Single-molecule detection of yeast cytochrome c by Surface-Enhanced Raman Spectroscopy

2005 ◽  
Vol 113 (1) ◽  
pp. 41-51 ◽  
Author(s):  
Ines Delfino ◽  
Anna Rita Bizzarri ◽  
Salvatore Cannistraro
Keyword(s):  
Raman Spectroscopy ◽  
Cytochrome C ◽  
Single Molecule ◽  
Surface Enhanced Raman Spectroscopy ◽  
Single Molecule Detection ◽  
Surface Enhanced ◽  
Surface Enhanced Raman

Single-molecule surface-enhanced Raman spectroscopy with nanowatt excitation

2014 ◽  
Vol 16 (43) ◽  
pp. 23895-23899 ◽  
Author(s):  
Brendan L. Darby ◽  
Pablo G. Etchegoin ◽  
Eric C. Le Ru
Keyword(s):  
Raman Spectroscopy ◽  
Single Molecule ◽  
Surface Enhanced Raman Spectroscopy ◽  
Single Molecule Detection ◽  
Surface Enhanced ◽  
Surface Enhanced Raman ◽  
Molecule Surface

Bi-analyte experiments demonstrate that single-molecule detection via SERS can be achieved at ultra-low excitation powers.

scholarly journals Fundamental Investigations into Single Molecule Surface Enhanced Raman Spectroscopy

2021 ◽  
Author(s):  
◽  
Camille G. Artur
Keyword(s):  
Raman Spectroscopy ◽  
Temperature Dependence ◽  
Single Molecule ◽  
Nile Blue ◽  
Surface Enhanced Raman Spectroscopy ◽  
Inhomogeneous Broadening ◽  
Single Molecule Detection ◽  
Surface Enhanced ◽  
Surface Enhanced Raman ◽  
Homogeneous Broadening

<p>After the first claim of single molecule (SM) detection by surface enhanced Raman spectroscopy (SERS) was published in 1997 and years of debate and maturing, SM-SERS can now be considered as an established subfield of SERS. Besides the obvious promising advances in analytical spectroscopy that SM-SERS enables, some more fundamental studies are now also accessible. The main focus of this thesis is to understand certain aspects and tackle some outstanding issues in SM-SERS, both in methods and applications. In the first part of this thesis, we focus on the application of SM-SERS to the study of the homogeneous broadening of molecular vibrations. We show that the homogeneous linewidth of the dye Nile blue as measured on single molecule SERS spectra is much smaller than the inhomogeneous broadening obtained from the average signal. Individual molecules having the central Raman frequency occurring at slightly different positions is therefore the main cause of the inhomogeneous broadening in this system. Furthermore, we show that the homogeneous broadening of the mode of single molecules exhibits a strong temperature dependence from 80K to 300 K. This is suggestive of the vibrational energy exchange model which explicitly relates the temperature dependence of the linewidth of a vibrational mode to its interaction with other modes of the molecule or its environment. The average signal does not show this temperature dependence, this property is indeed washed out by ensemble averaging and its unravelling is made possible by SM-SERS. This study is the first example of direct measurement and study of the homogeneous broadening of a Raman peak. In the second part of this work, we focus on a particular method to prove single molecule sensitivity and demonstrate the single molecule detection of the iconic C₆₀ by SM-SERS using its peculiar spectral properties regarding isotopic substitution. A change in one unit mass in one of the carbon atoms is readily observed as a detectable frequency shift in the Ag(2) mode on the Raman spectrum of one C₆₀. This remarkable result is a direct consequence of the high symmetry of the molecule and is only accessible experimentally by measuring individual molecules. We perform SM-SERS detection of a isotopically enriched C₆₀ and show how the distribution of frequencies for the Ag(2) mode reflects the isotopic spread of the sample. Density Functional Theory (DFT) calculations support the experimental results. This provides the first ever evidence of single molecule detection of C₆₀ via SERS. Finally, we focus on the photostability of dyes excited resonantly in SERS conditions. Photobleaching of the molecule is an issue when doing SERS (and SM-SERS) at resonance. Nile blue is deposited on a highly ordered gold nanolithographic substrate and the time dependence of the SERS signal is monitored. Using a simple two-level system model to describe the mechanisms of photobleaching and express the photobleaching rate, we analyse the SERS intensity decay at different powers. This study is the first to be dedicated to the photobleaching decay rates of molecules on metallic surfaces and to highlight that the decay dynamics contains rates spanning four orders of magnitude. This work can potentially reveal information on the distribution of SERS enhancement factors on the surface.</p>

scholarly journals Fundamental Investigations into Single Molecule Surface Enhanced Raman Spectroscopy

2021 ◽  
Author(s):  
◽  
Camille G. Artur
Keyword(s):  
Raman Spectroscopy ◽  
Temperature Dependence ◽  
Single Molecule ◽  
Nile Blue ◽  
Surface Enhanced Raman Spectroscopy ◽  
Inhomogeneous Broadening ◽  
Single Molecule Detection ◽  
Surface Enhanced ◽  
Surface Enhanced Raman ◽  
Homogeneous Broadening

<p>After the first claim of single molecule (SM) detection by surface enhanced Raman spectroscopy (SERS) was published in 1997 and years of debate and maturing, SM-SERS can now be considered as an established subfield of SERS. Besides the obvious promising advances in analytical spectroscopy that SM-SERS enables, some more fundamental studies are now also accessible. The main focus of this thesis is to understand certain aspects and tackle some outstanding issues in SM-SERS, both in methods and applications. In the first part of this thesis, we focus on the application of SM-SERS to the study of the homogeneous broadening of molecular vibrations. We show that the homogeneous linewidth of the dye Nile blue as measured on single molecule SERS spectra is much smaller than the inhomogeneous broadening obtained from the average signal. Individual molecules having the central Raman frequency occurring at slightly different positions is therefore the main cause of the inhomogeneous broadening in this system. Furthermore, we show that the homogeneous broadening of the mode of single molecules exhibits a strong temperature dependence from 80K to 300 K. This is suggestive of the vibrational energy exchange model which explicitly relates the temperature dependence of the linewidth of a vibrational mode to its interaction with other modes of the molecule or its environment. The average signal does not show this temperature dependence, this property is indeed washed out by ensemble averaging and its unravelling is made possible by SM-SERS. This study is the first example of direct measurement and study of the homogeneous broadening of a Raman peak. In the second part of this work, we focus on a particular method to prove single molecule sensitivity and demonstrate the single molecule detection of the iconic C₆₀ by SM-SERS using its peculiar spectral properties regarding isotopic substitution. A change in one unit mass in one of the carbon atoms is readily observed as a detectable frequency shift in the Ag(2) mode on the Raman spectrum of one C₆₀. This remarkable result is a direct consequence of the high symmetry of the molecule and is only accessible experimentally by measuring individual molecules. We perform SM-SERS detection of a isotopically enriched C₆₀ and show how the distribution of frequencies for the Ag(2) mode reflects the isotopic spread of the sample. Density Functional Theory (DFT) calculations support the experimental results. This provides the first ever evidence of single molecule detection of C₆₀ via SERS. Finally, we focus on the photostability of dyes excited resonantly in SERS conditions. Photobleaching of the molecule is an issue when doing SERS (and SM-SERS) at resonance. Nile blue is deposited on a highly ordered gold nanolithographic substrate and the time dependence of the SERS signal is monitored. Using a simple two-level system model to describe the mechanisms of photobleaching and express the photobleaching rate, we analyse the SERS intensity decay at different powers. This study is the first to be dedicated to the photobleaching decay rates of molecules on metallic surfaces and to highlight that the decay dynamics contains rates spanning four orders of magnitude. This work can potentially reveal information on the distribution of SERS enhancement factors on the surface.</p>

Marangoni Convection Assisted Single Molecule Detection with Nanojet Surface Enhanced Raman Spectroscopy

ACS Sensors ◽  
2017 ◽  
Vol 2 (8) ◽  
pp. 1133-1138 ◽  
Author(s):  
Te-Wei Chang ◽  
Xinhao Wang ◽  
Amirreza Mahigir ◽  
Georgios Veronis ◽  
Gang Logan Liu ◽  
...  
Keyword(s):  
Raman Spectroscopy ◽  
Single Molecule ◽  
Marangoni Convection ◽  
Surface Enhanced Raman Spectroscopy ◽  
Single Molecule Detection ◽  
Surface Enhanced ◽  
Surface Enhanced Raman

Engineering nanostructures for single-molecule surface-enhanced Raman spectroscopy

2004 ◽  
Author(s):  
Martin Moskovits ◽  
Dae-Hong Jeong ◽  
Tsachi Livneh ◽  
Yiying Wu ◽  
Galen D. Stucky
Keyword(s):  
Raman Spectroscopy ◽  
Single Molecule ◽  
Surface Enhanced Raman Spectroscopy ◽  
Surface Enhanced ◽  
Surface Enhanced Raman ◽  
Molecule Surface

scholarly journals Surface-enhanced Raman spectroscopy: benefits, trade-offs and future developments

2020 ◽  
Vol 11 (18) ◽  
pp. 4563-4577 ◽  
Author(s):  
Ana Isabel Pérez-Jiménez ◽  
Danya Lyu ◽  
Zhixuan Lu ◽  
Guokun Liu ◽  
Bin Ren
Keyword(s):  
Raman Spectroscopy ◽  
Single Molecule ◽  
Surface Enhanced Raman Spectroscopy ◽  
Direct Identification ◽  
Molecular Fingerprints ◽  
Single Molecule Level ◽  
Trade Offs ◽  
Target Analytes ◽  
Surface Enhanced ◽  
Surface Enhanced Raman

Surface-enhanced Raman spectroscopy (SERS) is a vibrational spectroscopy technique with sensitivity down to the single molecule level that provides fine molecular fingerprints, allowing for direct identification of target analytes.

scholarly journals Surface-enhanced Raman spectroscopy at single-molecule scale and its implications in biology

2013 ◽  
Vol 368 (1611) ◽  
pp. 20120026 ◽  
Author(s):  
Yuling Wang ◽  
Joseph Irudayaraj
Keyword(s):  
Raman Spectroscopy ◽  
Single Molecule ◽  
Surface Enhanced Raman Spectroscopy ◽  
Biomedical Sciences ◽  
Surface Enhanced ◽  
Surface Enhanced Raman ◽  
Raman Measurement ◽  
Low Levels ◽  
Exciting Area ◽  
Significant Opportunity

Single-molecule (SM) spectroscopy has been an exciting area of research offering significant promise and hope in the field of sensor development to detect targets at ultra-low levels down to SM resolution. To the experts and developers in the field of surface-enhanced Raman spectroscopy (SERS), this has often been a challenge and a significant opportunity for exploration. Needless to say, the opportunities and excitement of this multidisciplinary area impacts span the fields of physics, chemistry and engineering, along with a significant thrust in applications constituting areas in medicine, biology, environment and agriculture among others. In this review, we will attempt to provide a quick snapshot of the basics of SM-SERS, nanostructures and devices that can enable SM Raman measurement. We will conclude with a discussion on SERS implications in biomedical sciences.

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