Smart supramolecular sensing with cucurbit[<i>n</i>]urils: probing hydrogen bonding with SERS

Nijs, Bart de; Kamp, Marlous; Szabó, István; Barrow, Steven J.; Benz, Felix; Wu, Guanglu; Carnegie, Cloudy; Chikkaraddy, Rohit; Wang, Wenting; Deacon, William; Rosta, Edina; Baumberg, Jeremy J.; Scherman, Oren A.

doi:10.1039/c7fd00147a

Cited by 20 publications

(25 citation statements)

References 46 publications

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“…This is in line with earlier observations for ethanol/methanol sensing using CB[5]. 36 PCA is used to isolate the spectral changes and identify their corresponding chemical moieties (Figure 2c, bottom). PCA allows correlated variables (in this case, spectral features) to be identified and through orthogonal transformations to be combined into uncorrelated linear combinations of spectra.…”

Section: Resultssupporting

confidence: 87%

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Inhibiting Analyte Theft in Surface-Enhanced Raman Spectroscopy Substrates: Subnanomolar Quantitative Drug Detection

et al. 2019

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Quantitative applications of surface-enhanced Raman spectroscopy (SERS) often rely on surface partition layers grafted to SERS substrates to collect and trap-solvated analytes that would not otherwise adsorb onto metals. Such binding layers drastically broaden the scope of analytes that can be probed. However, excess binding sites introduced by this partition layer also trap analytes outside the plasmonic “hotspots”. We show that by eliminating these binding sites, limits of detection (LODs) can effectively be lowered by more than an order of magnitude. We highlight the effectiveness of this approach by demonstrating quantitative detection of controlled drugs down to subnanomolar concentrations in aqueous media. Such LODs are low enough to screen, for example, urine at clinically relevant levels. These findings provide unique insights into the binding behavior of analytes, which are essential when designing high-performance SERS substrates.

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Section: Resultssupporting

confidence: 87%

“…When using the smaller CB[5] molecule, size selection prevents the binding of anything larger than methane or methanol inside the small CB volume. 25,36 This prevents analytes from adsorbing at sites outside the hotspot leaving only the interstitial incorporation mechanism to capture analytes (Figure 2b).…”

Section: Resultsmentioning

confidence: 99%

Inhibiting Analyte Theft in Surface-Enhanced Raman Spectroscopy Substrates: Subnanomolar Quantitative Drug Detection

et al. 2019

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“…The extreme sensitivity of surface-enhanced Raman spectroscopy (SERS) makes this technique a promising and powerful sensing platform. [1] With hardware components such as lasers and detectors rapidly reducing in cost, SERS has the potential to become an economically viable technique [2] with broad adoption in medical diagnosis, [2] environmental monitoring, [3] drug detection, [4] food quality control [5][6][7][8][9][10] and continuous health screening. [11] As first identified by Jeanmaire and van Duyne in 1977, this extraordinary sensitivity stems from the powerful field enhancements that can arise in nanostructured metal surfaces.…”

Section: Introductionmentioning

confidence: 99%

Eliminating irreproducibility in SERS substrates

Grys

Chikkaraddy

Kamp

et al. 2020

J Raman Spectroscopy

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Irreproducibility in surface-enhanced Raman spectroscopy (SERS) due to variability among substrates is a source of recurrent debate within the field. It is regarded as a major hurdle towards the widespread adoption of SERS as a sensing platform. Most of the literature focused on developing substrates for various applications considers reproducibility of lower importance. Here, we address and analyse the sources of this irreproducibility in order to show how these can be minimised. We apply our findings to a simple substrate demonstrating reproducible SERS measurements with relative standard deviations well below 1% between different batches and days. Identifying the sources of irreproducibility and understanding how to reduce these can aid in the transition of SERS from the lab to real-world applications.

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“…In comparison with other linker molecules, such as dithiols, CB[ n ]-mediated dimer assembly enables to reduce the interparticle gap sizes down to the sub-nanometer regime. As a consequence, nanoparticle aggregates induced by interactions with CB[ n ]s have been shown to provide strong interparticle hot-spots, and thus, to be well-suited as SERS substrates [54–55]. The high reactivity of CB[ n ]s with Au surfaces may lead to the uncontrolled formation nanoparticle aggregates in solution, and often prevents a controlled self-assembly into dimers or small oligomer structures.…”

Section: Resultsmentioning

confidence: 99%

Dumbbell gold nanoparticle dimer antennas with advanced optical properties

Herrmann

Höppener

2018

Beilstein J. Nanotechnol.

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Plasmonic nanoantennas have found broad applications in the fields of photovoltaics, electroluminescence, non-linear optics and for plasmon enhanced spectroscopy and microscopy. Of particular interest are fundamental limitations beyond the dipolar approximation limit. We introduce asymmetric gold nanoparticle antennas (AuNPs) with improved optical near-field properties based on the formation of sub-nanometer size gaps, which are suitable for studying matter with high-resolution and single molecule sensitivity. These dumbbell antennas are characterized in regard to their far-field and near-field properties and are compared to similar dimer and trimer antennas with larger gap sizes. The tailoring of the gap size down to sub-nanometer length scales is based on the integration of rigid macrocyclic cucurbituril molecules. Stable dimer antennas are formed with an improved ratio of the electromagnetic field enhancement and confinement. This ratio, taken as a measure of the performance of an antenna, can even exceed that exhibited by trimer AuNP antennas composed of comparable building blocks with larger gap sizes. Fluctuations in the far-field and near-field properties are observed, which are likely caused by distinct deviations of the gap geometry arising from the faceted structure of the applied colloidal AuNPs.

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Smart supramolecular sensing with cucurbit[n]urils: probing hydrogen bonding with SERS

Cited by 20 publications

References 46 publications

Inhibiting Analyte Theft in Surface-Enhanced Raman Spectroscopy Substrates: Subnanomolar Quantitative Drug Detection

Inhibiting Analyte Theft in Surface-Enhanced Raman Spectroscopy Substrates: Subnanomolar Quantitative Drug Detection

Eliminating irreproducibility in SERS substrates

Dumbbell gold nanoparticle dimer antennas with advanced optical properties

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