Computational Design of Molecular Probes for Electronic Preresonance Raman Scattering Microscopy
Abstract
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.
Additional Information
© 2023 American Chemical Society. L.W. acknowledges support from NIH Director's New Innovator Award (GM140919). T.B. acknowledges financial support from the Swiss National Science Foundation through the Early Postdoc Mobility Fellowship (Grant Number P2ELP2-199757). We thank Dr. Martin J. Schnermann for sharing the FC10 dye. The computations presented here were conducted in the Resnick High Performance Computing Center, a facility supported by the Resnick Sustainability Institute at the California Institute of Technology. Author Contributions: J.D. and X.T. contributed equally to this work. The authors declare no competing financial interest.Attached Files
Supplemental Material - jp3c00699_si_001.pdf
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Additional details
- Alternative title
- Computational Design of Molecular Probes for Electronic Pre-resonance Raman Scattering Microscopy
- Eprint ID
- 122439
- Resolver ID
- CaltechAUTHORS:20230725-856834000.3
- PMCID
- PMC10676804
- DOI
- 10.1021/acs.jpcb.3c00699
- NIH
- GM140919
- Swiss National Science Foundation (SNSF)
- P2ELP2-199757
- Resnick Sustainability Institute
- Created
-
2023-08-17Created from EPrint's datestamp field
- Updated
-
2023-08-17Created from EPrint's last_modified field
- Caltech groups
- Resnick Sustainability Institute