Role of chemical interface damping for tuning chemical enhancement in resonance surface-enhanced Raman scattering of plasmonic gold nanorods

Seo, Min; Kim, Geun Wan; Tsalu, Philippe Vuka; Moon, Seong Woo; Ha, Ji Won

doi:10.1039/c9nh00524b

Cited by 49 publications

(43 citation statements)

References 26 publications

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“…[13][14][15][16][17][18][19] In these chemical processes, the presence of closely or strongly interacting adsorbate molecules induces the direct generation of hot electrons for the empty lowest unoccupied molecular orbitals (LUMOs) of the adsorbate (Scheme 1A). 1,[20][21][22][23] In addition to the direct electron transfer, CID has a component of scattering of the electronic waves by a disordered potential at the surface. Accordingly, the LSPR spectral frequency is red-shifted and suffers a loss in intensity and a broadening of the full linewidth at half maximum (FWHM).…”

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confidence: 99%

In situ reversible tuning of chemical interface damping in single gold nanorod-based recyclable platforms through manipulation of supramolecular host–guest interactions

et al. 2021

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confidence: 99%

In situ reversible tuning of chemical interface damping in single gold nanorod-based recyclable platforms through manipulation of supramolecular host–guest interactions

et al. 2021

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“…The conceptual mathematical processing for obtaining these spectra can be found in the Supporting Information section Mathematical Approach for Deriving Cluster Analysis Spectra. We identified six regions of interest: 931 (C–C ring stretching in, e.g., proline), 1095 (PO 2– stretching, C–C stretching, C–O–C stretching, glycosidic link in DNA/RNA), 1360 (CH 2 , CH 3 wagging in proteins), 1445 (CH 2 and CH 3 deformations in proteins and lipids), 1590 (C–C ring vibration in aromatic groups), and 1620 cm –1 (C=C vibration in, e.g., proteins) (Table ). Based on these peak assignments, the measured EVs forming the blue cluster are seemingly enriched in nucleic acid (DNA/RNA)-related vibrations whereas the red cluster represents the majority of the EVs, which are relatively consistent with the overall global average spectrum with the exception of fewer CH 2 /CH 3 wagging vibrations from proteins.…”

Section: Results and Discussionmentioning

confidence: 99%

Hybrid Nanoplasmonic Porous Biomaterial Scaffold for Liquid Biopsy Diagnostics Using Extracellular Vesicles

et al. 2020

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For more effective early-stage cancer diagnostics, there is a need to develop sensitive and specific, non-or minimally invasive, and cost-effective methods for identifying circulating nanoscale extracellular vesicles (EVs). Here, we report the utilization of a simple plasmonic scaffold composed of a microscale biosilicate substrate embedded with silver nanoparticles for surface-enhanced Raman scattering (SERS) analysis of ovarian and endometrial cancer EVs. These substrates are rapidly and inexpensively produced without any complex equipment or lithography. We extensively characterize the substrates with electron microscopy and outline a reproducible methodology for their use in analyzing EVs from in vitro and in vivo biofluids. We report effective chemical treatments for (i) decoration of metal surfaces with cysteamine to nonspecifically pull down EVs to SERS hotspots and (ii) enzymatic cleavage of extraluminal moieties at the surface of EVs that prevent localization of complementary chemical features (lipids/proteins) to the vicinity of the metal-enhanced fields. We observe a major loss of sensitivity for ovarian and endometrial cancer following enzymatic cleavage of EVs' extraluminal domain, suggesting its critical significance for diagnostic platforms. We demonstrate that the SERS technique represents an ideal tool to assess and measure the high heterogeneity of EVs isolated from clinical samples in an inexpensive, rapid, and label-free assay.

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“…This study therefore used p ‐NTP (or 4‐NTP) as the adsorbate molecule for inducing CID in single AuNRs@mSiO 2 . We first checked the effective adsorption of p ‐NTP on the AuNR cores through the mesoporous silica shell using SERS, a vibrational spectroscopy tool prividing fine molecular fingerprints 29,30 . We recently demonstrated that CID is closely connected to the chemical enhancement mechanism of SERS, as depicted in Figure 1a, 30 and hence, an SERS study can also enable us to acquire a better insight into the CID effect in single AuNRs@mSiO 2 .…”

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Single‐particle correlation study: Chemical interface damping in gold nanorods coated with mesoporous silica shell

Heo

2022

Bulletin Korean Chem Soc

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Chemical interface damping (CID) is the most recently suggested plasmon damping pathway induced by adsorbate molecules in gold nanoparticles. Despite recent advances in this field, CID has not been studied in gold nanorods coated with mesoporous silica shells (AuNRs@mSiO2). Herein, we conducted a single‐particle correlation study to elucidate CID using p‐nitrothiophenol (p‐NTP) as adsorbates in single AuNRs@mSiO2. Through surface‐enhanced Raman spectroscopy studies, we confirmed that p‐NTP with a strong electron‐withdrawing group was effectively adsorbed on the AuNR cores. Following the chemisorption of p‐NTP, a strong CID was observed with localized surface plasmon resonance (LSPR) linewidth broadening through the preferred interaction between sulfur and the Au surfaces. Furthermore, we presented the molecular binding effect on the LSPR linewidth of single AuNRs@mSiO2 during the reaction with p‐NTP in real‐time. Thus, the result further supported that the CID could be used to develop LSPR sensors having low sensitivity to the medium dielectric constant.

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Role of chemical interface damping for tuning chemical enhancement in resonance surface-enhanced Raman scattering of plasmonic gold nanorods

Abstract: Chemical interface damping in plasmonic gold nanoparticles is closely connected with chemical enhancement in resonance SERS.

Cited by 49 publications

References 26 publications

In situ reversible tuning of chemical interface damping in single gold nanorod-based recyclable platforms through manipulation of supramolecular host–guest interactions

In situ reversible tuning of chemical interface damping in single gold nanorod-based recyclable platforms through manipulation of supramolecular host–guest interactions

Hybrid Nanoplasmonic Porous Biomaterial Scaffold for Liquid Biopsy Diagnostics Using Extracellular Vesicles

Single‐particle correlation study: Chemical interface damping in gold nanorods coated with mesoporous silica shell

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