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Toward photoswitchable electronic pre-resonance stimulated Raman probes

Lee, Dongkwan and Qian, Chenxi and Wang, Haomin and Li, Lei and Miao, Kun and Du, Jiajun and Shcherbakova, Daria M. and Verkhusha, Vladislav V. and Wang, Lihong V. and Wei, Lu (2021) Toward photoswitchable electronic pre-resonance stimulated Raman probes. Journal of Chemical Physics, 154 (13). Art. No. 135102. ISSN 0021-9606. PMCID PMC8019356. doi:10.1063/5.0043791. https://resolver.caltech.edu/CaltechAUTHORS:20210416-071920882

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Abstract

Reversibly photoswitchable probes allow for a wide variety of optical imaging applications. In particular, photoswitchable fluorescent probes have significantly facilitated the development of super-resolution microscopy. Recently, stimulated Raman scattering (SRS) imaging, a sensitive and chemical-specific optical microscopy, has proven to be a powerful live-cell imaging strategy. Driven by the advances of newly developed Raman probes, in particular the pre-resonance enhanced narrow-band vibrational probes, electronic pre-resonance SRS (epr-SRS) has achieved super-multiplex imaging with sensitivity down to 250 nM and multiplexity up to 24 colors. However, despite the high demand, photoswitchable Raman probes have yet to be developed. Here, we propose a general strategy for devising photoswitchable epr-SRS probes. Toward this goal, we exploit the molecular electronic and vibrational coupling, in which we switch the electronic states of the molecules to four different states to turn their ground-state epr-SRS signals on and off. First, we showed that inducing transitions to both the electronic excited state and triplet state can effectively diminish the SRS peaks. Second, we revealed that the epr-SRS signals can be effectively switched off in red-absorbing organic molecules through light-facilitated transitions to a reduced state. Third, we identified that photoswitchable proteins with near-infrared photoswitchable absorbance, whose states are modulable with their electronic resonances detunable toward and away from the pump photon energy, can function as the photoswitchable epr-SRS probes with desirable sensitivity (<1 µM) and low photofatigue (>40 cycles). These photophysical characterizations and proof-of-concept demonstrations should advance the development of novel photoswitchable Raman probes and open up the unexplored Raman imaging capabilities.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1063/5.0043791DOIArticle
ORCID:
AuthorORCID
Lee, Dongkwan0000-0001-6091-1349
Qian, Chenxi0000-0003-4815-5565
Wang, Haomin0000-0001-7193-8651
Li, Lei0000-0001-6164-2646
Miao, Kun0000-0001-6567-3650
Shcherbakova, Daria M.0000-0003-3384-6363
Verkhusha, Vladislav V.0000-0002-2083-8121
Wang, Lihong V.0000-0001-9783-4383
Wei, Lu0000-0001-9170-2283
Additional Information:© 2021 Published under license by AIP Publishing. Submitted: 11 January 2021; Accepted: 15 March 2021; Published Online: 2 April 2021. This work was supported by the grants from the National Institutes of Health, Grant No. DP2 GM140919 (to L.W.) and Grant No. R35 GM122567 (to V.V.), and by the start-up fund from the California Institute of Technology (to L.W.). Data Availability: The data that support the findings of this study are available from the corresponding author upon reasonable request.
Funders:
Funding AgencyGrant Number
NIHDP2 GM140919
NIHR35 GM122567
CaltechUNSPECIFIED
Issue or Number:13
PubMed Central ID:PMC8019356
DOI:10.1063/5.0043791
Record Number:CaltechAUTHORS:20210416-071920882
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20210416-071920882
Official Citation:Toward photoswitchable electronic pre-resonance stimulated Raman probes. J. Chem. Phys. 154, 135102 (2021); doi: 10.1063/5.0043791
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:108748
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:19 Apr 2021 16:37
Last Modified:05 Aug 2021 16:39

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