Ketone Incorporation Extends the Emission Properties of the Xanthene Scaffold Beyond 1000 Nm

Overview

Journal Photochem Photobiol

Specialties Biochemistry
Biology
Chemistry

Date 2021 Oct 22

PMID 34676539

Citations 12

Authors

Harrison C Daly

Siddharth S Matikonda

Helena C Steffens

Bastian Ruehle

Ute Resch-Genger

Joseph Ivanic

Martin J Schnermann

Affiliations

Soon will be listed here.

Abstract

Imaging in the shortwave-infrared region (SWIR, λ = 1000-2500 nm) has the potential to enable deep tissue imaging with high resolution. Critical to the development of these methods is the identification of low molecular weight, biologically compatible fluorescent probes that emit beyond 1000 nm. Exchanging the bridging oxygen atom on the xanthene scaffold (C10' position) with electron withdrawing groups has been shown to lead to significant redshifts in absorbance and emission. Guided by quantum chemistry computational modeling studies, we investigated the installation of a ketone bridge at the C10' position. This simple modification extends the absorbance maxima to 860 nm and the emission beyond 1000 nm, albeit with reduced photon output. Overall, these studies demonstrate that broadly applied xanthene dyes can be extended into the SWIR range.

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References

Yuan L, Lin W, Zheng K, He L, Huang W . Far-red to near infrared analyte-responsive fluorescent probes based on organic fluorophore platforms for fluorescence imaging. Chem Soc Rev. 2012; 42(2):622-61. DOI: 10.1039/c2cs35313j. View

Grimm J, Gruber T, Ortiz G, Brown T, Lavis L . Virginia Orange: A Versatile, Red-Shifted Fluorescein Scaffold for Single- and Dual-Input Fluorogenic Probes. Bioconjug Chem. 2015; 27(2):474-80. DOI: 10.1021/acs.bioconjchem.5b00566. View

Sibbersen C, Palmfeldt J, Hansen J, Gregersen N, Anker Jorgensen K, Johannsen M . Development of a chemical probe for identifying protein targets of α-oxoaldehydes. Chem Commun (Camb). 2013; 49(38):4012-4. DOI: 10.1039/c3cc41099d. View

Hatami S, Wurth C, Kaiser M, Leubner S, Gabriel S, Bahrig L . Absolute photoluminescence quantum yields of IR26 and IR-emissive Cd(1-x)Hg(x)Te and PbS quantum dots--method- and material-inherent challenges. Nanoscale. 2014; 7(1):133-43. DOI: 10.1039/c4nr04608k. View

Zhou X, Lai R, Beck J, Li H, Stains C . Nebraska Red: a phosphinate-based near-infrared fluorophore scaffold for chemical biology applications. Chem Commun (Camb). 2016; 52(83):12290-12293. PMC: 5108567. DOI: 10.1039/c6cc05717a. View

Grimm J, English B, Chen J, Slaughter J, Zhang Z, Revyakin A . A general method to improve fluorophores for live-cell and single-molecule microscopy. Nat Methods. 2015; 12(3):244-50, 3 p following 250. PMC: 4344395. DOI: 10.1038/nmeth.3256. View

Wan H, Yue J, Zhu S, Uno T, Zhang X, Yang Q . A bright organic NIR-II nanofluorophore for three-dimensional imaging into biological tissues. Nat Commun. 2018; 9(1):1171. PMC: 5862886. DOI: 10.1038/s41467-018-03505-4. View

Bariak V, Malastova A, Almassy A, Sebesta R . Retro-Brook Rearrangement of Ferrocene-Derived Silyl Ethers. Chemistry. 2015; 21(38):13445-53. DOI: 10.1002/chem.201501711. View

Garland M, Yim J, Bogyo M . A Bright Future for Precision Medicine: Advances in Fluorescent Chemical Probe Design and Their Clinical Application. Cell Chem Biol. 2016; 23(1):122-136. PMC: 4779185. DOI: 10.1016/j.chembiol.2015.12.003. View

10.

Zhang X, Chen L, Huang Z, Ling N, Xiao Y . Cyclo-Ketal Xanthene Dyes: A New Class of Near-Infrared Fluorophores for Super-Resolution Imaging of Live Cells. Chemistry. 2020; 27(11):3688-3693. DOI: 10.1002/chem.202005296. View

11.

Frei M, Hoess P, Lampe M, Nijmeijer B, Kueblbeck M, Ellenberg J . Photoactivation of silicon rhodamines via a light-induced protonation. Nat Commun. 2019; 10(1):4580. PMC: 6783549. DOI: 10.1038/s41467-019-12480-3. View

12.

Zheng Q, Ayala A, Chung I, Weigel A, Ranjan A, Falco N . Rational Design of Fluorogenic and Spontaneously Blinking Labels for Super-Resolution Imaging. ACS Cent Sci. 2019; 5(9):1602-1613. PMC: 6764213. DOI: 10.1021/acscentsci.9b00676. View

13.

Li H . Quantum mechanical/molecular mechanical/continuum style solvation model: linear response theory, variational treatment, and nuclear gradients. J Chem Phys. 2009; 131(18):184103. DOI: 10.1063/1.3259550. View

14.

Friedman H, Cosco E, Atallah T, Jia S, Sletten E, Caram J . Establishing design principles for emissive organic SWIR chromophores from energy gap laws. Chem. 2021; 7(12):3359-3376. PMC: 8664240. DOI: 10.1016/j.chempr.2021.09.001. View

15.

Cosco E, Spearman A, Ramakrishnan S, Lingg J, Saccomano M, Pengshung M . Shortwave infrared polymethine fluorophores matched to excitation lasers enable non-invasive, multicolour in vivo imaging in real time. Nat Chem. 2020; 12(12):1123-1130. PMC: 7680456. DOI: 10.1038/s41557-020-00554-5. View

16.

Grimm J, Brown T, Tkachuk A, Lavis L . General Synthetic Method for Si-Fluoresceins and Si-Rhodamines. ACS Cent Sci. 2017; 3(9):975-985. PMC: 5620978. DOI: 10.1021/acscentsci.7b00247. View

17.

Roskop L, Gordon M . Quasi-degenerate second-order perturbation theory for occupation restricted multiple active space self-consistent field reference functions. J Chem Phys. 2011; 135(4):044101. DOI: 10.1063/1.3609756. View

18.

Homma M, Takei Y, Murata A, Inoue T, Takeoka S . A ratiometric fluorescent molecular probe for visualization of mitochondrial temperature in living cells. Chem Commun (Camb). 2015; 51(28):6194-7. DOI: 10.1039/c4cc10349a. View

19.

Li H, Jensen J . Improving the efficiency and convergence of geometry optimization with the polarizable continuum model: new energy gradients and molecular surface tessellation. J Comput Chem. 2004; 25(12):1449-62. DOI: 10.1002/jcc.20072. View

20.

Chai X, Cui X, Wang B, Yang F, Cai Y, Wu Q . Near-Infrared Phosphorus-Substituted Rhodamine with Emission Wavelength above 700 nm for Bioimaging. Chemistry. 2015; 21(47):16754-8. DOI: 10.1002/chem.201502921. View