Owing to its extreme sensitivity and easy execution, surface-enhanced Raman spectroscopy (SERS) now finds application for a wide variety of problems requiring sensitive and targeted analyte detection. This widespread application has prompted a proliferation of different SERS-based sensors, suggesting the need for a framework to classify existing methods and guide the development of new techniques. After a brief discussion of the general SERS modalities, we classify SERS-based sensors according the origin of the signal. Three major categories emerge from this analysis: surface-affinity strategy, SERS-tag strategy, and probe-mediated strategy. For each case, we describe the mechanism of action, give selected examples, and point out general misconceptions to aid the construction of new devices. We hope this review serves as a useful tutorial guide and helps readers to better classify and design practical and effective SERS-based sensors.

A method for the nanofabrication of periodic arrays of gold nanostars yielding a unique morphology of relevance to SERS applications.

The proliferation of N-heterocyclic carbene (NHC) self-assembled monolayers (SAMs) on gold surfaces stems from their exceptional stability compared to conventional thiol-SAMs. The prospect of biological applications for NHC-SAMs on gold shows the need for biocompatible techniques (e.g., large biomolecule detection and high throughput) that assesses SAM molecular composition. Herein, we demonstrate that laser desorption ionization mass spectrometry (LDI-MS) is a powerful and facile probe of NHC surface chemistry. LDI-MS of prototypical imidazole-NHC-and benzimidazole-NHC-functionalized AuNPs yields exclusively [NHC 2 Au] + ions and not larger gold clusters. Employing benzimidazole-NHC isotopologues, we explore how monolayers pack on a single AuNP and the lability of the NHCs once ligated. Quantitative analysis of the homoleptic and heteroleptic [NHC 2 Au] + ions is performed by comparing to a binomial model representative of a randomized monolayer. Lastly, the reduction of nitro-NHC-AuNPs to amine-NHC-AuNPs is tracked via LDI-MS signals, illustrating the ability of LDI-MS to probe postsynthetic modifications of the anchored NHCs, which is critical for current and future applications of NHC surfaces.

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Multiphoton microscopy using short-wave infrared (SWIR) radiation offers nondestructive and high-resolution imaging through tissue. Two-photon fluorescence (TPF), for example, is commonly employed to increase the penetration depth and spatial resolution of SWIR imaging, but the broad spectral peaks limit its multiplexing capabilities. Hyper-Raman scattering, the vibrational analog of TPF, yields spectral features on the order of 20 cm À1 and reporter-functionalized noble metal nanoparticles (NPs) provide a platform for both hyper-Raman signal enhancement and selective targeting in biological media. Herein we report the first tissue imaging study employing surfaceenhanced resonance hyper-Raman scattering (SERHRS), the two-photon analog of surface-enhanced resonance Raman scattering. Specifically, we employ multicore gold-silica NPs (Au@SiO 2 NPs) functionalized with a near infrared-resonant cyanine dye, 3,3 0 -diethylthiatricarbocyanine iodide as a SERHRS reporter. SWIR SERHRS spectra are efficiently acquired from mouse spleen tissue. SWIR SERHRS combines two-photon imaging advantages with narrow vibrational peak widths, presenting future applications of multitargeted bioimaging. K E Y W O R D Sshort-wave infrared (SWIR), surface-enhanced Raman scattering (SERS), surface-enhanced hyper Raman scattering (SEHRS), surface-enhanced resonance hyper-Raman scattering (SERHRS)