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Surface plasmons (SPs) of metals enable the tight focusing and strong absorption of light to realize an efficient utilization of photons at nanoscale. In particular, the SP-generated hot carriers have emerged as a promising way to efficiently drive photochemical and photoelectric processes under moderate conditions. In situ measuring of the transport process and spatial distribution of hot carriers in real space is crucial to efficiently capture the hot carriers. Here, we use electrochemical tip-enhanced Raman spectroscopy (EC-TERS) to in situ monitor an SP-driven decarboxylation and resolve the spatial distribution of hot carriers with a nanometer spatial resolution. The transport distance of about 20 nm for the reactive hot carriers is obtained from the TERS imaging result. The hot carriers with a higher energy have a shorter transport distance. These conclusions can be guides for the design and arrangement of reactants and devices to efficiently make use of plasmonic hot carriers., Revealing the spatial distribution of hot carriers in real space is crucial to their efficient utilization. Here, the authors show that in-situ electrochemical tip-enhanced Raman spectroscopy is able to resolve the spatial distribution of reactive hot carriers with a nanometer spatial resolution.

Detecting matter at a single-molecule level is the ultimate target in many branches of study. Nanosensors based on plasmonics have garnered significant interest owing to their ultrahigh sensitivity even at single-molecule level. However, currently, plasmonic-enhanced nanosensors have not achieved excellent performances in practical applications and their detection at femtomolar or attomolar concentrations remains highly challenging. Here we show a plasmonic sensing strategy, called buoyant plasmonic-particulate-based few-to-single particle-nanosensors. Large-sized floating particles combined with a slippery surface may prevent the coffee-ring effect and enhance the spatial enrichment capability of the analyte in plasmonic sensitive sites via the aggregation and lifting effect. Dimer and single particle-nanosensors demonstrate an enhanced surface-enhanced Raman spectroscopy (SERS) and a high fluorescence sensitivity with an enrichment factor up to an order of ∼104 and the limit of detection of CV molecules down to femto- or attomolar levels. The current buoyant particulate strategy can be exploited in a wide range of plasmonic enhanced sensing applications for a cost-effective, simple, fast, flexible, and portable detection., Plasmonic-enhanced nanosensors are limited in practical applications, as it remains challenging to detect molecules at low concentrations. Here, the authors introduce a buoyant particulate strategy in order to enrich analytes in the plasmonic hot spots.

Defects can induce drastic changes of the electronic properties of two-dimensional transition metal dichalcogenides and influence their applications. It is still a great challenge to characterize small defects and correlate their structures with properties. Here, we show that tip-enhanced Raman spectroscopy (TERS) can obtain distinctly different Raman features of edge defects in atomically thin MoS2, which allows us to probe their unique electronic properties and identify defect types (e.g., armchair and zigzag edges) in ambient. We observed an edge-induced Raman peak (396 cm−1) activated by the double resonance Raman scattering (DRRS) process and revealed electron–phonon interaction in edges. We further visualize the edge-induced band bending region by using this DRRS peak and electronic transition region using the electron density-sensitive Raman peak at 406 cm−1. The power of TERS demonstrated in MoS2 can also be extended to other 2D materials, which may guide the defect engineering for desired properties. Probing inevitable defects in two- dimensional materials is challenging. Here, the authors tackle this issue by using tip-enhanced Raman spectroscopy (TERS) to obtain distinctly different Raman features of edge defects in atomically thin MoS2, and further probe their unique electronic properties as well as identify the armchair and zigzag edges.

Many phytopathogens secrete cell wall degradation enzymes (CWDEs) to damage host cells and facilitate colonization. As the major components of the plant cell wall, cellulose and hemicellulose are the targets of CWDEs. Damaged plant cells often release damage-associated molecular patterns (DAMPs) to trigger plant immune responses. Here, we establish that the fungal pathogen Magnaporthe oryzae secretes the endoglucanases MoCel12A and MoCel12B during infection of rice (Oryza sativa). These endoglucanases target hemicellulose of the rice cell wall and release two specific oligosaccharides, namely the trisaccharide 31-β-D-Cellobiosyl-glucose and the tetrasaccharide 31-β-D-Cellotriosyl-glucose. 31-β-D-Cellobiosyl-glucose and 31-β-D-Cellotriosyl-glucose bind the immune receptor OsCERK1 but not the chitin binding protein OsCEBiP. However, they induce the dimerization of OsCERK1 and OsCEBiP. In addition, these Poaceae cell wall-specific oligosaccharides trigger a burst of reactive oxygen species (ROS) that is largely compromised in oscerk1 and oscebip mutants. We conclude that 31-β-D-Cellobiosyl-glucose and 31-β-D-Cellotriosyl-glucose are specific DAMPs released from the hemicellulose of rice cell wall, which are perceived by an OsCERK1 and OsCEBiP immune complex during M. oryzae infection in rice.

Underpotential deposition offers a predominant way to tailor the electronic structure of the catalytic surface at the atomic level, which is key to engineering materials with a high activity for (electro)catalysis. However, it remains challenging to precisely control and directly probe the underpotential deposition of a (sub)monolayer of atoms on nanoparticle surfaces. In this work, we in situ observe silver electrodeposited on gold nanocrystals surface from sub-monolayer to one monolayer by designing a highly sensitive electrochemical dark field scattering setup. The spectral variation is used to reconstruct the optical “cyclic voltammogram” of every single nanocrystal for understanding the underpotential deposition process on nanocrystals, which cannot be achieved by any other methods but are essential for creating novel nanomaterials., Underpotential deposition (UPD) is important to modify the surface properties of nanocrystals. Here, the authors show the application of in situ electrochemical dark field spectroscopy in identifying the UPD processes of silver on different facets of gold nanocrystals at the single nanoparticle level.

Plasmon-mediated chemical reactions (PMCRs) constitute a vibrant research field, advancing such goals as using sunlight to convert abundant precursors such as CO2 and water to useful fuels and chemicals. A key question in this burgeoning field which has not, as yet, been fully resolved, relates to the precise mechanism through which the energy absorbed through plasmonic excitation, ultimately drives such reactions. Among the multiple processes proposed, two have risen to the forefront: plasmon-increased temperature and generation of energetic charge carriers. However, it is still a great challenge to confidently separate these two effects and quantify their relative contribution to chemical reactions. Here, we describe a strategy based on the construction of a plasmonic electrode coupled with photoelectrochemistry, to quantitatively disentangle increased temperature from energetic charge carriers effects. A clear separation of the two effects facilitates the rational design of plasmonic nanostructures for efficient photochemical applications and solar energy utilization., Confidently separating the photothermal effect from the generation of energetic charge carriers and quantifying their relative contribution to chemical reactions remain a great challenge in plasmon-mediated chemical reactions. Here, authors describe a strategy based on the construction of a plasmonic electrode coupled with photoelectrochemistry to quantitatively disentangle these two effects.

Surface-enhanced Raman scattering (SERS) spectroscopy has attracted tremendous interests as a highly sensitive label-free tool. The local field produced by the excitation of localized surface plasmon resonances (LSPRs) dominates the overall enhancement of SERS. Such an electromagnetic enhancement is unfortunately accompanied by a strong modification in the relative intensity of the original Raman spectra, which highly distorts spectral features providing chemical information. Here we propose a robust method to retrieve the fingerprint of intrinsic chemical information from the SERS spectra. The method is established based on the finding that the SERS background originates from the LSPR-modulated photoluminescence, which contains the local field information shared also by SERS. We validate this concept of retrieval of intrinsic fingerprint information in well controlled single metallic nanoantennas of varying aspect ratios. We further demonstrate its unambiguity and generality in more complicated systems of tip-enhanced Raman spectroscopy (TERS) and SERS of silver nanoaggregates., We acknowledge support from NSFC (21633005, 21621091 and J1310024), MOST (2013CB933703 and 2016YFA0200601), MOE (IRT13036), and MINECO (FIS2016-80174-P) and Basque Government grant of UPV/EHU Grupos Consolidados IT-756-13. R.E. also acknowledges Fellow Gipuzkoa of the Gipuzkoako Foru Aldundia through the European Union’s FEDER program ‘Una manera de hacer Europa’.

The conductance of single-molecule junctions may be governed by the structure of the molecule in the gap or by the way it bonds with the leads, and the information contained in a Raman spectrum is ideal for examining both. Here we demonstrate that molecule-to-surface bonding may be characterized during electron transport by 'fishing-mode' tip-enhanced Raman spectroscopy (FM-TERS). This technique allows mutually verifiable single-molecule conductance and Raman signals with single-molecule contributions to be acquired simultaneously at room temperature. Density functional theory calculations reveal that the most significant spectral change seen for a gold-4,4′-bipyridine-gold junction results from the deformation of the pyridine ring in contact with the drain electrode at high voltage, and these calculations suggest that a stronger bonding interaction between the molecule and the drain may account for the nonlinear dependence of conductance on bias voltage. FM-TERS will lead to a better understanding of electron-transport processes in molecular junctions., The conductance of single-molecule junctions is affected by the structure of the molecule and how it is bound to the electrodes, which may be examined using Raman spectroscopy. Liu et al. have developed 'fishing-mode' tip-enhanced Raman spectroscopy, which allows the simultaneous determination of conductance and Raman spectra.