Appearance of SERS activity in single silver nanoparticles by laser-induced reshaping.
TL;DR: Time-lapse observations have shown that laser-induced changes in the plasmonic properties of AgNPs resulted in the appearance of SERS, and it is shown that the release of silver ions by silver nanoparticles can be the probable reason for their plAsmonic changes.
Abstract: We report simultaneous plasmonic scattering and Raman spectroscopic observations of single citrate capped silver nanoparticles (AgNPs) which exhibit surface enhanced Raman scattering (SERS) upon meeting specific conditions induced by laser (532 nm) exposure. We show that nanoparticles which are not initially SERS active become SERS active by laser-induced reshaping/reorientation. A set-up developed for these observations enabled in situ high speed time-lapse characterization using plasmonic and Raman spectroscopies in conjunction with dark-field microscopy (DFM). Changes in the AgNPs were confirmed by monitoring plasmonic scattering spectra and DFM images. Time-lapse observations have shown that laser-induced changes in the plasmonic properties of AgNPs resulted in the appearance of SERS. Spectral matching between plasmon resonance and downward molecular vibronic transitions for molecules adsorbed on the surface of plasmonic nanomaterials is attributed to the nanoparticle SERS. We have further shown that the release of silver ions by silver nanoparticles can be the probable reason for their plasmonic changes. Gold nanoparticles inert to such mild (850 μW, 532 nm) laser-induced changes do not exhibit the appearance of SERS.
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TL;DR: In this paper, the authors developed an easy and eco-friendly method for the synthesis of three different concentrations of silver nanoparticles (1mMCvAgNPs, 2m MCvAgNs, and 3mMcvNPs) using aqueous whole plant extract of Cleome viscosa and evaluated their antibacterial, antioxidant and antidiabetic properties.
23 citations
Cites background from "Appearance of SERS activity in sing..."
...Among these metal-NPs, silver nanoparticles (AgNPs) are considered as most suitable for to the surface plasmon resonance (SPR), which can be effectively seen by UV–vis spectrophotometer (Chaudhari et al., 2019)....
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TL;DR: This work emphasizes the role of Ag+, Ca2+, Pb2+ and Al3+ adions in the specific adsorption of anionic analytes such as the citrate capping agent and three organic acids and suggests an adion-specific adsorptive mechanism.
Abstract: In our recent studies we highlighted the role of adsorbed ions (adions) in turning on the surface-enhanced Raman scattering (SERS) effect in a specific mode for anionic and cationic analytes. In this work, we emphasize the role of Ag+, Ca2+, Pb2+ and Al3+ adions in the specific adsorption of anionic analytes such as the citrate capping agent and three organic acids. Our results suggest an adion-specific adsorption mechanism: the adsorption of anionic analytes is facilitated by positively charged adions such as Ag+, Ca2+, Pb2+ or Al3+, which provide adsorption sites specific for the anionic analytes. The turn-on of the SERS effect is explained in the context of the chemical mechanism of SERS. The adions form SERS-active sites on the silver surface enabling a charge transfer between the adsorbate and the silver surface. High-intensity SERS spectra of uric acid, salicylic acid and fumaric acid could be recorded at a concentration of 50 µM only after activation of the colloidal silver nanoparticles by Ca2+, Pb2+ or Al3+ (50 µM). The chemisorption of the three anionic species to the silver surface occurs competitively and is enhanced with the anions of higher affinities to the silver surface as indicated by the SERS spectra of corresponding mixed solutions.
19 citations
TL;DR: For maintaining water quality, planning remediation strategies and ecosystem restoration, the detection of metal ions in aquatic water bodies is very important as discussed by the authors, where colorimetry as well as plasmon-enhan...
Abstract: For maintaining water quality, planning remediation strategies and ecosystem restoration, the detection of metal ions in aquatic water bodies is very important. Colorimetry as well as plasmon-enhan...
14 citations
TL;DR: Reduced analysis time and improved reproducibility of the data in every analysis, which is generally difficult in SERS, the amount of AgNPs required is an order of magnitude lower in this method, which could also be used to probe the real-time changes in molecular and biological species under ambient conditions.
Abstract: We introduce a technique called ambient electrospray deposition Raman spectroscopy (AESD RS) for rapid and sensitive surface-enhanced Raman scattering (SERS) based detection of analytes using a miniature Raman spectrometer. Using electrospray, soft landing of preformed silver nanoparticles (AgNPs) was performed for 30-40 seconds for different concentrations of analytes deposited on conducting glass slides. Using AESD RS, SERS signals were collected within 4-6 minutes, including sample preparation. Transmission electron microscopy (TEM) and dark-field microscopy (DFM) were used to characterize the preformed AgNPs before and after electrospray. We achieved the nanomolar and micromolar detection of p-mercaptobenzoic acid (p-MBA) and 2,4-dinitrotoluene (2,4-DNT), respectively. In this work, 0.3 μL of preformed AgNPs were used, which is ∼33 times less in volume than the quantity needed for conventional SERS. Quantitation of unknown concentration of analytes was also possible. A similar amount of electrosprayed AgNPs was utilized to characterize Escherichia coli (E. coli) bacteria of different concentrations. Viability of bacteria was tested using fluorescence microscopic imaging. Besides reduced analysis time and improved reproducibility of the data in every analysis, which is generally difficult in SERS, the amount of AgNPs required is an order of magnitude lower in this method. This method could also be used to probe the real-time changes in molecular and biological species under ambient conditions.
9 citations
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TL;DR: While nanorods with a higher aspect ratio along with a smaller effective radius are the best photoabsorbing nanoparticles, the highest scattering contrast for imaging applications is obtained from nanorod of high aspect ratio with a larger effective radius.
Abstract: The selection of nanoparticles for achieving efficient contrast for biological and cell imaging applications, as well as for photothermal therapeutic applications, is based on the optical properties of the nanoparticles. We use Mie theory and discrete dipole approximation method to calculate absorption and scattering efficiencies and optical resonance wavelengths for three commonly used classes of nanoparticles: gold nanospheres, silica−gold nanoshells, and gold nanorods. The calculated spectra clearly reflect the well-known dependence of nanoparticle optical properties viz. the resonance wavelength, the extinction cross-section, and the ratio of scattering to absorption, on the nanoparticle dimensions. A systematic quantitative study of the various trends is presented. By increasing the size of gold nanospheres from 20 to 80 nm, the magnitude of extinction as well as the relative contribution of scattering to the extinction rapidly increases. Gold nanospheres in the size range commonly employed (∼40 nm)...
4,065 citations
TL;DR: It is found that gold particles can be produced in a wide range of sizes, from 9 to 120 nm, with defined size distribution, following the earlier work of Turkevich and Frens.
Abstract: The growth of gold nanoparticles by reduction by citrate and ascorbic acid has been examined in detail to explore the parameter space of reaction conditions. It is found that gold particles can be produced in a wide range of sizes, from 9 to 120 nm, with defined size distribution, following the earlier work of Turkevich and Frens. The reaction is initiated thermally or in comparison by UV irradiation, which results in similar final products. The kinetics of the extinction spectra show the multiple steps of primary and secondary clustering leading to polycrystallites.
1,906 citations
TL;DR: By utilizing dual excitation of plasmons at metal-fluid interface, this work creates interacting assemblies of metal nanoparticles, which may be further harnessed in dynamic lithography of dispersed nanostructures and have implications in realizing optically addressable, plasmofluidic, single-molecule detection platforms.
Abstract: Single-molecule surface-enhanced Raman scattering (SM-SERS) is one of the vital applications of plasmonic nanoparticles. The SM-SERS sensitivity critically depends on plasmonic hot-spots created at the vicinity of such nanoparticles. In conventional fluid-phase SM-SERS experiments, plasmonic hot-spots are facilitated by chemical aggregation of nanoparticles. Such aggregation is usually irreversible, and hence, nanoparticles cannot be re-dispersed in the fluid for further use. Here, we show how to combine SM-SERS with plasmon polariton-assisted, reversible assembly of plasmonic nanoparticles at an unstructured metal–fluid interface. One of the unique features of our method is that we use a single evanescent-wave optical excitation for nanoparticle assembly, manipulation and SM-SERS measurements. Furthermore, by utilizing dual excitation of plasmons at metal–fluid interface, we create interacting assemblies of metal nanoparticles, which may be further harnessed in dynamic lithography of dispersed nanostructures. Our work will have implications in realizing optically addressable, plasmofluidic, single-molecule detection platforms. Plasmonic hot-spot generation in solution is not reversible for single-molecule surface-enhanced Raman scattering, which limits its applications. Patra et al.tackle this problem by integrating this technique with thermo-plasmon-assisted reconfiguration of nanoparticles at a metal–fluid interface.
1,705 citations
TL;DR: Raman spectral imaging with spatial resolution below one nanometre is demonstrated, resolving the inner structure and surface configuration of a single molecule by spectrally matching the resonance of the nanocavity plasmon to the molecular vibronic transitions, particularly the downward transition responsible for the emission of Raman photons.
Abstract: Chemical mapping of a single molecule by optical means down to subnanometre resolution is achieved by spectrally matching the resonance of a nanocavity plasmon to the vibronic transitions of the molecules being studied, using tip-enhanced Raman scattering. Raman spectroscopy is widely used to identify molecules by detecting their signature molecular vibrations. The technology has been refined to be effective at the single-molecule level by making use of strong localized plasmonic fields that can enhance spectral signals. This study goes further, with the demonstration of a technique related to 'tip-enhanced Raman scattering' (TERS) that allows precise tuning of the plasmon resonance and Raman spectral imaging with a spatial resolution below 1 nm, resolving even the inner structure of a single molecule and its configuration on the surface. The technique opens a new path to photochemistry at the single-molecule level, offering the potential to design, control and engineer the functionality of molecules on demand. Visualizing individual molecules with chemical recognition is a longstanding target in catalysis, molecular nanotechnology and biotechnology. Molecular vibrations provide a valuable ‘fingerprint’ for such identification. Vibrational spectroscopy based on tip-enhanced Raman scattering allows us to access the spectral signals of molecular species very efficiently via the strong localized plasmonic fields produced at the tip apex1,2,3,4,5,6,7,8,9,10,11. However, the best spatial resolution of the tip-enhanced Raman scattering imaging is still limited to 3−15 nanometres5,12,13,14,15,16, which is not adequate for resolving a single molecule chemically. Here we demonstrate Raman spectral imaging with spatial resolution below one nanometre, resolving the inner structure and surface configuration of a single molecule. This is achieved by spectrally matching the resonance of the nanocavity plasmon to the molecular vibronic transitions, particularly the downward transition responsible for the emission of Raman photons. This matching is made possible by the extremely precise tuning capability provided by scanning tunnelling microscopy. Experimental evidence suggests that the highly confined and broadband nature of the nanocavity plasmon field in the tunnelling gap is essential for ultrahigh-resolution imaging through the generation of an efficient double-resonance enhancement for both Raman excitation and Raman emission. Our technique not only allows for chemical imaging at the single-molecule level, but also offers a new way to study the optical processes and photochemistry of a single molecule.
1,425 citations
TL;DR: An electroluminescent material is presented that is capable of large uniaxial stretching and surface area changes while actively emitting light and is combined in a stretchable electronic material suitable for soft robotics.
Abstract: Cephalopods such as octopuses have a combination of a stretchable skin and color-tuning organs to control both posture and color for visual communication and disguise. We present an electroluminescent material that is capable of large uniaxial stretching and surface area changes while actively emitting light. Layers of transparent hydrogel electrodes sandwich a ZnS phosphor-doped dielectric elastomer layer, creating thin rubber sheets that change illuminance and capacitance under deformation. Arrays of individually controllable pixels in thin rubber sheets were fabricated using replica molding and were subjected to stretching, folding, and rolling to demonstrate their use as stretchable displays. These sheets were then integrated into the skin of a soft robot, providing it with dynamic coloration and sensory feedback from external and internal stimuli.
1,008 citations