4.6 Article

Electrochemical Control of the Time-Dependent Intensity Fluctuations in Surface-Enhanced Raman Scattering (SERS)

Journal

JOURNAL OF PHYSICAL CHEMISTRY C
Volume 113, Issue 41, Pages 17737-17744

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/jp907389v

Keywords

-

Funding

  1. FAPESP [01/09497-8]
  2. NSERC
  3. CNPq
  4. Canadian Bureau for International Education Department of Foreign Affairs
  5. International Trade (CBIEDFAIT) of Canada
  6. Fundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP) [01/09497-8] Funding Source: FAPESP

Ask authors/readers for more resources

Time-dependent fluctuations in surface-enhanced Raman scattering (SERS) intensities were recorded from a roughened silver electrode immersed in diluted solutions of rhodamine 6G (R6G) and congo red (CR). These fluctuations were attributed to a small number of SERS-active molecules probing regions of extremely high electromagnetic field (hot spots) at the nanostructured surface. The time-dependent distribution of SERS intensities followed a tailed statistics at certain applied potentials, which has been linked to single-molecule dynamics. The shape of the distribution was reversibly tuned by the applied voltage. Mixtures of both dyes, R6G and CR, at low concentrations were also investigated. Since R6G is a cationic dye and CR is an anionic dye, the statistics of the SERS intensity distribution of either dye in a mixture were independently controlled by adjusting the applied potential. The potential-controlled distribution of SERS intensities was interpreted by considering the modulation of the surface coverage of the adsorbed dye by the interfacial electric field. This interpretation was supported by a two-dimensional Monte Carlo simulation that took into account the time evolution of the surface configuration of the adsorbed species and their probability to populate a hypothetical hot spot. The potential-controlled SERS dynamics reported here is a first step toward the spectroelectrochemical investigation of redox processes at the single-molecule level by SERS.

Authors

I am an author on this paper
Click your name to claim this paper and add it to your profile.

Reviews

Primary Rating

4.6
Not enough ratings

Secondary Ratings

Novelty
-
Significance
-
Scientific rigor
-
Rate this paper

Recommended

Article Instruments & Instrumentation

Group and Basis Restricted Non-Negative Matrix Factorization and Random Forest for Molecular Histotype Classification and Raman Biomarker Monitoring in Breast Cancer

Xinchen Deng, Kirsty Milligan, Ramie Ali-Adeeb, Phillip Shreeves, Alexandre Brolo, Julian J. Lum, Jeffrey L. Andrews, Andrew Jirasek

Summary: Raman spectroscopy, when combined with GBR-NMF-RF framework, can be a powerful tool in monitoring radiation response profiles and biochemical dynamics in different molecular histotypes of irradiated breast cancer cells. The framework yields high accuracy, sensitivity, and specificity in classifying molecular histotypes and assessing the importance of Raman biochemical basis spectra for each classification test. High contributions from glycogen and lipids were found to be important in molecular histotype classifications.

APPLIED SPECTROSCOPY (2022)

Article Chemistry, Physical

Single-Molecule SERS Hotspot Dynamics in Both Dry and AqueousEnvironments

Nathan C. Lindquist, Ariadne Tuckmantel Bido, Alexandre G. Brolo

Summary: This paper investigates the mechanism of fluctuations in Surface Enhanced Raman Spectroscopy (SERS) signals and finds that the underlying source of these fluctuations is a complex interplay of different effects. High-speed SIF activity is present in both dry and wet nanoparticle environments, and a simple model is proposed to explain the contributions to the fluctuations.

JOURNAL OF PHYSICAL CHEMISTRY C (2022)

Article Chemistry, Analytical

Quantification of a COVID-19 Antibody Assay Using a Lateral Flow Test and a Cell Phone

Pearl Thompson, Ana Livia de Carvalho Bovolato, Gisela Ibanez-Redin, Alexandre G. Brolo

Summary: A rapid lateral flow screening tool using saliva samples and cell phone quantification has been developed, providing sensitive detection of IgG antibodies against SARS-CoV-2 within 10 minutes.

CHEMOSENSORS (2022)

Article Chemistry, Analytical

Exploring Intensity Distributions and Sampling in SERS-Based Immunoassays

Ariadne Tuckmantel Bido, Alexandre G. Brolo, Arash Azarakhshi

Summary: Surface-enhanced Raman scattering (SERS) is a sensitive spectroscopic technique, but its reproducibility has been an issue in analytical chemistry applications. This study demonstrates that reliable quantification of SERS immunoassay at low concentrations is possible with careful experimental design and appropriate data analysis statistics.

ANALYTICAL CHEMISTRY (2022)

Article Chemistry, Multidisciplinary

An Economical and Scalable Method to Synthesize Graphitic-Like Films

Minh-Hai Tran, Ian Booth, Bruno G. daFonseca, Peter Berrang, Jeremy E. Wulff, Alexandre G. Brolo

Summary: An economical and facile method has been developed to synthesize a precursor for carbon films and materials. This precursor can be easily coated onto substrates and converted into a graphitic-like structure after mild thermal treatment. This method allows for the coating of glass surfaces of different shapes and forms.

ACS OMEGA (2022)

Article Chemistry, Multidisciplinary

High-Speed Spectral Characterization of Single-Molecule SERS Fluctuations

Makayla M. Schmidt, Emily A. Farley, Marit A. Engevik, Trey N. Adelsman, Ariadne Tuckmantel Bido, Nathan D. Lemke, Alexandre G. Brolo, Nathan C. Lindquist

Summary: The concept of plasmonic hotspots is central to nanophotonics, specifically in surface-enhanced Raman scattering (SERS). SERS signals from single molecules often exhibit fluctuations, challenging the concept of static hotspots. Recent experiments have shown SERS intensity fluctuations (SIFs) to occur over a wide range of timescales due to various physical mechanisms causing SERS and the dynamic nature of light-matter interaction. This study presents a high-speed acquisition system that captures SERS spectra with microsecond time resolution, revealing that high-speed SIF events occur with relatively equal probability over a broad spectral range.

ACS NANO (2023)

Article Instruments & Instrumentation

Reconstruction of Raman Spectra of Biochemical Mixtures Using Group and Basis Restricted Non-Negative Matrix Factorization

Kirsty Milligan, Kendra Scarrott, Jeffrey L. Andrews, Alexandre G. Brolo, Julian J. Lum, Andrew Jirasek

Summary: Raman spectroscopy is a useful tool for obtaining biochemical information, but interpreting the data can be challenging. Our group has demonstrated a non-negative matrix factorization framework as an alternative to dimensionality reduction techniques for Raman spectroscopy data related to radiation response monitoring. We evaluated the accuracy of the model in reconstructing mixture solutions of known concentrations and considered factors such as spectral bases, noise thresholds, and different biochemical groups. Overall, the model performed well and solid bases spectra were comparable to solution bases spectra. The inclusion of an unconstrained component did not significantly affect the deconstruction, as long as all biochemicals were included in the model.

APPLIED SPECTROSCOPY (2023)

Article Chemistry, Analytical

A Direct Immunoassay Based on Surface-Enhanced Spectroscopy Using AuNP/PS-b-P2VP Nanocomposites

Moyra F. Vieira, Ana Livia de Carvalho Bovolato, Bruno G. da Fonseca, Celly M. S. Izumi, Alexandre G. Brolo

Summary: A biosensor was developed for directly detecting human immunoglobulin G (IgG) and adenosine triphosphate (ATP) using gold nanoparticles/polystyrene-b-poly(2-vinylpyridine) (AuNP/PS-b-P2VP) nanocomposites. The substrates were functionalized with carboxylic acid groups to bind anti-IgG and anti-ATP and detect IgG and ATP. SEM images showed gold nanoparticles adsorbed onto a porous thin film. UV-VIS and SERS were used to characterize substrate functionalization and antibody-target interaction. PCA discriminated between samples before and after affinity tests. The biosensor was sensitive to IgG concentrations with a limit of detection of 1 μg/mL.

SENSORS (2023)

Article Chemistry, Multidisciplinary

Synthesis, Thermal Analysis, Spectroscopic Properties, and Degradation Process of Tutton Salts Doped with AgNO3 or H3BO3

Tiago S. Pacheco, Zelia M. C. Ludwig, Victor H. Oliveira, Ingrid D. Barcelos, Rafael L. de Souza, Edinei C. Paiva, Maximiliano D. Martins, Flavia C. Marques, Gustavo F. S. Andrade, Santunu Ghosh

Summary: In this study, we synthesized and studied the spectroscopic properties of (NH4)2(SO4)2Y(H2O)6 (Y = Ni, Mg) crystals doped with AgNO3 or H3BO3. The effects of dopants on the vibrational modes of the ligands NH4 and SO4, complexes Mg(H2O)6 and Ni(H2O)6, and H2O molecules present in these crystals were investigated using Raman and infrared spectroscopies. The presence of Ag and B dopants and their influence on the crystal lattice were identified through band analysis. Thermogravimetric measurements showed an increase in the initial temperature of crystal degradation due to the presence of dopants. Raman spectroscopy of the crystal residues after thermogravimetric measurements provided insights into the degradation processes occurring after crystal pyrolysis.

ACS OMEGA (2023)

Article Spectroscopy

A machine learning approach for the automated classification of bulk sp2 and sp3 carbon materials

Bruno G. daFonseca, Sapanbir S. Thind, Ian Booth, Alexandre G. Brolo

Summary: Principal component analysis (PCA) and linear discriminant analysis (LDA) were used to classify different types of carbon material based on their Raman spectra, providing an avenue for automated classification of carbon materials using Raman spectroscopy and machine learning.

JOURNAL OF RAMAN SPECTROSCOPY (2023)

Article Chemistry, Multidisciplinary

Synthesis of Graphene and Graphene Films with Minimal Structural Defects

Minh-Hai Tran, Ian Booth, Arash Azarakhshi, Peter Berrang, Jeremy Wulff, Alexandre G. Brolo

Summary: This paper introduces a new method for large-scale synthesis of graphene that minimizes the creation of structural defects. The method involves hydrogen functionalization of graphite followed by thermal dehydrogenation, and it is demonstrated to be effective for the preparation of high-quality graphene films.

ACS OMEGA (2023)

Article Chemistry, Analytical

Detection of SARS-CoV-2 in saliva by a low-cost LSPR-based sensor

Ariadne Tuckmantel Bido, Katherine J. I. Ember, Dominique Trudel, Madeleine Durand, Frederic Leblond, Alexandre G. Brolo

Summary: The SARS-CoV-2 pandemic has posed a challenge in containing the spread of the virus, especially in low and middle-income countries due to limited access to screening tests. In this study, a low-cost biosensor device based on localized surface plasmon resonance (LSPR) was developed for the screening of SARS-CoV-2. The sensor showed high sensitivity and specificity in detecting the virus in saliva samples, providing a potential solution for screening challenges in underserved communities.

ANALYTICAL METHODS (2023)

Article Chemistry, Multidisciplinary

High-Speed Spectral Characterization of Single-Molecule SERS Fluctuations

Makayla M. Schmidt, Emily A. Farley, Marit A. Engevik, Trey N. Adelsman, Ariadne Tuckmantel Bido, Nathan D. Lemke, Alexandre G. Brolo, Nathan C. Lindquist

Summary: The concept of plasmonic hotspots plays a crucial role in the field of nanophotonics, particularly in surface-enhanced Raman scattering (SERS). Recent experiments have shown that these hotspots exhibit significant fluctuations at different timescales, which are likely caused by the complex interplay of multiple effects. This study presents a high-speed acquisition system that captures the dynamic processes of SERS fluctuations and finds that these fluctuations occur over a wide spectral range.

ACS NANO (2023)

Article Chemistry, Physical

Surface-enhanced Raman spectroscopy of one and a few molecules of acid 4-mercaptobenzoic in AgNP enabled by hot spots generated by hydrogen bonding

Flavia C. Marques, Raisa Siqueira Alves, Diego Pereira dos Santos, Gustavo F. S. Andrade

Summary: The present study reports a direct approach to generate efficient hot spots using a nonresonant molecule bound to the inner part or hot spots that can increase the SERS sensitivity to obtain spectra of one and a few molecules. The study also investigates the self-assembly process of AgNP triggered by the 4-MBA adsorbate bonded to the Ag surface, and explores the SERS intensification of 4-MBA in low concentrations.

PHYSICAL CHEMISTRY CHEMICAL PHYSICS (2022)

Article Chemistry, Analytical

Radiation treatment response and hypoxia biomarkers revealed by machine learning assisted Raman spectroscopy in tumour cells and xenograft tissues

Xinchen Deng, Kirsty Milligan, Alexandre Brolo, Julian J. Lum, Jeffrey L. Andrews, Andrew Jirasek

Summary: The use of Raman spectroscopy combined with a data analytical framework allows for the monitoring of biochemical responses and spatial correlation with hypoxic regions in radiation therapy. This provides a deeper understanding of individual biochemical dynamics in radiation responses, which can be applied in cancer therapy.

ANALYST (2022)

No Data Available