Unraveling a self-assembling mechanism of isomeric aminothiophenol on Ag dendrite by correlated SERS and matrix-free LDI-MS
Abstract
Correlated spectroscopic analysis can provide complementary chemical insights that are often unattainable by either approach used in isolation. We distinguished the different self-assembling behavior of isomeric aminothiophenols (ATPs) on Ag dendrite by the correlation of surface-enhanced Raman spectroscopy and laser-induced desorption ionization mass spectrometry, demonstrating that steric effect impinged significantly upon surface molecular density and plasmon-driven catalytic reaction yield, which led to drastic variations in the resulting SERS spectra. The correlative measurement shows that ortho-substitute barely formed a self-assemble monolayer, relative to the para-isomer, which can form a close-packed self-assembled monolayer and perform a decent azo-coupling reaction. Comparison between normal and SERS spectra of ATP isomers supports the fact that additional disulfide- or hydrogen-bonding interactions are established in para-ATP solid crystal, but neither of ortho- nor meta-isomers. This work is expected to create a significant impact on the development of an orthogonally correlated spectroscopic tool in deciphering chemical insights and underlying reaction mechanism.
Graphical abstract
Keywords
Correlative spectroscopy Self-assembling monolayer Aminothiophenol Surface-enhanced Raman scattering Laser-induced desorption ionization mass spectrometryAbbreviations
- ATP
Aminothiophenol
- SAM
Self-assembling monolayer
- SERS
Surface-enhanced Raman spectroscopy
- MALDI-TOF
Matrix-assisted laser desorption ionization-time of flight
- LDI-MS
Laser-induced desorption ionization mass spectrometry
- CRM
Confocal Raman microscopy
- SIMS
Second ion mass spectrometer
- DMAB
Dimercaptoazobenzene
- NRS
Normal Raman spectrum
- TNI
Transient negative ion
Notes
Funding information
This work was supported by South-central University of Nationalities Start-up funds under Grant YZZ16004 and China Central University Administration under Grant CZZ18002.
Compliance with ethical standards
Conflict of interest
The authors declare that they have no conflict of interest.
Supplementary material
References
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