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Controlling the Fluctuating Tip-Enhanced Raman Spectra of Chloramben on Silver Nanocubes.
Oliva M Primera-Pedrozo1, Alexander B C Mantilla2, Tanya L Myers1
1Physical Sciences Division, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352, United States.
Analytical Chemistry
|February 5, 2024
Summary
Tip-enhanced Raman (TER) scattering allows single-molecule detection. Controlling plasmonic interactions, particularly avoiding direct tip contact, is crucial for obtaining clear TER spectra of complex molecules like chloramben.
Area of Science:
- Plasmonics
- Spectroscopy
- Nanotechnology
Background:
- Tip-enhanced Raman (TER) scattering enables single-molecule detection and imaging.
- Complex molecules with multiple conformations or charge states yield intricate TER spectra.
- Controlling molecular orientation and plasmonic interactions is key for accurate analysis.
Purpose of the Study:
- To investigate the influence of plasmonic junctions on TER spectra of complex molecules.
- To demonstrate control over TER spectral complexity using chloramben on silver nanocubes.
- To develop a less invasive approach for analytical TER spectral imaging.
Main Methods:
- Utilizing silver nanocubes as plasmonic substrates.
- Coating substrates with chloramben molecules.
- Employing TER scattering microscopy under varying tip-substrate interaction conditions.
- Analyzing spectral complexity related to molecular conformation and protonation states.
Main Results:
- TER spectra were significantly altered when tunneling plasmons were operative (direct tip contact).
- Characteristic molecular Raman spectra were unobtainable under direct contact conditions.
- The study illustrates control over spectral complexity for chloramben molecules.
- Direct tip contact with plasmonic nanoparticles disrupts spectral acquisition.
Conclusions:
- Direct tip contact with plasmonic nanoparticles hinders obtaining characteristic molecular Raman spectra.
- A less invasive TER approach is proposed for more analytical spectral imaging.
- Understanding and controlling plasmonic interactions are vital for advanced molecular analysis using TER.
