Au Nanorods Research Articles

Correlative Multi-Scale Characterization of Nanoparticles Using Transmission Electron Microscopy

Chemical and physical properties of nanoparticles (NPs) are strongly influenced not only by the crystal structure of the respective material, including crystal structure defects but also by the NP size and shape. Contemporary transmission electron microscopy (TEM) can describe all these NP characteristics, however typically with a different statistical relevance. While the size and shape of NPs are frequently determined on a large ensemble of NPs and thus with good statistics, the characteristics on the atomic scale are usually quantified for a small number of individual NPs and thus with low statistical relevance. In this contribution, we present a TEM-based characterization technique, which can determine relevant characteristics of NPs in a scale-bridging way—from the crystal structure and crystal structure defects up to the NP size and morphology—with sufficient statistical relevance. This technique is based on a correlative multi-scale TEM approach that combines information on atomic scale obtained from the high-resolution imaging with the results of the low-resolution imaging assisted by a semi-automatic segmentation routine. The capability of the technique is illustrated in several examples, including Au NPs with different shapes, Au nanorods with different facet configurations, and multi-core iron oxide nanoparticles with a hierarchical structure.

Magnetoplasmonic Triblock Nanorods for Collective Linear Dichroism.

Polarized light detection is crucial for advancements in optical imaging, positioning, and obstacle avoidance systems. While optical nanomaterials sensitive to polarization are well-established, the ability to align these materials remains a significant challenge. Here, we introduce Au-Fe3O4-Au triblock nanorods as a novel solution. Synthesized via a space-confined seeded growth method, these magnetoplasmonic nanocomposites uniquely combine the strong polarization capabilities of Au nanorods with the magnetic alignment properties of Fe3O4 nanorods. This architecture results in exceptional collective linear dichroism, achieving a polarization ratio of approximately 14 at the device level. Our nanorods exhibit high detection sensitivity and laser damage resistance, positioning them as a promising platform for developing advanced optical devices.

Salmonella Biomimetic Nanoparticles for Photothermal-Chemotherapy of Colorectal Cancer.

Nanomedicines have been widely used in colorectal cancer treatment, but their suboptimal targeting and deficient penetration capabilities remain obstacles in the delivery of therapeutics. In this study, inspired by the natural tumor tropism and intestinal invasion of Salmonella, we engineered highly biomimetic nanoparticles (SM-AuNRs) utilizing a Salmonella membrane to coat bacilliform Au nanorods. The engineered SM-AuNRs were able to mimic the germ's morphology and biological surface. SM-AuNRs containing the specific proteins inherited from the Salmonella membrane facilitated specific targeting and internalization into tumor cells. Meanwhile, SM-AuNRs with the rod-shaped morphology effectively traversed mucus barriers and tumor stroma. Due to the superior biological barrier penetrating and tumor targeting capabilities, doxorubicin-loaded SM-AuNRs with near-infrared laser irradiation displayed remarkable photothermal-chemotherapeutic antitumor effects in mouse orthotopic colorectal cancer models. Our findings pave the way for the design of bacteria-mimicking nanoparticles, presenting a promising avenue for the targeting and efficient treatment of colorectal cancer.

Additive-Free Synthesis of (Chiral) Gold Bipyramids from Pentatwinned Nanorods.

The production of colloidal metal nanostructures with complex geometries usually involves shape-directing additives, such as metal ions or thiols, which stabilize high-index facets. These additives may however affect the nanoparticles' surface chemistry, hindering applications, e.g., in biology or catalysis. We report herein the preparation of gold bipyramids with no need for additives and shape yields up to 99%, using pentatwinned Au nanorods as seeds and cetyltrimethylammonium chloride as surfactant. For high-growth solution:seed ratios, the bipyramids exhibit an unusual "belted" structure. Three-dimensional electron microscopy revealed the presence of high-index {117}, {115}, and {113} side facets, with {113} and {112} facets at the belt. Belted bipyramids exhibit strong near-field enhancement and high extinction in the near-infrared, in agreement with electromagnetic simulations. These Ag-free bipyramids were used to seed chiral overgrowth using 1,1'-binaphthyl-2,2'-diamine as a chiral inducer, with g-factor up to 0.02, likely the highest reported for bipyramid seeds so far.

Highly Branched Au Superparticles as Efficient Photothermal Transducers for Optical Neuromodulation.

Precise neuromodulation is critical for interrogating cellular communication and treating neurological diseases. Nanoscale transducers have emerged as effective interfaces to exert photothermal effects and modulate neural activities with a high spatiotemporal resolution. Ideal materials for this application should possess strong light absorption, high photothermal conversion efficiency, and great biocompatibility for clinical translation. Here, we show that the structurally designed 3D Au superparticles with a highly branched morphology can be promising candidates for nongenetic and remote neuromodulation. The structure-induced blackbody-like absorption endows Au superparticles with photothermal conversion efficiency over 90%, much higher than that of conventional Au nanorods. With the biocompatible polydopamine ligands, Au superparticles can be readily interfaced with primary mouse hippocampal neurons and other cells and can photostimulate or inhibit their activities in both cell networks or with a single-cell resolution. These findings highlight the importance of structural designs as powerful tools to promote the performance of plasmonic materials in neuromodulation and related research of neuroscience and neuroengineering.

Cascade enzyme-mimicking with spatially separated gold-ceria for dual-mode detection of superoxide anions

Metal-semiconductor nanozyme of dumbbell Au-CeO2 with spatially separated heterostructure has cascade superoxide dismutase (SOD)-like and peroxidase (POD)-like activities for superoxide anions detection. It was synthesized by selective growth of CeO2 at the ends of Au nanorod (Au NR). Taking advantage of the excellent local surface plasmon resonance (LSPR) effect of Au NR, the spatially separated Au-CeO2 has a higher photothermal effect than the continuously growing core-shell structure of Au@CeO2. Meanwhile, the hot electrons of Au NR could transfer to CeO2 under 808 nm laser irradiation, changing the ratio of Ce3+/Ce4+ redox couples over CeO2 and facilitating H2O2 decomposition thus enhancing POD-like activity. Based on the SOD-like activity of Au-CeO2, superoxide anion (O2·−) can be transformed into hydrogen peroxide (H2O2). Dual-mode including absorbance and temperature sensing detection of O2·−, with the detection range from nM to μM i.e., 0.1–150 μM and LOD of 0.033 μM (S/N = 3) was achieved through the cascade catalysis and photothermal effect. The as-proposed method was applicable to both cancer and normal cell samples with satisfactory accuracy and recovery.

Investigation of long-range plasmonic field effects in Au@SiO2 nanostructures using p-nitrophenol reduction

As an emerging field, plasmonic photocatalysis has gradually garnered attention from researchers. It is generally accepted that localized surface plasmonic resonance (LSPR) in noble metallic nanostructures enhances photocatalysis through the induction of a long-range plasmonic field. Furthermore, nanostructures in close proximity can enhance the electromagnetic (EM) field via plasmonic coupling, which also contributes to improved photocatalytic activity. In this study, core-shell nanostructures composed of Au nanorods (AuNRs) with pinhole-free SiO2 shells (pf-AuNRs@SiO2) are synthesized as non-contact, long-range photocatalysts. By tuning the aspect ratios (ARs) of the AuNRs to match the LSPR peaks with the wavelength of the irradiation light source, an optimized photocatalytic effect was achieved in the reduction of p-nitrophenol (p-NP). Additionally, by comparing shell thicknesses of 5 nm and 10 nm, it was observed that the 5 nm thickness exhibited superior catalytic efficiency. This enhancement is attributed to the thinner shell allowing reactants to be placed within a stronger plasmonic field.

Hollow Gold-Silver Nanorods-A New, Very Efficient Nanomaterial for Surface-Enhanced Raman Scattering (SERS) Measurements.

Anisotropic plasmonic nanoparticles usually generate SERS enhancement factors that are significantly larger than those generated by spherical plasmonic nanostructures, so the former are usually preferred as substrates for SERS measurements. Gold nanorods are one of the most commonly used anisotropic nanomaterials for SERS experiments. Unfortunately, even a slight contamination of the surfactant used in the process of the synthesis of gold nanorods has a significant impact on the geometry of the resulting nanostructures. In this work, using easily formed silver nanorods as templates, hollow AuAg nanorods are formed by means of a silver-gold galvanic exchange reaction (in this process, nanostructures with a cavity inside form because one gold atom replaces three silver atoms). Hollow AuAg nanorods are highly active during SERS measurements-for shorter wavelengths of the excitation radiation, they display greater SERS activity than Au nanorods. To our knowledge, this is the first example of the use of hollow plasmonic nanorods for SERS measurements. Elemental mapping of the rods showed that the silver, some of which remained after the galvanic replacement, is mainly located close to the internal cavity that was formed, whereas the gold is mainly located at the outermost regions of the nanostructure. This explains the high chemical stability of these nanostructures.

Using TiO2 to capture hot electrons for self-powered position-sensitive photodetection.

As environmental issues arise, the demand for self-powered position-sensitive detectors (PSDs) is increasing because of their advantages in miniaturization and low power consumption. Finding higher efficiency schemes for energy conversion is paramount for realizing high-performance self-powered PSDs. Here, a surface plasmon-based approach was used to improve the energy conversion efficiency, and a plasmon-enhanced lateral photovoltaic effect (LPE) was observed in PSD with TiO2/Au nanorods (NRs)/Si structure. The Au NRs convert absorbed light energy into electricity by generating hot electrons, which are efficiently captured by the TiO2 layer, and the PSD is capable of generating position sensitivity as high as 251.75 mV/mm when illuminated by a 780 nm laser without any external power supply, i.e. about five times higher than similar sensors in previous studies. In addition, the position sensitivity can be tailored by the thickness of TiO2 films. The enhancement mechanism is investigated by a localized surface plasmon (LSP)-driven carrier diffusion model. These findings reveal an important strategy for high sensitivity and low energy cost PSDs while opening up new avenues for energy harvesting self-powered position sensors.

Controlling the growth mode of Au depositing on Au nanobipyramids via ligand coverage for SERS enhancement

Gold deposition on Au nanoparticles is a common method to control the shape and further modify the properties of nanoparticles as their properties have a strong correlation with their nanostructures. For Au nanobipyramid (Au NBP), it has advantages such as the enhancement of electric field and a higher tunability in plasmon wavelength than the Au nanorod and thus owns a greater potential in shape control. In this paper, we demonstrate a scheme of depositing Au on the surface of Au NBP with the presence of a type of ligand 2-mercaptobenzoimidazole-5-carboxylic acid (MBIA) to synthesize Au NBP@Au dimers. The growth mode of Au depositing on Au NBP can be controlled by the coverage of MBIA. As the coverage is low, with a concentration of MBIA below 0.4 mM, the rough core–shell nanostructure is synthesized; However, as the coverage is high, with a concentration of MBIA over 0.8 mM, gold deposition may form islands on the surface of Au NBP. The SERS performance of Au depositing on Au NBP can also be enhanced by growth mode. For the rough-surface core–shell growth mode, the enhancement is more significant as the EF is improved from 3.5 × 105 to 1.06 × 106 than the islands-growing growth mode due to the coupling between core and shell. And our results show that with multiple types of nanosturctures easy to obtained by changing modified ligand coverage, the controlled growth has a great potential in the dimer design and SERS enhancement using Au NBP.

Fe3O4/Au@SiO2 nanocomposites with recyclable and wide spectral photo-thermal conversion for a direct absorption solar collector

The Fe3O4-based photothermal materials have been widely applied for the recycling of heavy metal nanoparticles to avoid secondary pollution in the utilization of solar energy owing to excellent magnetic properties. However, the narrow absorption band of Fe3O4 or metal nanoparticles limits their capacity for solar energy harvesting. In this paper, a recyclable and wide spectral photo-thermal conversion system (Fe3O4/Au@SiO2) based on Fe3O4 nanospheres and SiO2-modified Au nanorods (NRs) is prepared. Owing to the strong coupling effect between Fe3O4 and different Au NRs, the wide and strong absorption band from 400 nm to 1100 nm is obtained. Under the influence of magnetic field, the temperature change of nanofluids (NFs) at different positions can be controlled. When the concentration is 0.0467 vol%, the solar energy absorption fraction reaches 96.50 %. Besides, the photothermal performance of Fe3O4/Au@SiO2 NFs at different flow rates is investigated and the results show that temperature rise decreases as increasing flow rate. Finally, a water evaporator device based Fe3O4/Au@SiO2 NFs is developed. The maximum water evaporation rate of 2.6 kg m−2 h−1 can be reached and the movement of evaporator on water can be operated using magnetic field, showing great photothermal conversion performance and recovery potential in practical applications.

Highly Efficient and Rapid Surface-Enhanced Raman Spectroscopy Active Platform Based on Au Nanorods for Ultrasensitive Traumatic Brain Injury Detection

Highly Efficient and Rapid Surface-Enhanced Raman Spectroscopy Active Platform Based on Au Nanorods for Ultrasensitive Traumatic Brain Injury Detection

Near Infrared-Triggered Nitric Oxide-Release Nanovesicles with Mild-Photothermal Antibacterial and Immunomodulation for Healing MRSA-Infected Diabetic Wounds.

Bacterial infection-induced excessive inflammation is a major obstacle in diabetic wound healing. Nitric oxide (NO) exhibits significant antibacterial activity but is extremely deficient in diabetes. Hence, a near-infrared (NIR)-triggered NO release system is constructed through codelivery of polyarginine (PArg) and gold nanorods (Au) in an NIR-activatable methylene blue (MB)polypeptide-assembled nanovesicle (Au/PEL-PBA-MB/PArg). Upon NIR irradiation, the quenched MB in the nanovesicles is photoactivated to generate more reactive oxygen species (ROS) to oxidize PArg and release NO in an on-demand controlled manner. With the specific bacterial capture of phenylboronic acid (PBA), NO elevated membrane permeability and boosted bacterial vulnerability in the photothermal therapy (PTT) of the Au nanorods, which is displayed by superior mild PTT antibacterial activity against methicillin-resistant Staphylococcus aureus (MRSA) at temperatures<49.7°C in vitro. Moreover, in vivo, the antibacterial nanovesicles greatly suppressed the burst of MRSA-induced excessive inflammation, NO relayed immunomodulated macrophage polarization from M1 to M2, and the excessive inflammatory phase is successfully transferred to the repair phase. In cooperation with angiogenesis by NO, tissue regeneration is accelerated in MRSA-infected diabetic wounds. Therefore, nanoplatform has considerable potential for accelerating the healing of infected diabetic wounds.

Plasmon-mediated photocatalytic conversion in Au or Ag nanorod aggregates by surface-enhanced Raman spectroscopy

Plasmonic nanoparticles (NPs) hold considerable potential as photocatalysts owing to their robust light–matter interactions across diverse electromagnetic wavelengths, which significantly influence the photophysical characteristics of the adjacent molecular entities. Despite the widespread use of noble-metal NPs in surface-enhanced Raman scattering (SERS) applications, little is known about the kinetics of nanoparticle aggregation and how it affects their configurations. This study investigates the plasmon-driven photochemical conversion of 4-nitrobenzenethiol (NBT) to 4,4′-dimercaptoazobenzene (DMAB) on Au and Ag nanorods (NRs) through SERS. Significantly, photoconversion phenomena were observed on Ag NRs but not on Au NRs upon laser excitation at 633 nm. Finite-difference time-domain simulations revealed the presence of stronger electromagnetic fields on Ag NRs than on Au NRs. The aspect ratios and gaps between individual NPs in dimer configurations were determined to elucidate their effects on electromagnetic fields. The Ag NR dimer with an end-to-end configuration, an aspect ratio of 3.3, and a 1-nm gap exhibited the highest enhancement factor of 1.05 × 1012. Our results demonstrate that the primary contribution from diverse configurations in NR aggregates is the end-to-end configuration. The proposed NP design with adjustable parameters is expected to advance research in plasmonics, sensing, and wireless communications. These findings also contribute to the understanding of plasmon-driven photochemical processes in metallic nanostructures.

Monitoring of nanoplasmonics-assisted deuterium production in a polymer seeded with resonant Au nanorods using in situ femtosecond laser induced breakdown spectroscopy

In this brief report, we present laser induced breakdown spectroscopy (LIBS) evidence of deuterium (D) production in a 3:1 urethane dimethacrylate (UDMA) and triethylene glycol dimethacrylate (TEGDMA) polymer doped with resonant gold nanorods, induced by intense, 40 fs laser pulses. The in situ recorded LIBS spectra revealed that the D/(2D + H) increased to 4–8% in the polymer samples in selected events. The extent of transmutation was found to linearly increase with the laser pulse energy (intensity) between 2 and 25 mJ (up to 3 × 1017W/cm2). The observed effect is attributed only to the field enhancing effects due to excited localized surface plasmons on the gold nanoparticles.

Construction of intelligent response gene vector based on MOF/Fe3O4/AuNRs for tumor-targeted gene delivery

Metal-organic frameworks (MOFs) have the potential to efficiently carry cargo due to their excellent porosity and high surface area. Nevertheless, conventional MOFs and their derivatives exhibit low efficiency in transporting nucleic acids and other small molecules, as well as having poor colloidal stability. In this study, a ZIF-90 loaded with iron oxide nanoparticles and Au nanorods was prepared, and then surface-functionalized with polyethyleneimine (PEI) to create a multifunctional nanocomposite (AFZP25k) with pH, photothermal, and magnetic responsiveness. AFZP25k can condense plasmid DNA to form AFZP25k/DNA complexes, with a maximum binding efficiency of 92.85 %. DNA release assay showed significant light and pH responsiveness, with over 80 % cumulative release after 6 h of incubation. When an external magnetic field is applied, the cellular uptake efficiency in HeLa cells reached 81.51 %, with low cytotoxicity and specific distribution. In vitro transfection experiments demonstrated a gene transfection efficiency of 44.77 % in HeLa cells. Following near-infrared irradiation, the uptake efficiency and transfection efficiency of AFZP25k in HeLa cells increased by 21.3 % and 13.59 % respectively. The findings indicate the potential of AFZP25k as an efficient and targeted gene delivery vector in cancer gene therapy.

Microfluidic assay devices integrated with Au nanorods for rapid and sensitive detection of cardiac troponin I

Microfluidic assay devices integrated with Au nanorods for rapid and sensitive detection of cardiac troponin I

Photocontrolled Reversible Solid-Fluid Transitions of Azopolymer Nanocomposites for Intelligent Nanomaterials.

Intelligent polymer nanocomposites are multicomponent and multifunctional materials that show immense potential across diverse applications. However, to exhibit intelligent traits such as adaptability, reconfigurability and dynamic properties, these materials often require a solvent or heating environment to facilitate the mobility of polymer chains and nanoparticles, rendering their applications in everyday settings impractical. Here intelligent azopolymer nanocomposites that function effectively in a solvent-free, room-temperature environment based on photocontrolled reversible solid-fluid transitions via switching flow temperatures (Tfs) are shown. A range of nanocomposites is synthesized through the grafting of Au nanoparticles, Au nanorods, quantum dots, or superparamagnetic nanoparticles with photoresponsive azopolymers. Leveraging the reversible cis-trans photoisomerization of azo groups, the azopolymer nanocomposites transition between solid (Tf above room temperature) and fluid (Tf below room temperature) states. Such photocontrolled reversible solid-fluid transitions empower the rewriting of nanopatterns, correction of nanoscale defects, reconfiguration of complex multiscale structures, and design of intelligent optical devices. These findings highlight Tf-switchable polymer nanocomposites as promising candidates for the development of intelligent nanomaterials operative in solvent-free, room-temperature conditions.

Quantitative 3D structural analysis of small colloidal assemblies under native conditions by liquid-cell fast electron tomography

Electron tomography has become a commonly used tool to investigate the three-dimensional (3D) structure of nanomaterials, including colloidal nanoparticle assemblies. However, electron microscopy is typically done under high-vacuum conditions, requiring sample preparation for assemblies obtained by wet colloid chemistry methods. This involves solvent evaporation and deposition on a solid support, which consistently alters the nanoparticle organization. Here, we suggest using electron tomography to study nanoparticle assemblies in their original colloidal liquid environment. To address the challenges related to electron tomography in liquid, we devise a method that combines fast data acquisition in a commercial liquid-cell with a dedicated alignment and reconstruction workflow. We present the advantages of this methodology in accurately characterizing two different systems. 3D reconstructions of assemblies comprising polystyrene-capped Au nanoparticles encapsulated in polymeric shells reveal less compact and more distorted configurations for experiments performed in a liquid medium compared to their dried counterparts. A similar expansion can be observed in quantitative analysis of the surface-to-surface distances of self-assembled Au nanorods in water rather than in a vacuum, in agreement with bulk measurements. This study, therefore, emphasizes the importance of developing high-resolution characterization tools that preserve the native environment of colloidal nanostructures.

All-Optical Control of Ultrafast Switching between the Hybridized Plasmonic Fields of Au Nanorod Dimer in fs-nm Scale with Dispersed Femtosecond Laser.

With the increasing demand for ultrafast communication and information processing in future optical chips, arbitrary manipulation of electromagnetic fields in the femtosecond-nanometer spatiotemporal scale has attracted great attention in integrated optics. Manipulation of the nanoscale light field in the real femtosecond temporal domain is challenging work. Here, we have demonstrated all-optical control of ultrafast switching between the hybridized plasmonic fields of a Au nanorod dimer in the fs-nm scale using a dispersed femtosecond laser and revealed the transformation process with ultrahigh spatiotemporal resolved technology via the combination of a pump-probe technique and photoemission electron microscopy (PEEM). The results show that we can actively and coherently control the transformation sequence and time (with the shortest temporal interval of around 15 fs) of the two hybridized modes in the Au nanorod dimer by tuning the dispersion of the laser pulse. The nanoscale light manipulation achieved by all-optical control may contribute to the design of high-speed miniaturized signal-processing systems.