reducing agent and stabilizer, sodium citrate as a dispersant, and sodium borohydride as an accessory reducing agent, GNPs of 200 nm were synthesized in a one pot reaction. Besides the roles of reducing agent and GNP stabilizer, ferrocene also served a role of quantitative marker for ligand loading, allowing an accurate determinate of surface ligands.

The Interplay of Ligand Properties and Core Size Dictates the Hydrophobicity of Monolayer-Protected Gold Nanoparticles.

The hydrophobicity of monolayer-protected gold nanoparticles is a crucial design parameter that influences self-assembly, preferential binding to proteins and membranes, and other nano-bio interactions. Predicting the effects of monolayer components on nanoparticle hydrophobicity is challenging due to the nonadditive, cooperative perturbations to interfacial water structure that dictate hydrophobicity at the nanoscale. In this work, we quantify nanoparticle hydrophobicity by using atomistic molecular dynamics simulations to calculate local hydration free energies at the nanoparticle-water interface. The simulations reveal that the hydrophobicity of large gold nanoparticles is determined primarily by ligand end group chemistry, as expected. However, for small gold nanoparticles, long alkanethiol ligands interact to form anisotropic bundles that lead to substantial spatial variations in hydrophobicity even for homogeneous monolayer compositions. We further show that nanoparticle hydrophobicity is modulated by changing the ligand structure, ligand chemistry, and gold core size, emphasizing that single-ligand properties alone are insufficient to characterize hydrophobicity. Finally, we illustrate that hydration free energy measurements correlate with the preferential binding of propane as a representative hydrophobic probe molecule. Together, these results show that both physical and chemical properties influence the hydrophobicity of small nanoparticles and must be considered together when predicting gold nanoparticle interactions with biomolecules.

Generalized non-integer Lennard-Jones potential function vs. generalized Morse potential function for calculating cohesive energy and melting point of nanoparticles

A generalized non-integer Lennard-Jones (L-J) potential function with an additional parameter m is proposed to calculate the cohesive energy and melting point of nanoparticles. The model based on the new generalized non-integer L-J potential function has been successful in predicting experimental values. The calculated cohesive energies show an excellent agreement with the experimental values of the cohesive energies of molybdenum (Mo) and tungsten (W) nanoparticles (Kim et al., 2002). Moreover, the calculated melting points based on the generalized non-integer L-J potential function agree with the experimental values for large gold (Au) nanoparticles including n≥1000 atoms (Buffat and Borel, 1976) and small silica-encapsulated gold (Au) nanoparticles including n≤1500 atoms (Dick et al., 2002). The stability of nanoparticles is due to two conditions: the increase of the range of the attractive force and the high gradient attractive interaction in the potential function when rij≈r0.