Abstract
Photoacids on the basis of pyrenol have been extensively studied in the past 60 years. As their photophysical properties strongly depend on the substituents at the aromatic scaffold, we introduced two reactive moieties with different electronic coefficients thus creating multi-wavelength fluorescent probes. One probe is capable of monitoring two orthogonal transformations by four fluorescence colors, distinguishable even by the naked human eye. Another derivative can act as a three-color sensor for a wide range of different pH values. Both the presented compounds allow for mimicking of fundamental and advanced two-input logic operations due to the multi-wavelength emission. Furthermore, these compounds can process information in a logically reversible way (Feynman gate).
Article PDF
Similar content being viewed by others
Notes and references
A. Baruch, D. A. Jeffery and M., Bogyo, Enzyme activity - it’s all about image, Trends Cell Biol., 2004, 14 29–35
K., Kikuchi, Design, synthesis and biological application of chemical probes for bio-imaging, Chem. Soc. Rev., 2010, 39 2048–2053
M. H. Lee, J. S. Kim and J. L., Sessler, Small molecule-based ratiometric fluorescence probes for cations, anions, and biomolecules, Chem. Soc. Rev., 2015, 44 4185–4191
J. R. Lakowicz, Principles of Fluorescence Spectroscopy, Springer, 3rd edn, 2006
I. Johnson and M. T. Z. Spence, The Molecular Probes Handbook, 2010
X. Li, X. Gao, W. Shi and H., Ma, Design strategies for water-soluble small molecular chromogenic and fluorogenic probes, Chem. Rev., 2014, 114 590–659
D. J. Yee, V. Balsanek, D. R. Bauman, T. M. Penning and D., Sames, Fluorogenic metabolic probes for direct activity readout of redox enzymes: Selective measurement of human AKR1C2 in living cells, Proc. Natl. Acad. Sci. U. S. A., 2006, 103 13304–13309
H. Shi, R. T. K. Kwok, J. Liu, B. Xing, B. Z. Tang and B., Liu, Real-time monitoring of cell apoptosis and drug screening using fluorescent light-up probe with aggregation-induced emission characteristics, J. Am. Chem. Soc., 2012, 134 17972–17981
M. Kamiya, D. Asanuma, E. Kuranaga, A. Takeishi, M. Sakabe, M. Miura, T. Nagano and Y., Urano, β-galactosidase fluorescence probe with improved cellular accumulation based on a spirocyclized rhodol scaffold, J. Am. Chem. Soc., 2011, 133 12960–12963
A. P., Demchenko, Practical aspects of wavelength ratiometry in the studies of intermolecular interactions, J. Mol. Struct., 2014, 1077 51–67
A. P., Demchenko, The concept of λ-ratiometry in fluorescence sensing and imaging, J. Fluoresc., 2010, 20 1099–1128
Z.-M. Liu, L. Feng, G.-B. Ge, X. Lv, J. Hou, Y.-F. Cao, J.-N. Cui and L., Yang, A highly selective ratiometric fluorescent probe for in vitro monitoring and cellular imaging of human carboxylesterase 1, Biosens. Bioelectron., 2014, 57 30–35
Z. Song, R. T. K. Kwok, E. Zhao, Z. He, Y. Hong, J. W. Y. Lam, B. Liu and B. Z., Tang, A ratiometric fluorescent probe based on ESIPT and AIE processes for alkaline phosphatase activity assay and visualization in living cells, ACS Appl. Mater. Interfaces, 2014, 6 17245–17254
Y. Kurishita, T. Kohira, A. Ojida and I., Hamachi, Rational design of FRET-based ratiometric chemosensors for in vitro and in cell fluorescence analyses of nucleoside polyphosphates, J. Am. Chem. Soc., 2010, 132 13290–13299
L., Chen, et al., The first ratiometric fluorescent probes for aminopeptidase N cell imaging, Org. Biomol. Chem., 2013, 11 378–382
T. Komatsu, Y. Urano, Y. Fujikawa, T. Kobayashi, H. Kojima, T. Terai, K. Hanaoka and T., Nagano, Development of 2,6-carboxy-substituted boron dipyrromethene (BODIPY) as a novel scaffold of ratiometric fluorescent probes for live cell imaging, Chem. Commun., 2009, 7015–7017
S. Debieu and A., Romieu, Dual enzyme-responsive ‘turn-on’ fluorescence sensing systems based on in situ formation of 7-hydroxy-2-iminocoumarin scaffolds, Org. Biomol. Chem., 2015, 13 10348–10361
J. Halámek, et al., Multiplexing of injury codes for the parallel operation of enzyme logic gates, Analyst, 2010, 135 2249–2259
L. Halámková, J. Halámek, V. Bocharova, S. Wolf, K. E. Mulier, G. Beilman, J. Wang and E., Katz, Analysis of biomarkers characteristic of porcine liver injury-from biomolecular logic gates to an animal model, Analyst, 2012, 137 1768–1770
A., Romieu, ‘AND’ luminescent ‘reactive’ molecular logic gates: a gateway to multi-analyte bioimaging and biosensing, Org. Biomol. Chem., 2015, 13 1294–1306
Y. Li, H. Wang, J. Li, J. Zheng, X. Xu and R., Yang, Simultaneous intracellular β-D-glucosidase and phosphodiesterase I activities measurements based on a triple-signaling fluorescent probe, Anal. Chem., 2011, 83 1268–1274
M. Prost and J., Hasserodt, ‘Double gating’ - a concept for enzyme-responsive imaging probes aiming at high tissue specificity, Chem. Commun., 2014, 50 14896–14899
S.-Y. Li, L.-H. Liu, H. Cheng, B. Li, W.-X. Qiu and X.-Z. Zhang, A dual-FRET-based fluorescence probe for the sequential detection of MMP-2 and caspase-3, Chem. Commun., 2015, 51 14520–14523
T.-I. Kim, H. Kim, Y. Choi and Y., Kim, A fluorescent turn-on probe for the detection of alkaline phosphatase activity in living cells, Chem. Commun., 2011, 47 9825–9827
J. L. Millán and W. H., Fishman, Biology of human alkaline phosphatases with special reference to cancer, Crit. Rev. Clin. Lab. Sci., 1995, 32 1–39
Y. Zhang, W. Chen, D. Feng, W. Shi, X. Li and H., Ma, A spectroscopic off-on probe for simple and sensitive detection of carboxylesterase activity and its application to cell imaging, Analyst, 2012, 137 716–721
J. Andréasson and U., Pischel, Molecules with a sense of logic: a progress report, Chem. Soc. Rev., 2015, 1053–1069
A. P. De Silva, Molecular logic-based computation, RSC Publishing, 2013
K. Szaciłowski, Infochemistry: Information Processing at the Nanoscale, Wiley-VCH, 2012
P. Gassman and W., Schenk, A general procedure for the base-promoted hydrolysis of hindered esters at ambient temperatures, J. Org. Chem., 1977, 42 918–920
T. Förster, Elektrolytische Dissoziation angeregter Moleküle, Z. Elektrochem., 1950, 54 42–46
E. Pines, The Chemistry of Phenols, John Wiley & Sons Ltd, 2003
N., Agmon, Elementary steps in excited-state proton transfer, J. Phys. Chem. A, 2005, 109 13–35
L. M. Tolbert and J. E., Haubrich, Enhanced photoacidities of cyanonaphthols, J. Am. Chem. Soc., 1990, 112 8163–8165
L. M. Tolbert and J. E., Haubrich, Photoexcited proton transfer from enhanced photoacids, J. Am. Chem. Soc., 1994, 116 10593–10600
D. Huppert, L. M. Tolbert and S. Linares-Samaniego, Ultrafast excited-state proton transfer from cyano-substituted 2-naphthols, J. Phys. Chem. A, 1997, 101 4602–4605
C. Clower, K. M. Solntsev, J. Kowalik, L. M. Tolbert and D., Huppert, Photochemistry of ‘super’ photoacids. 3. excited-state proton transfer from perfluoroalkylsulfonyl-substituted 2-naphthols, J. Phys. Chem. A, 2002, 106 3114–3122
T.-H. Tran-Thi, C. Prayer, P. Millié, P. Uznanski and J. T., Hynes, Substituent and solvent effects on the nature of the transitions of pyrenol and pyranine. identification of an intermediate in the excited-state proton-transfer reaction, J. Phys. Chem. A, 2002, 106 2244–2255
K. M. Solntsev, E. N. Sullivan, L. M. Tolbert, S. Ashkenazi, P. Leiderman and D., Huppert, Excited-state proton transfer reactions of 10-hydroxycamptothecin, J. Am. Chem. Soc., 2004, 126 12701–12708
M. Prémont-Schwarz, T. Barak, D. Pines, E. T. J. Nibbering and E., Pines, Ultrafast excited state proton transfer reaction of 1-naphthol-3,6-disulfonate and several 5-substituted 1-naphthol derivatives, J. Phys. Chem. B, 2013, 117 4593–4594
C. Spies, B. Finkler, N. Acar and G., Jung, Solvatochromism of pyranine-derived photoacids, Phys. Chem. Chem. Phys., 2013, 15 19893–19905
C. Spies, S. Shomer, B. Finkler, D. Pines, E. Pines, G. Jung and D., Huppert, Solvent dependence of excited-state proton transfer from pyranine-derived photoacids, Phys. Chem. Chem. Phys., 2014, 16 9104–9114
B. Finkler, et al. Highly photostable ‘super’-photoacids for ultrasensitive fluorescence spectroscopy, Photochem. Photobiol. Sci., 2014, 13 548–562
C. Hansch, A. Leo and R. W., Taft, A survey of Hammett substituent constants and resonance and field parameters, Chem. Rev., 1991, 91 165–195
H. N. Fernley and P. G., Walker, Kinetic behaviour of calf-intestinal alkaline phosphatase with 4-methylumbelliferyl phosphate, Biochem. J., 1965, 97 95–103
S. Lun and W. R., Bishai, Characterization of a novel cell wall-anchored protein with carboxylesterase activity required for virulence in mycobacterium tuberculosis, J. Biol. Chem., 2007, 282 18348–18356
L. Provencher and J. B., Jones, A concluding specification of the dimensions of the active site model of pig liver esterase, J. Org. Chem., 1994, 59 2729–2732
P. D. De María, C. A. García-Burgos, G. Bargeman and R. W. Van Gemert, Pig liver esterase (PLE) as biocatalyst in organic synthesis: From nature to cloning and to practical applications, Synthesis, 2007, 10 1439–1452
J. L. Ward and C. M., Tse, Nucleoside transport in human colonic epithelial cell lines: evidence for two Na+-independent transport systems in T84 and Caco-2 cells, Biochim. Biophys. Acta, Biomembr., 1999, 1419 15–22
M. Pastor-Anglada, P. Cano-Soldado, M. Molina-Arcas, M. P. Lostao, I. Larráyoz, J. Martínez-Picado and F. J., Casado, Cell entry and export of nucleoside analogues, Virus Res., 2005, 107 151–164
M. N. Win and C. D., Smolke, Higher-order cellular information processing with synthetic RNA devices, Science, 2008, 322 456–460
M. Elstner, J. Axthelm and A., Schiller, Sugar-based molecular computing by material implication, Angew. Chem., Int. Ed., 2014, 53 7339–7343
J. Ditkovich, T. Mukra, D. Pines, D. Huppert and E., Pines, Bifunctional photoacids: Remote protonation affecting chemical reactivity, J. Phys. Chem. B, 2015, 119 2690–2701
B. Zelent, J. M. Vanderkooi, R. G. Coleman, I. Gryczynski and Z., Gryczynski, Protonation of excited state pyrene-1-carboxylate by phosphate and organic acids in aqueous solution studied by fluorescence spectroscopy, Biophys. J., 2006, 91 3864–3871
N. V. Nucci, B. Zelent and J. M., Vanderkooi, Pyrene-1-carboxylate in water and glycerol solutions: Origin of the change of pK upon excitation, J. Fluoresc., 2008, 18 41–49
B. Zelent, J. M. Vanderkooi, N. V. Nucci, I. Gryczynski and Z., Gryczynski, Phosphate assisted proton transfer in water and sugar glasses: A study using fluorescence of pyrene-1-carboxylate and IR spectroscopy, J. Fluoresc., 2009, 19 21–31
A., Weller, Outer and inner mechanism of reactions of excited molecules, Discuss. Faraday Soc., 1959, 27 28–33
A., Weller, Fast reactions of excited molecules, Prog. React. Kinet., 1961, 1 187–214
D. B. Spry and M. D., Fayer, Observation of slow charge redistribution preceding excited-state proton transfer, J. Chem. Phys., 2007, 127 204501
E. Pines, D. Pines, Y.-Z. Ma and G. R., Fleming, Femtosecond pump-probe measurements of solvation by hydrogen-bonding interactions, ChemPhysChem, 2004, 5 1315–1327
D. B. Spry and M. D., Fayer, Observation of slow charge redistribution preceding excited-state proton transfer, J. Chem. Phys., 2007, 127 204501
C. Spies, B. Finkler, N. Acar and G., Jung, Solvatochromism of pyranine-derived photoacids, Phys. Chem. Chem. Phys., 2013, 15 19893–19905
H. Offenbacher, O. S. Wolfbeis and E., Furlinger, Fluorescence optical sensors for continuous determination of near-neutral pH values, Sens. Actuators, 1986, 9 73–84
G. M., Ullmann, Relations between protonation constants and titration curves in polyprotic acids: A critical view, J. Phys. Chem. B, 2003, 107 1263–1271
R. Bizzarri, et al. Green fluorescent protein ground states: The influence of a second protonation site near the chromophore, Biochemistry, 2007, 46 5494–5504
A. P. De Silva, N. H. Q. Gunaratne and C. P., McCoy, A molecular photoionic AND gate based on fluorescent signalling, Nature, 1993, 364 42–44
J. Andréasson and U., Pischel, Smart molecules at work-mimicking advanced logic operations, Chem. Soc. Rev., 2010, 39 174–188
A. P. De Silva and N. D., McClenaghan, Molecular-scale logic gates, Chem. - Eur. J., 2004, 10 574–586
A. Coskun, E. Deniz and E. U., Akkaya, Effective PET and ICT switching of boradiazaindacene emission: A unimolecular, emission-mode, molecular half-subtractor with reconfigurable logic gates, Org. Lett., 2005, 7 5187–5189
J. Andréasson, U. Pischel, S. D. Straight, T. a. Moore, A. L. Moore and D., Gust, All-photonic multifunctional molecular logic device, J. Am. Chem. Soc., 2011, 133 11641–11648
J. Andréasson, S. D. Straight, T. A. Moore, A. L. Moore and D., Gust, Molecular all-photonic encoder-decoder, J. Am. Chem. Soc., 2008, 130 11122–11128
D. Kang, R. J. White, F. Xia, X. Zuo, A. Vallée-Bélisle and K. W., Plaxco, DNA biomolecular-electronic encoder and decoder devices constructed by multiplex biosensors, NPG Asia Mater., 2012, 4 e1
R. Orbach, F. Remacle, R. D. Levine and I., Willner, DNAzyme-based 2:1 and 4:1 multiplexers and 1:2 demultiplexer, Chem. Sci., 2014, 5 1074–1081
L. Zhao, W. Xia and C., Yang, Fluorescent 1:2 demultiplexer and half-subtractor based on the hydrolysis of N-salicylidene-3-aminopyridine, Spectrochim. Acta, Part A, 2014, 117 397–401
J. Andréasson, G. Kodis, Y. Terazono, P. A. Liddell, S. Bandyopadhyay, R. H. Mitchell, T. A. Moore, A. L. Moore and D., Gust, Molecule-based photonically switched half-adder, J. Am. Chem. Soc., 2004, 126 15926–15927
F. Remacle, R. Weinkauf and R. D., Levine, Molecule-based photonically switched half and full adder, J. Phys. Chem. A, 2006, 110 177–184
H. Pei, L. Liang, G. Yao, J. Li, Q. Huang and C., Fan, Reconfigurable three-dimensional DNA nanostructures for the construction of intracellular logic sensors, Angew. Chem., Int. Ed., 2012, 51 9020–9024
D. Margulies, G. Melman and A., Shanzer, Fluorescein as a model molecular calculator with reset capability, Nat. Mater., 2005, 4 768–771
D. Margulies, G. Melman and A., Shanzer, A molecular full-adder and full-subtractor, an additional step toward a moleculator, J. Am. Chem. Soc., 2006, 128 4865–4871
D. Margulies, C. E. Felder, G. Melman and A., Shanzer, A molecular keypad lock: A photochemical device capable of authorizing password entries, J. Am. Chem. Soc., 2007, 129 347–354
P. Remón, M. Hammarson, S. Li, A. Kahnt, U. Pischel and J. Andréasson, Molecular implementation of sequential and reversible logic through photochromic energy transfer switching, Chem. - Eur. J., 2011, 17 6492–6500
Q. Li, Y. Yue, Y. Guo and S., Shao, Fluoride anions triggered ‘OFF-ON’ fluorescent sensor for hydrogen sulfate anions based on a BODIPY scaffold that works as a molecular keypad lock, Sens. Actuators, B, 2012, 173 797–801
X.-J. Jiang and D. K. P., Ng, Sequential logic operations with a molecular keypad lock with four inputs and dual fluorescence outputs, Angew. Chem., Int. Ed., 2014, 53 10481–10484
B. Rout, P. Milko, M. A. Iron, L. Motiei and D., Margulies, Authorizing multiple chemical passwords by a combinatorial molecular keypad lock, J. Am. Chem. Soc., 2013, 135 15330–15333
G. Strack, M. Ornatska, M. Pita and E., Katz, Biocomputing security system: concatenated enzyme-based logic gates operating as a biomolecular keypad lock, J. Am. Chem. Soc., 2008, 130 4234–5235
J. Chen, S. Zhou and J., Wen, Concatenated logic circuits based on a three-way DNA junction: A keypad-lock security system with visible readout and an automatic reset function, Angew. Chem., Int. Ed., 2014, 54 446–450
A. P. De Silva and N. D., McClenaghan, Proof-of-principle of molecular-scale arithmetic, J. Am. Chem. Soc., 2000, 122 3965–3966
P. Remón, M. Bälter, S. Li, J. Andréasson and U., Pischel, An all-photonic molecule-based D flip-flop, J. Am. Chem. Soc., 2011, 133 20742–20745
Y. Liu, W. Jiang, H. Y. Zhang and C. J., Li, A multifunctional arithmetical processor model integrated inside a single molecule, J. Phys. Chem. B, 2006, 110 14231–14235
R. Gotor, A. M. Costero, S. Gil, M. Parra, P. Gaviña and K., Rurack, Boolean operations mediated by an ion-pair receptor of a multi-readout molecular logic gate, Chem. Commun., 2013, 49 11056–11058
M. Vester, T. Staut, J. Enderlein and G., Jung, Photon antibunching in a cyclic chemical reaction scheme, J. Phys. Chem. Lett., 2015, 6 1149–1154
M. Vester, A. Grueter, B. Finkler, R. Becker and G., Jung, Biexponential photon antibunching: Recombination kinetics within the Forster-cycle in DMSO, Phys. Chem. Chem. Phys., 2016, 18 10281–10288
R. K. Sehgal and S., Kumar, A simple preparation of 1-hydroxypyrene, Org. Prep. Proced. Int. New J. Org. Synth., 1989, 21 223–225
Author information
Authors and Affiliations
Corresponding author
Additional information
This work is dedicated to Andreas Zumbusch on the occasion of his 50th birthday.
Electronic supplementary information (ESI) available: Further compound characterization, determination of enzyme kinetics, further preliminary live-cell experiments and details for molecular logic. CCDC 1443123. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6pp00290k
Rights and permissions
This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.
About this article
Cite this article
Finkler, B., Riemann, I., Vester, M. et al. Monomolecular pyrenol-derivatives as multi-emissive probes for orthogonal reactivities. Photochem Photobiol Sci 15, 1544–1557 (2016). https://doi.org/10.1039/c6pp00290k
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1039/c6pp00290k