Browse
Submit Data
Databases
API
Help

Dataset Information

26 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

High-resolution tip-enhanced Raman scattering probes sub-molecular density changes.

ABSTRACT: Tip-enhanced Raman spectroscopy (TERS) exhibits new selection rule and sub-nanometer spatial resolution, which is attributed to the plasmonic near-field confinement. Despite recent advances in simulations of TERS spectra under highly confined fields, a simply physical mechanism has remained elusive. In this work we show that single-molecule TERS images can be explained by local sub-molecular density changes induced by the confined near-field during the Raman process. The local sub-molecular density changes determine the spatial resolution in TERS and the gradient-based selection rule. Using this approach we find that the four-fold symmetry of meso-tetrakis(3,5-di-tert-butylphenyl)porphyrin (H₂TBPP) TERS images observed in experiments arises from the combination of degenerate normal modes localized in the functional side groups rather than the porphyrin ring as previously considered. As an illustration of the potential of the method, we demonstrate how this new theory can be applied to microscopic structure characterization.

SUBMITTER: Chen X

PROVIDER: S-EPMC6561954 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Resolving the Correlation between Tip-Enhanced Resonance Raman Scattering and Local Electronic States with 1 nm Resolution.

Project description:Low-temperature tip-enhanced Raman spectroscopy (TERS) enables chemical identification with single-molecule sensitivity and extremely high spatial resolution even down to the atomic scale. The large enhancement of Raman scattering obtained in TERS can originate from physical and/or chemical enhancement mechanisms. Whereas physical enhancement requires a strong near-field through excitation of localized surface plasmons, chemical enhancement is governed by resonance in the electronic structure of the sample, which is also known as resonance Raman spectroscopy. Here we report on tip-enhanced resonance Raman spectroscopy (TERRS) of ultrathin ZnO layers epitaxially grown on a Ag(111) surface, where both enhancement mechanisms are operative. In combination with scanning tunneling spectroscopy (STS), it is demonstrated that the TERRS intensity strongly depends on the local electronic resonance of the ZnO/Ag(111) interface. We also reveal that the spatial resolution of TERRS is dependent on the tip-surface distance and reaches nearly 1 nm in the tunneling regime, which can be rationalized by strong-field confinement resulting from an atomic-scale protrusion on the tip apex. Comparison of STS and TERRS mapping clearly shows a correlation between resonantly enhanced Raman scattering and the local electronic states at near-atomic resolution. Our results suggest that TERRS is a new approach for the atomic-scale optical characterization of local electronic states.

| S-EPMC6748789 | biostudies-literature

First-Principles Simulations of Tip Enhanced Raman Scattering Reveal Active Role of Substrate on High-Resolution Images.

Project description:Tip-enhanced Raman scattering (TERS) has emerged as a powerful tool to obtain subnanometer spatial resolution fingerprints of atomic motion. Theoretical calculations that can simulate the Raman scattering process and provide an unambiguous interpretation of TERS images often rely on crude approximations of the local electric field. In this work, we present a novel and first-principles-based method to compute TERS images by combining Time Dependent Density Functional Theory (TD-DFT) and Density Functional Perturbation Theory (DFPT) to calculate Raman cross sections with realistic local fields. We present TERS results on free-standing benzene and C60 molecules, and on the TCNE molecule adsorbed on Ag(100). We demonstrate that chemical effects on chemisorbed molecules, often ignored in TERS simulations of larger systems, dramatically change the TERS images. This observation calls for the inclusion of chemical effects for predictive theory-experiment comparisons and an understanding of molecular motion at the nanoscale.

| S-EPMC10405274 | biostudies-literature

Resonant tip-enhanced Raman scattering by CdSe nanocrystals on plasmonic substrates.

Project description:Tip-enhanced Raman scattering (TERS) has recently emerged as a powerful technique for studying the local properties of low dimensional materials. Being a plasmon driven system, a dramatic enhancement of the TERS sensitivity can be achieved by an appropriate choice of the plasmonic substrate in the so-called gap-mode configuration. Here, we investigate the phonon properties of CdSe nanocrystals (NCs) utilizing gap-mode TERS. Using the Langmuir-Blodgett technique, we homogeneously deposited submonolayers of colloidal CdSe NCs on two different nanostructured plasmonic substrates. Amplified by resonant gap-mode TERS, the scattering by the optical phonon modes of CdSe NCs is markedly enhanced making it possible to observe up to the third overtone of the LO mode reliably. The home-made plasmonic substrates and TERS tips allow the analysis of the TERS images of CdSe phonon modes with nanometer spatial resolution. The CdSe phonon scattering intensity is strongly correlated with the local electromagnetic field distribution across the plasmonic substrates.

| S-EPMC9417628 | biostudies-literature

Tip-Enhanced Raman Scattering Imaging of Two-Dimensional Tungsten Disulfide with Optimized Tip Fabrication Process.

Project description:We successfully achieve the tip-enhanced nano Raman scattering images of a tungsten disulfide monolayer with optimizing a fabrication method of gold nanotip by controlling the concentration of etchant in an electrochemical etching process. By applying a square-wave voltage supplied from an arbitrary waveform generator to a gold wire, which is immersed in a hydrochloric acid solution diluted with ethanol at various ratios, we find that both the conical angle and radius of curvature of the tip apex can be varied by changing the ratio of hydrochloric acid and ethanol. We also suggest a model to explain the origin of these variations in the tip shape. From the systematic study, we find an optimal condition for achieving the yield of ~60% with the radius of ~34?nm and the cone angle of ~35°. Using representative tips fabricated under the optimal etching condition, we demonstrate the tip-enhanced Raman scattering experiment of tungsten disulfide monolayer grown by a chemical vapor deposition method with a spatial resolution of ~40?nm and a Raman enhancement factor of ~4,760.

| S-EPMC5234014 | biostudies-literature

Effect of electric field gradient on sub-nanometer spatial resolution of tip-enhanced Raman spectroscopy.

Project description:Tip-enhanced Raman spectroscopy (TERS) with sub-nanometer spatial resolution has been recently demonstrated experimentally. However, the physical mechanism underlying is still under discussion. Here we theoretically investigate the electric field gradient of a coupled tip-substrate system. Our calculations suggest that the ultra-high spatial resolution of TERS can be partially attributed to the electric field gradient effect owning to its tighter spatial confinement and sensitivity to the infrared (IR)-active of molecules. Particularly, in the case of TERS of flat-lying H₂TBPP molecules,we find the electric field gradient enhancement is the dominating factor for the high spatial resolution, which qualitatively coincides with previous experimental report. Our theoretical study offers a new paradigm for understanding the mechanisms of the ultra-high spatial resolution demonstrated in tip-enhanced spectroscopy which is of importance but neglected.

| S-EPMC4363867 | biostudies-literature

Probing Membrane Receptor-Ligand Specificity with Surface- and Tip- Enhanced Raman Scattering.

Project description:The specific interaction between a ligand and a protein is a key component in minimizing off-target effects in drug discovery. Investigating these interactions with membrane protein receptors can be quite challenging. In this report, we show how spectral variance observed in surface-enhanced Raman scattering (SERS) and tip-enhanced Raman scattering (TERS) can be correlated with ligand specificity in affinity-based assays. Variations in the enhanced Raman spectra of three peptide ligands (i.e., cyclic-RGDFC, cyclic-isoDGRFC, and CisoDGRC), which have different binding affinity to αvβ3 integrin, are reported from isolated proteins and from receptors in intact cancer cell membranes. The SERS signal from the purified proteins provides basis spectra to analyze the signals in cells. Differences in the spectral variance within the SERS and TERS data for each ligand indicate larger variance for nonspecific ligand-receptor interactions. The SERS and TERS results are correlated with single particle tracking experiments of the ligand-functionalized nanoparticles with purified receptors on glass surfaces and living cells. These results demonstrate the ability to elucidate protein-ligand recognition using the observed vibrational spectra and provide perspective on binding specificity for small-molecule ligands in intact cell membranes, demonstrating a new approach for investigating drug specificity.

| S-EPMC5616087 | biostudies-literature

Improving resolution in quantum subnanometre-gap tip-enhanced Raman nanoimaging.

Project description:Two-dimensional (2D) materials beyond graphene such as transition metal dichalcogenides (TMDs) have unique mechanical, optical and electronic properties with promising applications in flexible devices, catalysis and sensing. Optical imaging of TMDs using photoluminescence and Raman spectroscopy can reveal the effects of structure, strain, doping, edge states, and surface functionalization from materials to bioscience. However, Raman signals are inherently weak and so far have been limited in spatial resolution in TMDs to a few hundred nanometres which is much larger than the intrinsic scale of these effects. Here we overcome the diffraction limit by using resonant tip-enhanced Raman scattering (TERS) of few-layer MoS2, and obtain nanoscale optical images with ~20 nm spatial resolution. This becomes possible due to electric field enhancement in an optimized subnanometre-gap resonant tip-substrate configuration. We investigate the limits of signal enhancement by varying the tip-sample gap with sub-Angstrom precision and observe a quantum quenching behavior, as well as a Schottky-Ohmic transition, for subnanometre gaps, which enable surface mapping based on this new contrast mechanism. This quantum regime of plasmonic gap-mode enhancement with a few nanometre thick MoS2 junction may be used for designing new quantum optoelectronic devices and sensors with a wide range of applications.

| S-EPMC4879532 | biostudies-literature

Dramatic Enhancement of Tip-Enhanced Raman Scattering Mediated by Atomic Point Contact Formation.

Project description:Tip-enhanced Raman scattering (TERS) in ångström-scale plasmonic cavities has drawn increasing attention. However, Raman scattering at vanishing cavity distances remains unexplored. Here, we show the evolution of TERS in transition from the tunneling regime to atomic point contact (APC). A stable APC is reversibly formed in the junction between an Ag tip and ultrathin ZnO or NaCl films on the Ag(111) surface at 10 K. An abrupt increase of the TERS intensity occurs upon APC formation for ZnO, but not for NaCl. This remarkable observation is rationalized by a difference in hybridization between the Ag tip and these films, which determines the contribution of charge transfer enhancement in the fused plasmonic junction. The strong hybridization between the Ag tip and ZnO is corroborated by the appearance of a new vibrational mode upon APC formation, whereas it is not observed for the chemically inert NaCl.

| S-EPMC7458471 | biostudies-literature

Computational Design of Molecular Probes for Electronic Preresonance Raman Scattering Microscopy.

Project description:Recently developed electronic preresonance stimulated Raman scattering (epr-SRS) microscopy, in which the Raman signal of a dye is significantly boosted by setting the incident laser frequency near the electronic excitation energy, has pushed the sensitivity of SRS microscopy close to that offered by confocal fluorescence microscopy. Prominently, the maintained narrow line-width of epr-SRS also offers high multiplexity that breaks the "color barrier" in optical microscopy. However, detailed understanding of the fundamental mechanism in these epr-SRS dyes still remains elusive. Here, we combine experiments with theoretical modeling to investigate the structure-function relationship, aiming to facilitate the design of new probes and expanding epr-SRS palettes. Our ab initio approach employing the displaced harmonic oscillator (DHO) model provides a consistent agreement between simulated and experimental SRS intensities of various triple-bond bearing epr-SRS probes with distinct scaffolds. We further review two popular approximate expressions for epr-SRS, namely the short-time and Albrecht A-term equations, and compare them to the DHO model. Overall, the theory allows us to illustrate how the observed intensity differences between molecular scaffolds stem from the coupling strength between the electronic excitation and the targeted vibrational mode, leading to a general design strategy for highly sensitive next-generation vibrational imaging probes.

| S-EPMC10676804 | biostudies-literature

Selective Detection of RGD-Integrin Binding in Cancer Cells Using Tip Enhanced Raman Scattering Microscopy.

Project description:Ligand-receptor interactions play important roles in many biological processes. Cyclic arginine-glycine-aspartic acid (RGD) containing peptides are known to mimic the binding domain of extracellular matrix protein fibronectin and selectively bind to a subset of integrin receptors. Here we report the tip enhanced Raman scattering (TERS) detection of RGD-functionalized nanoparticles bound to integrins produces a Raman scattering signal specific to the bound protein. These results demonstrate that this method can detect and differentiate between two different integrins (?5?1 and ?v?3) bound to RGD-conjugated gold nanoparticles both on surfaces and in a cancer cell membrane. In situ measurements of RGD nanoparticles bound to purified ?5?1 and ?v?3 receptors attached to a glass surface provide reference spectra for a multivariate regression model. The TERS spectra observed from nanoparticles bound to cell membranes are analyzed using this regression model and the identity of the receptor can be determined. The ability to distinguish between receptors in the cell membrane provides a new tool to chemically characterize ligand-receptor recognition at molecular level and provide chemical perspective on the molecular recognition of membrane receptors.

| S-EPMC4915994 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data