Enhancing Plasmonic Hot Electron Energy on Ag Surface by Amine Coordination.

Plasmonic catalysis has emerged as a promising approach to solar-chemical energy conversion. Notably, hot carriers play a decisive role in plasmonic catalysis since only when their energy matches with the LUMO or HOMO energy of the reactant molecule, can the reaction be activated. However, the hot carrier energy depends on the intrinsic physicochemical properties of the plasmonic metal substrate and the interaction with incident light. Tuning the hot carrier energy is of great significance for plasmonic catalysis but remains challenging. Here, we demonstrate that the energy of hot electrons can be significantly elevated to an unprecedented level through the coordination of amines on Ag surface. The bonding of amines and Ag reduces the work function of nanoparticles, leading to the increase of hot electron energy by 0.4 eV. This enhancement of energy promotes the cleavage of C-X (X=Cl, F) bonds upon excitation by visible light. This study provides new insights for promoting plasmonic charge transfer and enhancing the photocatalytic performance of plasmon-mediated systems.

In Situ Monitoring of Palladium-Catalyzed Chemical Reactions by Nanogap-Enhanced Raman Scattering using Single Pd Cube Dimers.

The central dilemma in label-free in situ surface-enhanced Raman scattering (SERS) for monitoring of heterogeneously catalyzed reactions is the need of plasmonically active nanostructures for signal enhancement. Here, we show that the assembly of catalytically active transition-metal nanoparticles into dimers boosts their intrinsically insufficient plasmonic activity at the monomer level by several orders of magnitude, thereby enabling the in situ SERS monitoring of various important heterogeneously catalyzed reactions at the single-dimer level. Specifically, we demonstrate that Pd nanocubes (NCs), which alone are not sufficiently plasmonically active as monomers, can act as a monometallic yet bifunctional platform with both catalytic and satisfactory plasmonic activity via controlled assembly into single dimers with an ∼1 nm gap. Computer simulations reveal that the highest enhancement factors (EFs) occur at the corners of the gap, which has important implications for the SERS-based detection of catalytic conversions: it is sufficient for molecules to come in contact with the "hot spot corners", and it is not required that they diffuse deeply into the gap. For the widely employed Pd-catalyzed Suzuki-Miyaura cross-coupling reaction, we demonstrate that such Pd NC dimers can be employed for in situ kinetic SERS monitoring, using a whole series of aryl halides as educts. Our generic approach based on the controlled assembly into dimers can easily be extended to other transition-metal nanostructures.

Several Key Factors for Efficient Electrocatalytic Water Splitting: Active Site Coordination Environment, Morphology Changes and Intermediates Identification.

Water-splitting has emerged as a promising alternative strategy to produce clean hydrogen fuel. However, current electrocatalytic water splitting suffers from sluggish kinetics, thus developing efficient electrocatalysts is crucial. Identifying reaction centers discloses the reaction mechanism and will undoubtedly facilitate the design and optimization of efficient water splitting electrocatalysts. This review summarizes several advances involving the identification of the actual active sites and intermediates capture on the catalytic surface. The morphology and valence states change on 2D materials are chose to illustrate how structural evolution affect catalytic activity. Specifically, in situ/ex situ electron microscopy techniques that used for the characterization of catalytic sites, and spectroscopy techniques that used to detect active intermediates at the molecular level are highlighted. In addition, several perspectives, such as the development of new in situ techniques and electrokinetic analysis methods, are emphasized to shed light on future research.

Plasmonic structure with nanocavity cavities for SERS detection of pesticide thiram.

Excessive thiram residues in food have the potential to negatively impact human health. Hence, the development of a convenient and fast detection method is highly desirable. In this study, an efficient, repeatable, and sensitive surface-enhanced Raman scattering (SERS) active chip was manufactured via a low-cost colloidal lithography technique. The plasmonic structure was composed of a series of silver nanospheres and nanowires. Interestingly, this type structure creates a nanocavity space with a characteristic geometry generating a strong electromagnetic field coupling. The finite-different time-domain software was employed to simulate the electromagnetic field distribute on the nanocavity. Accordingly, SERS active chip that displays ultra-low concentration detection of thiram (10-11 M) was realized. Moreover, the excellent reproducibility of thiram (10-6 M) practical detection on an apple pericarp has great potential for application in food safety.

Polarized SERS Controlled by Anisotropic Growth on Ordered Curvature Substrate.

Colloidal lithography is an efficient and low-cost method to prepare an ordered nanostructure array with new shapes and properties. In this study, square-shaped and cone-shaped Au nanostructures were obtained by 70° angle deposition onto polystyrene bead array with the diameter of 500 nm when a space of 120 nm is created between the neighbor beads by plasma etching. The gaps between the units decrease when the Au deposition time increases, which leads to the polarized enhanced local field, in agreement with the surface-enhanced Raman scattering spectra (SERS) observations and finite-difference time-domain (FDTD) simulations. When the Au deposition time increased to 5 min, 5 nm gaps form between the neighbor units, which gave an enhancement factor of 5 × 109. The SERS chip was decorated for the detection of the liver cancer cell marker Alpha-fetoprotein (AFP) with the detection limit down to 5 pg/mL.

Sunflower-Like Nanostructure with Built-In Hotspots for Alpha-Fetoprotein Detection.

In the present study, a sunflower-like nanostructure array composed of a series of synaptic nanoparticles and nanospheres was manufactured through an efficient and low-cost colloidal lithography technique. The primary electromagnetic field contribution generated by the synaptic nanoparticles of the surface array structures was also determined by a finite-difference time-domain software to simulate the hotspots. This structure exhibited high repeatability and excellent sensitivity; hence, it was used as a surface-enhanced Raman spectroscopy (SERS) active substrate to achieve a rapid detection of ultra-low concentrations of Alpha-fetoprotein (AFP). This study demonstrates the design of a plasmonic structure with strong electromagnetic coupling, which can be used for the rapid detection of AFP concentration in clinical medicine.

Taxifolin inhibits melanoma proliferation/migration impeding USP18/Rac1/JNK/ß-catenin oncogenic signaling.

BACKGROUND: Metastatic melanoma is a fatal cancer. Despite the advances in targeted therapy and immunotherapy for patients with melanoma, drug resistance and low response rates pose a considerable challenge. Taxifolin is a multifunctional natural compound with emerging antitumor potentials. However, its utility in melanoma treatment remains unclear. PURPOSE: The study aimed to investigate the effect of purified Taxifolin from Larix olgensis roots (Changbai Mountain, China) on melanoma and explore the underlying mechanism. METHODS: Purified Taxifolin from Larix olgensis roots was evaluated for its antimelanoma effects in vitro and in vivo settings. RNA-seq analysis was performed to explore the underlying mechanism. RESULTS: Purified Taxifolin (> 99 %) from Larix olgensis roots inhibited the proliferation and migration of B16F10 melanoma cells at 200 and 400 µM, and of A375 cells at 100 and 200 µM. Taxifolin administered at 60 mg/kg suppressed tumor growth and metastasis in mouse models without causing significant toxicity. Taxifolin modulated USP18/Rac1/JNK/ß-catenin axis to exert its antitumor effect. CONCLUSION: These findings indicate that Taxifolin derived from Larix olgensis roots may be a promising antimelanoma therapy.

Light inhibition of hydrogenation reactions on Au-Pd nanocoronals as plasmonic switcher in catalysis.

Light, as a powerful energy source, has motivated the many endeavors of chemists in photochemical transformations. We were delighted to find that light has an inhibition effect on hydrogenation reactions. Exploring this previously unperceived effect will bring renewed understanding of interactions of light and matter. This work provides a breakthrough in ways to remotely control chemical reactions by light.

Enhanced Surface Plasmon by Clusters in TiO2-Ag Composite.

The surface plasmon in the composite composed of the noble metals and the semiconductors is interesting because of the various charges and the potential applications in many fields. Based on a highly ordered 2D polystyrene spheres array, the ordered composite nanocap arrays composed of TiO2 and Ag were prepared by the co-sputtering technique, and the surface morphology was tuned by changing TiO2 sputtering power. When TiO2 sputtering power was 60 W and Ag sputtering power was 10 W, the composite unit arrays showed the nanocap shapes decorated by many composite clusters around. The composite clusters led to the additional local coupling of the electromagnetic fields and significant Surface-Enhanced Raman Scattering (SERS) observations, which was also confirmed by the finite-different time-domain simulation. The SERS-active substrate composed of the composite nanocaps decorated by clusters realized the accurate detection of the thiram with concentrations down to 10-9 M.

SERS Immunosensor of Array Units Surrounded by Particles: A Platform for Auxiliary Diagnosis of Hepatocellular Carcinoma.

Hepatocellular carcinoma (HCC) is one of the diseases with high mortality worldwide, so its early diagnosis and treatment have attracted much attention. Due to the advantages of the high sensitivity of surface-enhanced Raman scattering (SERS) detection, SERS has excellent application value in the diagnosis of HCC. In this paper, silver nanoparticles (AgNPs) are modified by magnetron sputtering on the surface of polystyrene (PS) templates with spheres of two different diameters. The array of units surrounded by particles is successfully prepared and the SERS performance is characterized. The effect of the gap between AgNPs on plasmon coupling and hot spot distribution is discussed. Finite-difference time domain (FDTD) simulation is used to verify the electric fields and hot spot distribution of the array. The differences in the concentrations of HCC markers are analyzed by using the change of SERS signal intensity of the array. The whole process proves that the preparation of structures with a strong local electric field to provide highly sensitive SERS signals is a key link in the detection of HCC markers, which is conducive to the diagnosis of HCC and has potential application value in clinical diagnosis.

Manipulation and Applications of Hotspots in Nanostructured Surfaces and Thin Films.

The synthesis of nanostructured surfaces and thin films has potential applications in the field of plasmonics, including plasmon sensors, plasmon-enhanced molecular spectroscopy (PEMS), plasmon-mediated chemical reactions (PMCRs), and so on. In this article, we review various nanostructured surfaces and thin films obtained by the combination of nanosphere lithography (NSL) and physical vapor deposition. Plasmonic nanostructured surfaces and thin films can be fabricated by controlling the deposition process, etching time, transfer, fabrication routes, and their combination steps, which manipulate the formation, distribution, and evolution of hotspots. Based on these hotspots, PEMS and PMCRs can be achieved. This is especially significant for the early diagnosis of hepatocellular carcinoma (HCC) based on surface-enhanced Raman scattering (SERS) and controlling the growth locations of Ag nanoparticles (AgNPs) in nanostructured surfaces and thin films, which is expected to enhance the optical and sensing performance.

Controlling the Growth Locations of Ag Nanoparticles at Nanoscale by Shifting LSPR Hotspots.

Controlling chemical reactions by plasma is expected to be a new method for improving the structural properties of substrates. An Au nanojar array was prepared when Au was deposited onto a 2D polystyrene (PS) array. The site-selective chemical growth of Ag nanoparticle rings was realized around the Au nanojar necks by a local surface plasmon resonance (LSPR)-assisted chemical reaction. The catalytic hotspots in the nanostructure array could be controlled by both etching the nanojars and Au or TiO2 sputtering onto the nanojars, which were confirmed by the growth sites of the Ag nanoparticle in the LSPR-assisted chemical reaction. The structure of the nanojars and the electric field distributions of the growing nanoparticles were simulated and analyzed using Finite-Difference Time-Domain. FDTD simulations showed that the changes in the nanojar shape led to the changed hotspot distributions. At the same time, tracking the hotspot shifts in the process of structural change was also achieved by the observation of Ag growth. Nanoarray structure prepared by LSPR-assisted chemical reaction is one of the hot fields in current research and is also of great significance for the application of Surface-Enhanced Raman Scattering.

Nanohoneycomb Surface-Enhanced Raman Spectroscopy-Active Chip for the Determination of Biomarkers of Hepatocellular Carcinoma.

Overexpression of the Lens culinaris agglutinin-reactive fraction of alpha-fetoprotein (AFP-L3) is an essential biomarker for early diagnosis of hepatocellular carcinoma (HCC). In this study, we designed a new surface-enhanced Raman spectroscopy active chip for the detection of AFP with high sensitivity and excellent repeatability. This chip was composed of a honeycomb gold nanostructure array with strong electromagnetic field coupling due to the special cavity geometric characteristics of the honeycomb structure. The honeycomb structure exhibited extraordinary performance for the specific detection of AFP in the range of 0.003-3 ng/mL and also determined the proportion of AFP-L3 with a high degree of accuracy, which has shown great potential for application in the clinical diagnosis of HCC.

Site-selective growth of Ag nanoparticles controlled by localized surface plasmon resonance of nanobowl arrays.

Hexagonal Ag nanoparticle arrays are exclusively grown on top of the interstices of Au nanobowl arrays. The photoinduced effect of the enhanced electromagnetic field between Au nanobowls accelerated the chemical reaction and is responsible for Ag growth in defined local positions. The enhanced electric field of the Au nanobowl array induced a photoreaction, which resulted in Ag growth in the hot area. Interestingly, the sizes and positions of the Ag nanoparticles distributed in the strong electric field of the Au nanobowl array are easily controlled. A six-axis symmetric pattern of Ag nanoparticle growth is realized based on the use of vertically incident circularly polarized light. Furthermore, a three-axis symmetric nanoperiodic structure is obtained through the use of linearly polarized oblique waves with specific incidence angles. This research shows that an electric field can be used to control a chemical reaction at the nanometer level, enabling the control and design of a wide variety of nanoperiodic structures.

Controlling the 3D Electromagnetic Coupling in Co-Sputtered Ag⁻SiO2 Nanomace Arrays by Lateral Sizes.

Ag⁻SiO2 nanomace arrays were prepared on a two-dimensional ordered colloidal (2D) polystyrene sphere template by co-sputtering Ag and SiO2 in a magnetron sputtering system. The lateral size of the nanomaces and the distance between the neighbor nanomaces were controlled by adjusting the etching time of the 2D template. The nanomaces were composed of SiO2-isolated Ag nanoparticles, which produced surface-enhanced Raman scattering (SERS) enhancement, and 3D hot spots were created between the neighbor nanomaces. When the distance between the nanomaces was sufficiently large, triangle-shaped nanostructures on silicon substrate were observed, which also contributed to the enhancement of the SERS signals. The finite-difference time-domain (FDTD) method was used to calculate the electromagnetic field distributions in the Ag⁻SiO2 nanomace arrays, which generated physical reasons for the change of the SERS signals.

Carrier Density-Dependent Localized Surface Plasmon Resonance and Charge Transfer Observed by Controllable Semiconductor Content.

We discuss how the controllable carrier influences the localized surface plasmon resonance (LSPR) and charge transfer (CT) in the same system based on ultraviolet-visible and surface-enhanced Raman scattering (SERS) measurements. The LSPR can be easily tuned from 580 to 743 nm by changing the sputtering power of Cu2S in the Ag and Cu2S composite substrate. During this process, surprisingly, we find that the LSPR is proportional to the sputtering power of Cu2S. This observation indicates that LSPR can be accurately adjusted by changing the content of the semiconductor, or even the carrier density. Moreover, we characterize the carrier density through the detection of the Hall effect to analyze the Raman shift caused by CT and obtain the relationships between them. These fundamental discussions provide a guideline for tunable LSPR and the investigation of CT.