This article summarizes lessons learnt from ambient tip-enhanced Raman (TER) mapping of molecules interacting with plasmonic nanostructures. It is shown that numerous physical and chemical phenomena contribute to high-resolution TER spectral images. As a result, selectively tracking interfacial chemical transformations TERS is more challenging than currently appreciated.
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http://dx.doi.org/10.1039/d3cc00434a | DOI Listing |
J Phys Chem Lett
October 2024
Univ. Bordeaux, CNRS, Bordeaux INP, ISM, UMR 5255, F-33400 Talence, France.
Total-internal-reflection tip-enhanced Raman spectroscopy (TIR-TERS) imaging of amyloid-β (Aβ-L34T) fibrils is performed with nanoscale spatial resolution in water, using TERS tips fabricated by bipolar electrodeposition. Ideal experimental parameters are corroborated by both theoretical simulations and TIR-TERS measurements. TIR-TERS imaging reveals the predominant parallel β-sheet secondary structure of Aβ-L34T fibrils as well as the nanoscale spatial distribution of tyrosine, histidine, and phenylalanine aromatic amino acids.
View Article and Find Full Text PDFAdv Mater
August 2024
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
Collective excitations including plasmons, magnons, and layer-breathing vibration modes emerge at an ultralow frequency (<1 THz) and are crucial for understanding van der Waals materials. Strain at the nanoscale can drastically change the property of van der Waals materials and create localized states like quantum emitters. However, it remains unclear how nanoscale strain changes collective excitations.
View Article and Find Full Text PDFProc Natl Acad Sci U S A
April 2024
Physical Sciences Division, Pacific Northwest National Laboratory, Richland, WA 99352.
Chemical transformations near plasmonic metals have attracted increasing attention in the past few years. Specifically, reactions occurring within plasmonic nanojunctions that can be detected via surface and tip-enhanced Raman (SER and TER) scattering were the focus of numerous reports. In this context, even though the transition between localized and nonlocal (quantum) plasmons at nanojunctions is documented, its implications on plasmonic chemistry remain poorly understood.
View Article and Find Full Text PDFAnal Chem
February 2024
Physical Sciences Division, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352, United States.
Tip-enhanced Raman (TER) scattering from molecules residing at plasmonic junctions can be used to detect, identify, and image single molecules. This is most evident for flat molecules interrogated under conditions of extreme temperatures and pressure. It is also the case for (bio)molecular systems that feature preferred orientations/conformations under ambient laboratory conditions.
View Article and Find Full Text PDFPhys Chem Chem Phys
March 2024
Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, USA.
Graphene oxide (GO) has attracted substantial interest for its tunable properties and as a possible intermediate for the bulk manufacture of graphene. GO and its reduced derivatives display electronic and optical properties that depend strongly on their chemical structure, and with proper functionalization, GO can have a desirable bandgap for semiconductor applications. However, its chemical activity leads to a series of unclear chemical changes under ambient conditions, resulting in changes in color and solubility upon exposure to light.
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