Gold Nanoplates Research Articles

Laser-Induced Stress-Driven Nanoplate Jumping Visualized by Ultrafast Electron Microscopy.

Understanding laser-induced jumping has attracted great interest in nanomaterial launching and transfer but requires a high spatiotemporal resolution visualization. Here, we report a jumping dynamics of nanoplate driven by ultrafast laser-induced stress using time-resolved transmission electron microscopy. Single-shot imaging reveals a nondestructive launching of gold nanoplates in several nanoseconds after the pulsed femtosecond laser excitation. The temperature rise and acoustic vibration, derived from ultrafast electron crystallography with a picosecond time resolution, confirm the existence of a laser-induced elastic stress wave. The generation, propagation, and reflection of thermal stress waves are further clarified by atomic simulation. The nonequilibrium ultrafast laser heating produces a compressive stress wave within several picoseconds, constrained by the supporting substrate under nanoplate to provide thrust force. This compressive stress is subsequently reflected into tensile stress by the substrate, promoting the nanoplate to jump off the substrate. Furthermore, the uneven interface adhesion results in the jumping flip of nanoplates, as well as, diminished their jumping speed. This study unveils the jumping regime driven by impulsive laser-excited stress and offers understanding of light-matter interaction.

Amine oxide surfactant-mediated synthesis of plate-based gold nanocrystals with tunable surface wrinkles and their applications in the ethylene glycol oxidation reaction

Gold nanoplates with tunable surface wrinkles are prepared using an amine oxide surfactant, showing improved EGOR activity due to enriched uncoordinated active sites.

Role of Plasmonic Antenna in Hot Carrier-Driven Reactions on Bimetallic Nanostructures.

Noble metal nanostructures can efficiently harvest electromagnetic radiation, which, in turn, is used to generate localized surface plasmon resonances. Surface plasmons decay, producing hot carriers, that is, short-lived species that can trigger chemical reactions on metallic surfaces. However, noble metal nanostructures catalyze only a very small number of chemical reactions. This limitation can be overcome by coupling such nanostructures with catalytic-active metals. Although the role of such catalytically active metals in plasmon-driven catalysis is well-understood, the mechanistics of a noble metal antenna in such chemistry remains unclear. In this study, we utilize tip-enhanced Raman spectroscopy, an innovative nanoscale imaging technique, to investigate the rates and yields of plasmon-driven reactions on mono- and bimetallic gold- and silver-based nanostructures. We found that silver nanoplates (AgNPs) demonstrate a significantly higher yield of 4-nitrobenzenehtiol to p,p'-dimercaptoazobisbenzene (DMAB) reduction than gold nanoplates (AuNPs). We also observed substantially greater yields of DMAB on silver-platinum and silver-palladium nanoplates (Ag@PtNPs and Ag@PdNPs) compared to their gold analogues, Au@PtNPs and Au@PdNPs. Furthermore, Ag@PtNPs exhibited enhanced reactivity in 4-mercatophenylmethanol to 4-mercaptobenzoic acid oxidation compared to Au@PtNPs. These results showed that silver-based bimetallic nanostructures feature much greater reactivity compared to their gold-based analogues.

Colorimetric and visual sensing of ferrous ion by Fenton reaction-stimulated etching of triangular gold nanoplates

In this study, a method for ultrasensitive sensing of Fe2+ based on Fenton reaction mediated etching of triangular gold nanoplates (Au NPLs) was developed. In this assay, the etching of Au NPLs by H2O2 was accelerated in the presence of Fe2+ due to the generation of superoxide free radical (O2·-) via Fenton reaction. With the concentration of Fe2+ increased, the shape of Au NPLs changed from triangular to sphere with the blue shifted localized surface plasmon resonance, accompanying a series of consecutive color changes from blue, bluish purple, purple, reddish purple and finally to pink. The rich color variations enable rapid visual quantitative determination of Fe2+ within 10 min. A good linear relationship between the peak shifts and the concentration of Fe2+ was obtained in the range of 0.035 to 1.5 μM (R2 = 0.996). Favorable sensitivity and selectivity in the presence of other tested metal ions were achieved in the proposed colorimetric assay. The detection limits (3ơ/k) for Fe2+ was 26 nM by UV–vis spectroscopy, and the clearly discernible concentration of Fe2+ was as low as 0.07 μM by naked eyes. The recoveries of fortified samples in pond water and serum samples ranged from 96% to 106% with interday relative standard deviations <3.6% in all cases, demonstrating the applicability of the assay for measuring Fe2+ in real samples.

Compressible viscoelasticity of cell membranes determined by gigahertz-frequency acoustic vibrations

Membrane viscosity is an important property of cell biology, which determines cellular function, development and disease progression. Various experimental and computational methods have been developed to investigate the mechanics of cells. However, there have been no experimental measurements of the membrane viscosity at high-frequencies in live cells. High frequency measurements are important because they can probe viscoelastic effects. Here, we investigate the membrane viscosity at gigahertz-frequencies through the damping of the acoustic vibrations of gold nanoplates. The experiments are modeled using a continuum mechanics theory which reveals that the membranes display viscoelasticity, with an estimated relaxation time of ca. 5.7+2.4/−2.7 ps. We further demonstrate that membrane viscoelasticity can be used to differentiate a cancerous cell line (the human glioblastoma cells LN-18) from a normal cell line (the mouse brain microvascular endothelial cells bEnd.3). The viscosity of cancerous cells LN-18 is lower than that of healthy cells bEnd.3 by a factor of three. The results indicate promising applications of characterizing membrane viscoelasticity at gigahertz-frequency in cell diagnosis.

Abstract 994: Chiroptical detection and mutation analysis of cancer-associated extracellular vesicles in microfluidic devices with oriented chiral nanoparticles

Abstract Small extracellular vesicles, often termed as “exosomes” carry informative cargo containing proteins and lipids, reflective of their cellular origin. Thus, they are promising biomarkers for early diagnosis of cancer. However, conventional profiling methods like quantitative polymerase chain reaction (qPCR) require complex procedures, thereby limiting the analytical sensitivity of exosomes for liquid biopsies. Here, we demonstrate a sensitive microfluidic device (CDEXO) that isolates and profiles cancer-associated exosomes directly from blood plasma using assembled chiral gold nanoparticles (AuNPs). The unique changes in chiral signals are associated with specific biomolecules on the exosomes’ membranes. Thus, we can distinguish exosomes of lung cancer patients from those of healthy individuals and detect mutated EGFR proteins on the membrane. Hence, this low-cost microfluidic device is an attractive technique for rapid, sensitive, and versatile profiling of various extracellular vesicles. Methods: The top layer of CDEXO devices were fabricated by soft lithography using polydimethylsiloxane (PDMS). The bottom glass slide was functionalized with a layer-by-layer assembly of cationic poly(dimethyl diallyl ammonium chloride) and anionic polystyrene sulfonate. AuNPs were prepared by adding gold nanoplates to a growth solution. Next, AuNPs were conjugated with biotinylated Annexin-V, using Neutravidin-biotin chemistry. Exosomes were harvested from lung cancer cell lines (A549, H1650, H3255) and lung fibroblasts (MRC5) and spiked into the CDEXO chip. EDTA was used to release the captured exosomes and quantified using nanoparticle tracking analysis (NTA). CD spectra were measured by spectrometry. Imaging of AuNPs and exosomes were done using scanning electron microscope (SEM). Results: CDEXO captures cancer-associated exosomes with an efficiency of 81.1±1.5%. H3255 derived exosomes that exhibited EGFR point mutation showed the greatest change in spectral signals from the baseline, followed by A549 (wild type), H1650, (EGFR exon19 deletion) and MRC5 (healthy). The CD responses were measurable at exosome numbers as low as 100. Further validation with 19 lung cancer patients showed an average 40% change in chiral signals from isolated exosomes that were 5.6 times higher in patients than healthy donors. Conclusions: A microfluidic device with chiral AuNPs allows sensitive and accurate detection of lung cancer-associated exosomes by conjugation with Annexin V. The resulting strong CD peaks that arise from specific interactions between exosomal surface proteins and chiral AuNPs facilitate in-depth profiling of target exosomes, including EGFR mutation expression. Citation Format: Yoon-Tae Kang, Ji-Young Kim, Emine Sumeyra Turali-Emre, Hee-Jeong Jang, Minjeong Cha, Abha Kumari, Colin Palacios-Rolston, Chitra Subramanian, Emma Purcell, Sarah Owen, Chung-Man Lim, Rishindra Reddy, Shruthi Jolly, Nithya Ramnath, Nicholas A. Kotov, Sunitha Nagrath. Chiroptical detection and mutation analysis of cancer-associated extracellular vesicles in microfluidic devices with oriented chiral nanoparticles [abstract]. In: Proceedings of the American Association for Cancer Research Annual Meeting 2023; Part 1 (Regular and Invited Abstracts); 2023 Apr 14-19; Orlando, FL. Philadelphia (PA): AACR; Cancer Res 2023;83(7_Suppl):Abstract nr 994.

32‐Symmetric Chiral Gold Nanoplates with Near‐Infrared Circular Dichroism

AbstractPlasmonic chiral nanostructures provide a novel route for extraordinary optical properties, such as light polarization control and enhancing chiroptical signals of molecules. The symmetry of chiral nanostructures, such as helices, gyroids, and irregular tetrahedrons, is strongly correlated to chiroptical responses; therefore, it is an important design parameter. In a previous study, a synthetic strategy is demonstrated for 432‐symmetric chiral gold nanoparticles by breaking the mirror symmetry of a 4/m 2/m‐symmetric crystal structure on a high‐index surface. Herein, the aim is to extend the chiral symmetry of gold nanoparticles and their chiroptical responses. The symmetry of gold nanoparticles can be modulated by inducing single or multiple twin planes in seed nanoparticles. The 32‐symmetric chiral gold nanoplates, referred to as 32 helicoids, are successfully synthesized using 3 2/m‐symmetric triangular and hexagonal plates. The growth mechanism of the 32 helicoids, which results in two different characteristic morphologies, is analyzed. The 32 helicoids are significantly important owing to their optical activity over a wide range from the visible to the near‐infrared region. This investigation provides an insight that symmetry control of the nanomorphology can represent an important research direction in chiral plasmonic applications.

Mode specific dynamics for the acoustic vibrations of a gold nanoplate

The vibrational modes of semiconductor and metal nanostructures occur in the MHz to GHz frequency range, depending on dimensions. These modes are at the heart of nano-optomechanical devices, and understanding how they dissipate energy is important for applications of the devices. In this paper ultrafast transient absorption microscopy has been used to examine the breathing modes of a single gold nanoplate, where up to four overtones were observed. Analysis of the frequencies and amplitudes of the modes using a simple continuum mechanics model shows that the system behaves as a free plate, even though it is deposited onto a surface with no special preparation. The overtones decay faster than the fundamental mode, which is not predicted by continuum mechanics calculations of mode damping due to radiation of sound waves. Possible reasons for this effect include frequency dependent thermoelastic effects in the nanoplate, and/or flow of acoustic energy out of the excitation region.

Tip-Enhanced Raman Chemical and Chemical Reaction Imaging in H2O with Sub-3-nm Spatial Resolution

Reproducible chemical and chemical reaction nanoimaging at solid-liquid interfaces remains challenging, particularly when resolutions on the order of a few nanometers are sought. In this work, we demonstrate the latter through liquid-tip-enhanced Raman (TER) measurements that target gold nanoplates functionalized with 4-mercaptobenzonitrile (MBN). In addition to chemical imaging and local optical field nanovisualization with high spatial resolution, we observe the signatures of 4-mercaptobenzoic acid, which forms as a result of plasmon-induced hydrolysis of MBN. Evidently, the solvent leads to distinct plasmon-induced/enhanced chemical reaction pathways that have not been documented. This work shows that such reactions that take place at solid-liquid interfaces can be tracked with a record sub-3-nm spatial resolution via TER spectral nanoimaging in liquids.

Amyloid fibrils with charge transportation facilitating the green synthesis of single-crystalline gold nanoplates for catalytic application

Peptide assemblies as the significant units in biological system play the key role in various activities i.e., charge transportation and metal ion reduction, which is rarely clarified with detailed mechanism. Herein, we determined the band gap of hIAPP20-29 to be about 2.5 eV by theoretical simulations, and peptides could self-assemble into amyloid fibrils. Further experiments confirmed the charge transport along the surface of amyloid fibril by setting electrical device. All the electroactive features of peptides combined with its capability of binding gold precursor and transferring electron to gold precursor would facilitate the reduction of gold ions to single-crystalline gold nanoplates. The obtained gold nanoplate-fibrils (Au-fibrils) hybrids were employed as catalysts in the reduction of 4-nitrophenol with good performances. We envision that amyloid fibrils with charge transportation inspired from the bio-system could be applied to manufacture peptide-metal nanomaterials in a green and precise manner for further catalytic applications.

Seed-Mediated Synthesis of Thin Gold Nanoplates with Tunable Edge Lengths and Optical Properties

Thin Au nanoplates show intriguing localized surface plasmon resonance (LSPR) properties with potential applications in various fields. The conventional synthesis of Au nanoplates usually involves the formation of spherical nanoparticles or produces nanoplates with large thicknesses. Herein, we demonstrate a synthesis of uniform thin Au nanoplates by using Au-Ag alloy nanoframes obtained by the galvanic replacement of Ag nanoplates with HAuCl4 as the seeds and a sulfite (SO32-) as a ligand. The SO32- ligand not only complexes with the Au salt for the controlled reduction kinetics but also strongly adsorbs on Au {111} facets for effectively constraining the crystal growth on both basal sides of the Au nanoplates for controlled shape and reduced thicknesses. This seed-mediated synthesis affords Au nanoplates with a thickness of only 7.5 nm, although the thickness increases with the edge length. The edge length can be customizable in a range of 48-167 nm, leading to tunable LSPR bands in the range of 600-1000 nm. These thin Au nanoplates are applicable not only to surface-enhanced Raman spectroscopy with enhanced sensitivity and reliability but also to a broader range of LSPR-based applications.

Improving the efficiency of the concentrating solar power plants using heat transfer nanofluids with gold nanoplates: An analysis from laboratory to industrial scale

We report about the remarkable changes in the thermophysical properties of the heat transfer fluid used in concentrating solar power plants with parabolic-trough collectors (Dowtherm A, a mixture of diphenyl oxide and biphenyl) by addition of Au nanoplates in mass fractions around 10−2 wt%. The resulting nanofluids are stable for weeks, and their enhanced physical properties make them good candidates for the application. Particularly, with 4.8·10−2 wt% of Au nanoplates, specific heat increases by 12.0 ± 1.2 % at 523 K and thermal conductivity increases by 24.9 ± 6.1 % at 373 K, with no measurable changes in density or dynamic viscosity. This set of physical properties allows to make a realistic estimation of the performance of a prototypical concentrating solar power plant using these nanofluids for solar-to-thermal energy conversion. We determine, using computational cost-free numerical models available in literature, that the performance of a concentrating solar power plant could increase up to 35.1 %, compared to the predicted 24.7 % with the conventional heat transfer fluid, with neither rheological penalties nor economically prohibitive structural changes. The findings here reported may contribute to encourage the application of heat transfer nanofluids in order to improve the efficiency of concentrating solar power plants, and to consolidate a working scheme that positively promotes the transition from laboratory scale to industrial scale.

Tip-enhanced Raman imaging of plasmon-driven dimerization of 4-bromothiophenol on nickel-decorated gold nanoplate bimetallic nanostructures.

We used tip-enhanced Raman spectroscopy (TERS) to examine plasmon-driven dimerization of 4-bromothiophenol (4-BTP) into thiophenol (TP) and 4,4'-biphenyldithiol (4,4'-BPDT) on Au and Ni@AuNPs. TERS revealed that cross-coupling of these molecular reactants into 4,4'-BPDT occurred primarily on Ni nano islands rather than the surrounding Au on the surface of Ni@AuNPs.

Substrate-Free Fabrication of Single-Crystal Two-Dimensional Gold Nanoplates for Catalytic Application.

Two-dimensional (2D) gold nanoplates (AuNPLs) have shown potential in catalysis, photonics, electronics, sensing, and biomedicine fields due to their high aspect ratio, fascinating surface chemistry, and quantum-size effect. Therefore, the synthesis of substrate-free, size-controlled single-crystal gold (Au) nanoplates is highly desirable for the development of catalysis and optical near-field enhancement applications. EDTA and hydroxide anions were used in this study to stimulate the formation of microscale single-crystal gold nanoplates under hydrothermal conditions. The reaction temperature, amount of EDTA, and hydroxyl anions all have a significant effect on the morphologies and size distributions of the gold nanoplates. The gold nanoplates had an average side length of between 3 and 11 μm. The application of the microscale single-crystal gold nanoplates as a nanocatalyst proved their excellent catalytic activity and recyclability for the catalysis of 4-nitrophenol to 4-aminophenol, implying that the large-size gold nanoplates were promising in heterogeneous catalysis applications.

Multipolar Raman Scattering vs Interfacial Nanochemistry: Case of 4-Mercaptopyridine on Gold.

Caution needs to be exercised in associating changes in plasmon-enhanced Raman spectra with chemical transformations. This is demonstrated through a detailed analysis of tip-enhanced Raman (TER) scattering from 4-mercaptopyridine (MPY) on gold. The substrate used consists of gold nanoplates atop a gold surface featuring heterogeneous grooves, all coated with a monolayer of MPY. The brightest spectra across the substrate exhibit features that can only be recovered by considering the generalized polarizability of oriented MPY molecules. The complex TER spectra we observe do not mark interfacial chemistry but rather multipolar TER scattering driven by local field gradients.

Can Light Alter the Yield of Plasmon-Driven Reactions on Gold and Gold-Palladium Nanoplates?

Noble-metal nanostructures, as well as their bimetallic analogues, catalyze a broad spectrum of plasmon-driven reactions. Catalytic properties of such nanostructures arise from light-generated surface plasmon resonances that decay forming transient hot electrons and holes. Hot carriers with "slower" dissipation rates accumulate on nanostructures generating an electrostatic potential. In this study, we examine whether light intensity can alter the electrostatic potential of mono- and bimetallic nanostructures changing yields of plasmon-driven reactions. Using tip-enhanced Raman spectroscopy (TERS), we quantified the yield of plasmon-driven transformations of 4-nitrobenzenethiol (4-NBT) and 3-mercaptobenzoic acid (3-MBA) on gold and gold-palladium nanoplates (AuNPs and Au@PdNPs, respectively). We found that on AuNPs 3-MBA decarboxylated forming thiophenol (TP), whereas 4-NBT was reduced to DMAB. The yield of both TP and DMAB gradually increased with increasing light intensity. On Au@PdNPs, 3-MBA could be reduced to 3-mercaptophenylmethanol (3-MPM), the yield of which was also directly dependent on the light intensity.

Thermal hysteresis of Casimir suspensions enabled by vanadium dioxide

In this work, the Casimir suspensions of a nanoplate (gold or Teflon) in a liquid environment are theoretically investigated. The substrate of the system is a three-layer structure of Teflon/vanadium dioxide(VO2)/Teflon. It is found that stable suspensions of nanoplates can be achieved due to the balances of repulsive Casimir forces, gravity and buoyancy. Remarkably, the suspension positions of gold and Teflon nanoplates are strongly associated with the preceding thermal history of VO2, i.e., heating or cooling. The differences in the suspension positions between the heating and cooling can reach tens of nanometers. Finally, a thermal hysteresis of Casimir suspensions via the temperature is shown for gold and Teflon nanoplates. Our findings offer the possibility of designing conceptually new devices in micro and nanoelectromechanical systems (MEMS and NEMS).

In Situ Surface-Enhanced Raman Scattering Detection of a SARS-CoV-2 Biomarker Using Flexible and Transparent Polydimethylsiloxane Films with Embedded Au Nanoplates.

Coronavirus disease 2019 (COVID-19) remains an ongoing issue worldwide and continues to disrupt daily life. Transmission of infection primarily occurs through secretions when in contact with infected individuals, but more recent evidence has shown that fomites are also a source of virus transmission, especially in cold-chain logistics. Traditional nucleic acid testing for severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) contamination in cold-chain logistics is time-consuming and inaccurate because of the multiplex sampling sites. Surface-enhanced Raman spectroscopy (SERS) provides a rapid, sensitive, and label-free detection route for various molecules, including viruses, through the identification of the characteristic peaks of their outer membrane proteins. In this study, we embedded arbitrarily orientated gold nanoplates (Au NPLs) in polydimethylsiloxane (PDMS) elastomer and used it as biosensor for the ultrasensitive detection of the SARS-CoV-2 spike protein in cold-chain logistics. This transparent and flexible substrate can be wrapped onto arbitrary surfaces and permits light penetration into the underlying contact surface, enabling in situ and point-of-care SERS diagnostics. The developed assay displayed high reproducibility (8.7%) and a low detection limit of 6.8 × 10–9 g mL–1, indicating its potential to serve as a promising approach with increased accuracy and sensitivity for the detection of the S protein.

Interface chemistry effects in nanofluids: Experimental and computational study of oil-based nanofluids with gold nanoplates

The chemistry of interfaces and its relation with energy storage at and transport through solid–liquid interfaces in heat transfer nanofluids is a very unexplored terrain. Here we discuss how the magnitude of the changes in specific heat and thermal conductivity of the base fluid, upon dispersion of a nanomaterial, depends on the surface chemistry of that nanomaterial. We focus on nanofluids with Au nanoplates from an integrated experimental and theoretical perspective, and compared our findings with those previously reported for nanofluids with Pd nanoplates in the same base fluid. Pd and Au are known to have different surface chemistry, and so are the structures of the solid–liquid interfaces and the thermal properties of these nanofluids. It was experimentally found that for mass fractions in the order of 0.01 wt%, Pd and Au nanoplates provide enhancements of 5.9% and 1.6% in specific heat, and enhancements of 12.5% and 17.9% in thermal conductivity, at 373 K. It was verified using density functional theory and classical molecular dynamics simulations that base fluid molecules can chemisorb on Pd surfaces, but not on Au surfaces. This work suggests that the stronger interactions between species at solid–liquid interfaces, the higher the specific heat enhancements and the lower the thermal conductivity enhancements at high temperature.

Simultaneous Thermal and Spectroscopic Screening of Morphologically Complex Theranostic Gold Nanoparticles

Gold nanoparticles absorb light energy and convert it to thermal energy that transfers to the surrounding environment, making them potentially useful for the hyperthermic treatments well known as photothermal therapy (PTT). Further, it is well documented that noble metal nanoparticles are capable of significantly enhancing the Raman scattering of molecules attached to their surfaces, a technique which is termed surface-enhanced Raman scattering (SERS). SERS combined with PTT has the ability to locate nanoparticles at depth and trigger heat production, providing an effective methodology to both seek and destroy diseased tissues. While PTT and SERS are often used in tandem and there are several ways of individually measuring SERS and thermal output, there is currently no method available that pre-screens both properties prior to in vitro or in vivo application. In this work, we have designed a 3D printed platform capable of coupling a commercially available Raman probe to a sample cuvette for SERS and heat output to be monitored simultaneously. We have compared the performance of morphologically complex gold nanoparticles, nanostars (AuNSs) and nanoplates (AuNPLs), which are both well utilized in SERS and photothermal experiments; and measured the SERS activity originating from common Raman reporter analytes 4-mercaptobenzoic acid (MBA) and 1,4-benzenedithiol (BDT). We were able to show that the system effectively measures the thermal output and SERS activity of the particles and can evaluate the effect that multiple irradiation cycles have on the SERS signal.