Can “Hot Spots” Be Stable Enough for Surface-Enhanced Raman Scattering?

Zhu, Manzhou; Li, Moxia; Su, Mengke; Liu, Jianfang; Liu, Bingwu; Ge, Yifei; Liu, Honglin; Hu, Jiawen

doi:10.1021/acs.jpcc.1c03321

Cited by 20 publications

(6 citation statements)

References 23 publications

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“…Tracking changes in the PL did not provide any obvious indication of a corresponding loss of nanoparticles during the potential step cycle. This suggests that some other alteration of the surface or nanoparticle arrangement, and thereby diminished Raman enhancement, has occurred that remains to be understood. − In contrast, the potentiodynamic version of the experiment (Figure S11, see SI for experimental details) performed within the same potential limits suggests, within the sensitivity of the measurement, that the loss in peak area observed for ν(c(2 × 2) Cl – ) may be a function of the time spent at potentials that yield complete Cl – desorption. Most interestingly, a new P3 mode emerges at potentials below −1.05 V with a broad peak near 205 cm –1 that overlaps with bulk hydride as well as clean surface lattice modes (Figure and Table ).…”

Section: Resultsmentioning

confidence: 99%

“…The present work investigates the halide adsorption on Cu (100) using a powerful variant of Raman spectroscopy known as shell-isolated nanoparticle enhanced Raman spectroscopy, or SHINERS, that enables the surface chemistry on otherwise Raman-inactive planar single crystal surfaces to be studied. ,− Specifically, chemically inert, silica-passivated plasmonic active gold nanoparticles are distributed on the flat surface of interest where they serve as antenna to focus the optical laser power for enhanced Raman spectroscopy of species adsorbed within and/or adjacent to the nanoparticle–substrate junction. − Attention is given to the potential dependence of halide coverage and the impact of the c(2 × 2) Cl – adlayer on step faceting at positive potentials and c(2 × 2) templating of the adjacent water and hydronium species. At more negative potentials, another phase transition, perhaps hydride formation, is evident, accompanied by the development of another vibrational mode that marks the boundary between Cl – desorption and the onset of significant hydrogen evolution.…”

Section: Introductionmentioning

confidence: 99%

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SHINERS Study of Chloride Order–Disorder Phase Transition and Solvation of Cu(100)

Raciti,

Cockayne,

Vinson

et al. 2024

J. Am. Chem. Soc.

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Shell-isolated nanoparticle enhanced Raman spectroscopy (SHINERS) and density functional theory (DFT) are used to probe Cl − adsorption and the order−disorder phase transition associated with the c(2 × 2) Cl − adlayer on Cu(100) in acid media. A two-component ν(Cu−Cl) vibrational band centered near 260 ± 1 cm −1 is used to track the potential dependence of Cl − adsorption. The potential dependence of the dominant 260 cm −1 component tracks the coverage of the fluctional c(2 × 2) Cl − phase on terraces in good agreement with the normalized intensity of the c(2 × 2) superstructure rods in prior surface X-ray diffraction (SXRD) studies. As the c(2 × 2) Cl − coverage approaches saturation, a second ν(Cu−Cl) component mode emerges between 290 and 300 cm −1 that coincides with the onset and stiffening of step faceting where Cl − occupies the threefold hollow sites to stabilize the metal kink saturated Cu <100> step edge. The formation of the c(2 × 2) Cl − adlayer is accompanied by the strengthening of ν(O−H) stretching modes in the adjacent non-hydrogen-bonded water at 3600 cm −1 and an increase in hydronium concentration evident in the flanking H 2 O modes at 3100 cm −1 . The polarization of the water molecules and enrichment of hydronium arise from the combination of Cl − anionic character and lateral templating provided by the c(2 × 2) adlayer, consistent with SXRD studies. At negative potentials, Cl − desorption occurs followed by development of a sulfate ν s (S�O) band. Below −1.1 V vs Hg/HgSO 4 , a new 200 cm −1 mode emerges congruent with hydride formation and surface reconstruction reported in electrochemical scanning tunneling microscopy studies.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

SHINERS Study of Chloride Order–Disorder Phase Transition and Solvation of Cu(100)

Raciti,

Cockayne,

Vinson

et al. 2024

J. Am. Chem. Soc.

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“…Of particular interest is the aggregation of colloidal metal nanoparticles, which provides a high EF. For example, the random aggregation of spherical and complex nanoparticles can lead to the formation of regions with a strongly enhanced electromagnetic field, known as “hot spots” [ 95 ]. When the biomolecule is close to this region, the Raman enhancement increases up to 10 15 orders of magnitude, and a single-molecule detection can be achieved [ 96 ].…”

Section: Application Of Sers and Sers-combined Raman Techniques In The Detection Of Biomoleculesmentioning

confidence: 99%

Raman Scattering-Based Biosensing: New Prospects and Opportunities

et al. 2021

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The growing interest in the development of new platforms for the application of Raman spectroscopy techniques in biosensor technologies is driven by the potential of these techniques in identifying chemical compounds, as well as structural and functional features of biomolecules. The effect of Raman scattering is a result of inelastic light scattering processes, which lead to the emission of scattered light with a different frequency associated with molecular vibrations of the identified molecule. Spontaneous Raman scattering is usually weak, resulting in complexities with the separation of weak inelastically scattered light and intense Rayleigh scattering. These limitations have led to the development of various techniques for enhancing Raman scattering, including resonance Raman spectroscopy (RRS) and nonlinear Raman spectroscopy (coherent anti-Stokes Raman spectroscopy and stimulated Raman spectroscopy). Furthermore, the discovery of the phenomenon of enhanced Raman scattering near metallic nanostructures gave impetus to the development of the surface-enhanced Raman spectroscopy (SERS) as well as its combination with resonance Raman spectroscopy and nonlinear Raman spectroscopic techniques. The combination of nonlinear and resonant optical effects with metal substrates or nanoparticles can be used to increase speed, spatial resolution, and signal amplification in Raman spectroscopy, making these techniques promising for the analysis and characterization of biological samples. This review provides the main provisions of the listed Raman techniques and the advantages and limitations present when applied to life sciences research. The recent advances in SERS and SERS-combined techniques are summarized, such as SERRS, SE-CARS, and SE-SRS for bioimaging and the biosensing of molecules, which form the basis for potential future applications of these techniques in biosensor technology. In addition, an overview is given of the main tools for success in the development of biosensors based on Raman spectroscopy techniques, which can be achieved by choosing one or a combination of the following approaches: (i) fabrication of a reproducible SERS substrate, (ii) synthesis of the SERS nanotag, and (iii) implementation of new platforms for on-site testing.

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“…[17,18] Colloidal nanoparticles such as silver (AgNPs) and gold (AuNPs) are commonly used SERS substrates, but use of nanoparticles can cause spectral fluctuations due to their uncontrolled and random aggregation. [19] Recently, a practical way to form reproducible hotspots is proposed by controlled aggregation of colloidal nanoparticles in presence of using inorganic salts such as NaCl, MgSO 4 , and CuSO 4 . [20,21] This method is relatively cost-effective and has a simple process for preparation of SERS substrate.…”

mentioning

confidence: 99%

Characterization and discrimination of spike protein in SARS‐CoV‐2 virus‐like particles via surface‐enhanced Raman spectroscopy

Akdeniz,

Al‐Shaebi,

Altunbek

et al. 2023

Biotechnology Journal

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Non‐infectious virus‐like particles (VLPs) are excellent structures for development of many biomedical applications such as drug delivery systems, vaccine production platforms, and detection techniques for infectious diseases including SARS‐CoV‐2 VLPs. The characterization of biochemical and biophysical properties of purified VLPs is crucial for development of detection methods and therapeutics. The presence of spike (S) protein in their structure is especially important since S protein induces immunological response. In this study, development of a rapid, low‐cost, and easy‐to‐use technique for both characterization and detection of S protein in the two VLPs, which are SARS‐CoV‐2 VLPs and HIV‐based VLPs was achieved using surface‐enhanced Raman spectroscopy (SERS). To analyze and classify datasets of SERS spectra obtained from the VLP groups, machine learning classification techniques including support vector machine (SVM), k‐nearest neighbors (kNN), and random forest (RF) were utilized. Among them, the SVM classification algorithm demonstrated the best classification performance for SARS‐CoV‐2 VLPs and HIV‐based VLPs groups with 87.5% and 92.5% accuracy, respectively. This study could be valuable for the rapid characterization of VLPs for the development of novel therapeutics or detection of structural proteins of viruses leading to a variety of infectious diseases.

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Can “Hot Spots” Be Stable Enough for Surface-Enhanced Raman Scattering?

Cited by 20 publications

References 23 publications

SHINERS Study of Chloride Order–Disorder Phase Transition and Solvation of Cu(100)

SHINERS Study of Chloride Order–Disorder Phase Transition and Solvation of Cu(100)

Raman Scattering-Based Biosensing: New Prospects and Opportunities

Characterization and discrimination of spike protein in SARS‐CoV‐2 virus‐like particles via surface‐enhanced Raman spectroscopy

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