Selenocystine and Photo-Irradiation Directed Growth of Helically Grooved Gold Nanoarrows.

The fabrication of discrete nanostructures with both plasmonic circular dichroism (PCD) and chiral features is still a challenge. Here, gold nanoarrows (GNAs) with both chiroptical responses and chiral morphologies are achieved by using L-selenocystine (L-SeCys2 ) as a chiral inducer. While L-SeCys2 generates GNAs with a weak PCD signal, the irradiated L-SeCys2 (irr-L-SeCys2 ) leads to GNAs with featured helical grooves (HeliGNAs) accompanying with a strong PCD signal. It is revealed that when L-SeCys2 is photo-irradiated, the emergence of selenyl radicals plays an important role in the formation of HeliGNAs and enhancement of the chiroptical signal. In comparison with L-SeCys2 and the other kinds of sulfur-containing amino acids, the formation mechanism of helical grooves on the surface of GNAs is proposed. Both HeliGNAs and GNAs are used to discriminate amino acids by utilizing surface enhanced Raman scattering (SERS) effect. In the presence of either GNAs or HeliGNAs as the substrate, Fmoc-L-Phe shows more significant SERS than Fmoc-D-Phe. This study may advance the design of discrete plasmonic nanomaterials with both chiral morphology and potential applications in discrimination of chiral molecules.

Reversible capturing and voltammetric determination of circulating tumor cells using two-dimensional nanozyme based on PdMo decorated with gold nanoparticles and aptamer.

A novel cytosensor was constructed for the ultrasensitive detection and nondestructive release of circulating tumor cells (CTCs) by combining Au nanoparticles-loaded two-dimensional bimetallic PdMo (2D Au@PdMo) nanozymes and electrochemical reductive desorption. The 2D Au@PdMo nanozymes possessed high-efficiency peroxidase-like activity and were assembled with an aptamer composed of a thiol-modified epithelial specific cell adhesion molecule (EpCAM) to strengthen CTCs adhesion. Moreover, the electrode surface was decorated with highly fractal Au nanostructures (HFAuNSs) composites due to the similarity in fractal nanostructure with the CTCs membrane to enhance the CTCs anchoring efficiency and release capability. The captured CTCs could be further efficiently dissociated and nondestructively released from the modified electrodes upon electrochemical reductive desorption. The designed cytosensor showed an excellent analytical performance, with a wide linear range from 2 to 1 × 105 cells mL-1 and low limit of detection (LOD) of 2 cells mL-1 (S/N = 3) at the working potential in the range  -0.6 to 0.2 V. A satisfactory CTCs release reaching a range of 93.7-97.4% with acceptable RSD from 3.55 to 6.41% and good cell viability was obtained. Thus, the developed cytosensor might provide a potential alternative to perform CTC-based liquid biopsies, with promising applications in early diagnosis of tumors. Preparation and mechanism of desorption of the cytosensor based on 2D Au@PdMo nanozymes and electrochemical reductive desorption for the detection and release of CTCs. A Preparation procedure of the Apt/Au@PbMo bioconjugates. B Fabrication process of the sandwich-type cytosensor. C Electrochemical signal produced by the Au@PdMo nanozymes. D Mechanism of electrochemical reductive desorption for CTCs release.

UV Irradiation-Induced SERS Enhancement in Randomly Distributed Au Nanostructures.

Currently used platforms for surface-enhanced Raman scattering (SERS) sensors generally employ metallic nanostructures for enrichment of the plasmonic hotspots in order to provide higher Raman signals, but this procedure is still considered challenging for analyte-surface affinity. This study reports a UV irradiation-induced SERS enhancement that amplifies the interactions between the analytes and metallic surfaces. The UV light can play critical roles in the surface cleaning to improve the SERS signal by removing the impurities from the surfaces and the formation of the negatively charged adsorbed oxygen species on the Au surfaces to enhance the analyte-surface affinity. To evaluate this scenario, we prepared randomly distributed Au nanostructures via thermal annealing with a sputtered Au thin film. The UV light of central wavelength 254 nm was then irradiated on the Au nanostructures for 60 min. The SERS efficiency of the Au nanostructures was subsequently evaluated using rhodamine 6G molecules as the representative Raman probe material. The Raman signal of the Au nanostructures after UV treatment was enhanced by up to approximately 68.7% compared to that of those that did not receive the UV treatment. We expect that the proposed method has the potential to be applied to SERS enhancement with various plasmonic platforms.

Crystal-Phase-Selective Etching of Heterophase Au Nanostructures.

Selective oxidative etching is one of the most effective ways to prepare hollow nanostructures and nanocrystals with specific exposed facets. The mechanism of selective etching in noble metal nanostructures mainly relies on the different reactivity of metal components and the distinct surface energy of multimetallic nanostructures. Recently, phase engineering of nanomaterials (PEN) offers new opportunities for the preparation of unique heterostructures, including heterophase nanostructures. However, the synthesis of hollow multimetallic nanostructures based on crystal-phase-selective etching has been rarely studied. Here, a crystal-phase-selective etching method is reported to selectively etch the unconventional 4H and 2H phases in the heterophase Au nanostructures. Due to the coating of Pt-based alloy and the crystal-phase-selective etching of 4H-Au in 4H/face-centered cubic (fcc) Au nanowires, the well-defined ladder-like Au@PtAg nanoframes are prepared. In addition, the 2H-Au in the fcc-2H-fcc Au nanorods and 2H/fcc Au nanosheets can also be selectively etched using the same method. As a proof-of-concept application, the ladder-like Au@PtAg nanoframes are used for the electrocatalytic hydrogen evolution reaction (HER) in acidic media, showing excellent performance that is comparable to the commercial Pt/C catalyst.

Periodic Folded Gold Nanostructures with a Sub-10 nm Nanogap for Surface-Enhanced Raman Spectroscopy.

Surface-enhanced Raman spectroscopy has emerged as a powerful spectroscopy technique for detection with its capacity for label-free, nondestructive analysis, and ultrasensitive characterization. High-performance surface-enhanced Raman scattering (SERS) substrates with homogeneity and low cost are the key factors in chemical and biomedical analysis. In this study, we propose the technique of atomic force microscopy (AFM) scratching and nanoskiving to prepare periodic folded gold (Au) nanostructures as SERS substrates. Initially, folded Au nanostructures with tunable nanogaps and periodic structures are created through the scratching of Au films by AFM, the deposition of Ag/Au films, and the cutting of epoxy resin, reducing fabrication cost and operational complexity. Periodic folded Au nanostructures show the three-dimensional nanofocusing effect, hotspot effect, and standing wave effect to generate an extremely high electromagnetic field. As a typical molecule to be tested, p-aminothiophenol has the lowest detection limit of up to 10-9 M, owing to the balance between the electromagnetic field energy concentration and the transmission loss in periodic folded Au nanostructures. Finally, by precisely controlling the periods and nanogap widths of the folded Au nanostructures, the synergistic effect of surface plasmon resonance is optimized and shows good SERS properties, providing a new strategy for the preparation of plasmonic nanostructures.

Self-assembly of Au nanocrystals into large-area 3-D ordered flexible superlattice nanostructures arrays for ultrasensitive trace multi-hazard detection.

Plasmonic nanoparticles that self-assemble into highly ordered superlattice nanostructures hold substantial promise for facilitating ultra-trace surface-enhanced Raman scattering (SERS) detection. Herein, we propose a boiling-point evaporation method to synthesize ordered monocrystal-like superlattice Au nanostructures (OML-Au NTs) with a polyhedral morphology. Combined with thermal nanoimprint technology, OML-Au NTs were directly transferred to impact-resistant polystyrene (IPS) flexible SERS substrates, the obtained flexible substrates (donated as OML-Au NTs/IPS) detection limit for R6G molecules as low as 10-13 M. These results were confirmed by simulating the electromagnetic field distribution of ordered/unordered two-dimensional single-layer and three-dimensional aggregated gold nanostructures. The OML-Au NTs/IPS substrates were successfully used to detect and quantify three commonly-used agricultural pesticides, achieving detection limits as low as 10-11 M and 10-12 M, and in situ real-time detection limit reached 0.24 pg/cm2 for thiram on apple peels, which was 3 orders of magnitude lower than the current detection limit. In addition, the Raman intensity from multiple locations showed a relative standard deviation lower than 7 %, exhibiting the reliability necessary for practical applications. As a result, this research demonstrates a highly reproducible method to enable the development of plasmonic nanomaterials with flexible superstructures.

Synthesis of Linear Black Gold Nanostructures Processable as Sunlight and Low-Energy Light Collecting Films for Photo-Thermoelectricity.

As one of the effort to cope with the energy crisis and carbon neutrality, utilization of low-grade energy generated indoors (e.g., light) is imperative because this saves building and house energy, which accounts for ≈40% of total energy consumption. Although photovoltaic devices could contribute to energy savings, it is also necessary to harvest heat from indoor lights to generate electricity because the light absorbed by materials is mostly transformed into heat. For daily life uses, materials should not only have high absorptance and low emittance but also be easily processed into various forms. To this end, this work synthesizes black aqueous suspensions containing winding and bent linear gold nanostructures with diameters of 3-5 nm and length-to-diameter ratios of ≈4-10. Their optical and photo-thermal characteristics are understood through experimental and theoretical investigations. Black gold nanostructures are conveniently processed into metal-dielectric films on metal, glass, and flexible substrates. The film on copper has an absorptance of 0.97 and an emittance of 0.08. Under simulated sunlight and indoor LED light illumination, the film has equivalent photo-thermal and photo-thermoelectric performances to a top-tier sunlight-collecting film. This work attempts to modify the film structure to generate more usable electricity from low-energy indoor light.

Recent developments in computational and experimental studies of physicochemical properties of Au and Ag nanostructures on cellular uptake and nanostructure toxicity.

Recent developments in studies of the uptake and toxicity of both gold (Au) and silver (Ag) nanostructures (NS) in drug delivery systems have shown that physicochemical properties play an important role. Physicochemical properties of engineered NS such as size, shape, coordination chemistry, surface charge, and surface chemistry generally manifest in reactivity, surface energetics and electronic properties of the nanomaterials. This review discusses the computational and experimental studies conducted to study the effects of physicochemical properties on cellular uptake and nanostructure toxicity. The studies show that properties like coordination chemistry have often been overlooked when studying the high surface energy of NS.

Methods of green synthesis of Au NCs with emphasis on their morphology: A mini-review.

Greener synthetic methods are becoming more popular as a means of reducing environmental pollution caused by reaction byproducts. Another important advantage of green methods is their low cost and the abundance of raw materials. Herein, we investigate the green Au nanoclusters (NCs) using microorganisms (bacteria and fungi) and plant extraction with various shapes and development routes. Natural products derived from plants, tea, coffee, banana, simple amino acids, enzyme, sugar, and glucose have been used as reductants and as capping agents during synthesis in literature. The synthesis techniques are generally chemical, physical and green methods. Green synthesis of Au NCs using bacteria and fungi can be divided into intracellular and extracellular. In an intracellular manner, bacterial cells are implanted in a culture medium containing salt and heated under suitable growth conditions. However, in an extracellular manner, the Au ions are directed from the outside into the cell. Thus, these methods are considered as a better alternative to chemical and physical synthesis. The research on green synthesis of Au nanoparticles (NPs) and its influence on their size and morphology are summarized in this review.

Electrochemical aptasensors based on the gold nanostructures.

Electrochemical aptasensors as novel diagnostic tools have attracted sufficient research interest in biomedical sciences. In this review, recent leading trends about gold (Au) nanostructures based electrochemical aptasensors have been collected, reviewed, and compared. Here, the considered electrochemical aptasensors were categorized based on the analytes and diagnostic techniques. Pharmaceutical analytes and biomolecules were reviewed in a separate section consisting of a variety of antibiotics, analgesics, and other biomolecules. Various aptasensors have also measured toxins, ions, and hazardous chemicals, and the findings of them have also been reviewed. Many aptasensors have been designed to detect different disease biomarkers that will play an essential role in the future of early diagnosis of diseases. Pathogen microorganisms have been considered as the analyte in several designed electrochemical aptasensors in recent researches, and their results have been reviewed and discussed as another section. Important aspects considered in the review of the mentioned aptasensors were the type of analyte, features of the aptamer as the biorecognition element, type of Au nanostructures, diagnostic technique, diagnostic mechanism, detection range and the limit of detection (LOD). In the last section, an in-depth analysis has been provided based on the crucial features of all included aptasensors.

Surface-Enhanced Raman Spectroscopy (SERS) of Neonicotinoid Insecticide Thiacloprid Assisted by Silver and Gold Nanostructures.

This study expresses our results on surface-enhanced Raman spectroscopy (SERS) analyses of neonicotinoid insecticide thiacloprid, i.e., Calypso 480 SC, in quantities much smaller than usually applied in the agricultural medicine. Advanced Ag and Au nanostructures created by the thermal deposition technique on Al2O3 ceramic were applied as active substrates for SERS analyses. The minimum concentration of thiacloprid detected was 380 µM and the enhancement factor was estimated to be about 3 × 103. The intensity of the SERS peaks increased by an order of magnitude after pulsed laser annealing of the films and formation of nanoparticle arrays and the enhancement factor reached ≈104, respectively. The proposed study has direct bearing on the environment and human health by detection of small amounts or residue of harmful pollutants using a relatively cheap and easy method to produce active SERS substrates.

Low-Temperature Vapor-Phase Synthesis of Single-Crystalline Gold Nanostructures: Toward Exceptional Electrocatalytic Activity for Methanol Oxidation Reaction.

Au nanostructures (Au NSs) have been considered promising materials for applications in fuel cell catalysis, electrochemistry, and plasmonics. For the fabrication of high-performance Au NS-based electronic or electrochemical devices, Au NSs should have clean surfaces and be directly supported on a substrate without any mediating molecules. Herein, we report the vapor-phase synthesis of Au NSs on a fluorine-doped tin oxide (FTO) substrate at 120 °C and their application to the electrocatalytic methanol oxidation reaction (MOR). By employing AuCl as a precursor, the synthesis temperature for Au NSs was reduced to under 200 °C, enabling the direct synthesis of Au NSs on an FTO substrate in the vapor phase. Considering that previously reported vapor-phase synthesis of Au NSs requires a high temperature over 1000 °C, this proposed synthetic method is remarkably simple and practical. Moreover, we could selectively synthesize Au nanoparticles (NPs) and nanoplates by adjusting the location of the substrate, and the size of the Au NPs was controllable by changing the reaction temperature. The synthesized Au NSs are a single-crystalline material with clean surfaces that achieved a high methanol oxidation current density of 14.65 mA/cm² when intimately supported by an FTO substrate. We anticipate that this novel synthetic method can widen the applicability of vapor-phase synthesized Au NSs for electronic and electrochemical devices.

Surface-Enhanced Raman Spectroscopy (SERS) of Mancozeb and Thiamethoxam Assisted by Gold and Silver Nanostructures Produced by Laser Techniques on Paper.

Advanced gold (Au) and silver (Ag) nanostructures were produced by laser techniques on printer paper substrate. Surface-enhanced Raman spectroscopy (SERS) analyses of the fungicide mancozeb (Dithane DG) and insecticide thiamethoxam (Aktara 25 BG) in quantities smaller than usually applied in agricultural medicine were performed for the first time assisted by the structures fabricated. The investigations and results show an easy alternative and cheap way to detect small amounts or residue of harmful environmental pollutants, which has a direct bearing on food quality and thus on human health.

Enzymatic biosensor based on entrapment of d-amino acid oxidase on gold nanofilm/MWCNTs nanocomposite modified glassy carbon electrode by sol-gel network: Analytical applications for d-alanine in human serum.

Sensing and determination of d-alanine is studied by using an enzymatic biosensor which was constructed on the basis of d-amino acid oxidase (DAAO) immobilization by sol-gel film onto glassy carbon electrode surface modified with nanocomposite of gold nanofilm (Au-NF) and multiwalled carbon nanotubes (MWCNTs). The Au-NF/MWCNT nanocomposite was prepared by applying the potentiostatic technique for electrodeposition of Au-NF on the MWCNT immobilized on glassy carbon electrode surface. The modified electrode is investigated by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), linear sweep voltammetry (LSV) and cyclic voltammetry(CV) techniques. The linear sweep voltammetry was used for determination of d-alanine and the results showed an excellent linear relationship between biosensor response and d-alanine concentration ranging from 0.25µM to 4.5µM with correction coefficient of 0.999 (n=20). Detection limit for the fabricated sensor was calculated about 20nM (for S/N=3) and sensitivity was about 56.1µAµM-1cm-2. The developed biosensor exhibited rapid and accurate response to d-alanine, a good stability (4 weeks) and an average recovery of 98.9% in human serum samples.

Au nanostructure fabrication by pulsed laser deposition in open air: Influence of the deposition geometry.

We present a fast and flexible method for the fabrication of Au nanocolumns. Au nanostructures were produced by pulsed laser deposition in air at atmospheric pressure. No impurities or Au compounds were detected in the resulting samples. The nanoparticles and nanoaggregates produced in the ablated plasma at atmospheric pressure led to the formation of chain-like nanostructures on the substrate. The dependence of the surface morphology of the samples on the deposition geometry used in the experimental set up was studied. Nanocolumns of different size and density were produced by varying the angle between the plasma plume and the substrate. The electrical, optical, and hydrophobic properties of the samples were studied and discussed in relation to their morphology. All of the nanostructures were conductive, with conductivity increasing with the accumulation of ablated material on the substrate. The modification of the electrical properties of the nanostructures was demonstrated by irradiation by infrared light. The Au nanostructures fabricated by the proposed technology are difficult to prepare by other methods, which makes the simple implementation and realization in ambient conditions presented in this work more ideal for industrial applications.

Electromagnetic Enhancement of Graphene Raman Spectroscopy by Ordered and Size-Tunable Au Nanostructures.

The size-controllable and ordered Au nanostructures were achieved by applying the self-assembled monolayer of polystyrene microspheres. Few-layer graphene was transferred directly on top of Au nanostructures, and the coupling between graphene and the localized surface plasmons (LSPs) of Au was investigated. We found that the LSP resonance spectra of ordered Au exhibited a redshift of ~20 nm and broadening simultaneously by the presence of graphene. Meanwhile, the surface-enhanced Raman spectroscopy (SERS) of graphene was distinctly observed; both the graphene G and 2D peaks increased induced by local electric fields of plasmonic Au nanostructures, and the enhancement factor of graphene increased with the particle size, which can be ascribed to the plasmonic coupling between the ordered Au LSPs and graphene.

Properties of plasmonic arrays produced by pulsed-laser nanostructuring of thin Au films.

A brief description of research advances in the area of short-pulse-laser nanostructuring of thin Au films is followed by examples of experimental data and a discussion of our results on the characterization of structural and optical properties of gold nanostructures. These consist of partially spherical or spheroidal nanoparticles (NPs) which have a size distribution (80 ± 42 nm) and self-organization characterized by a short-distance order (length scale ≈140 nm). For the NP shapes produced, an observably broader tuning range (of about 150 nm) of the surface plasmon resonance (SPR) band is obtained by renewal thin film deposition and laser annealing of the NP array. Despite the broadened SPR bands, which indicate damping confirmed by short dephasing times not exceeding 4 fs, the self-organized Au NP structures reveal quite a strong enhancement of the optical signal. This was consistent with the near-field modeling and micro-Raman measurements as well as a test of the electrochemical sensing capability.