Protonation of excited state pyrene-1-carboxylate by phosphate and organic acids in aqueous solution studied by fluorescence spectroscopy

Bogumil Zelent, Jane M. Vanderkooi, Ryan G. Coleman, Ignacy Gryczynski, Zygmunt Gryczynski

Research output: Contribution to journalArticle

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Abstract

Pyrene-1-carboxylic acid has a pK of 4.0 in the ground state and 8.1 in the singlet electronic excited state. In the pH range of physiological interest (pH∼5-8), the ground state compound is largely ionized as pyrene-1-carboxylate, but protonation of the excited state molecule occurs when a proton donor reacts with the carboxylate during the excited state lifetime of the fluorophore. Both forms of the pyrene derivatives are fluorescent, and in this work the protonation reaction was measured by monitoring steady-state and time-resolved fluorescence. The rate of protonation of pyrene-COO- by acetic, chloroacetic, lactic, and cacodylic acids is a function of ΓpK, as predicted by Marcus theory. The rate of proton transfer from these acids saturates at high concentration, as expected for the existence of an encounter complex. Trihydrogen-phosphate is a much better proton donor than dihydrogen- and monohydrogen-phosphate, as can be seen by the pH dependence. The proton-donating ability of phosphate does not saturate at high concentrations, but increases with increasing phosphate concentration. We suggest that enhanced rate of proton transfer at high phosphate concentrations may be due to the dual proton donating and accepting nature of phosphate, in analogy to the Grotthuss mechanism for proton transfer in water. It is suggested that in molecular structures containing multiple phosphates, such as membrane surfaces and DNA, proton transfer rates will be enhanced by this mechanism.

Original languageEnglish
Pages (from-to)3864-3871
Number of pages8
JournalBiophysical Journal
Volume91
Issue number10
DOIs
StatePublished - Nov 2006

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Organophosphates
Fluorescence Spectrometry
Protons
Phosphates
Acids
Cacodylic Acid
pyrene
Carboxylic Acids
Molecular Structure
Acetic Acid
Lactic Acid
Fluorescence
Membranes
Water
DNA

Cite this

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title = "Protonation of excited state pyrene-1-carboxylate by phosphate and organic acids in aqueous solution studied by fluorescence spectroscopy",
abstract = "Pyrene-1-carboxylic acid has a pK of 4.0 in the ground state and 8.1 in the singlet electronic excited state. In the pH range of physiological interest (pH∼5-8), the ground state compound is largely ionized as pyrene-1-carboxylate, but protonation of the excited state molecule occurs when a proton donor reacts with the carboxylate during the excited state lifetime of the fluorophore. Both forms of the pyrene derivatives are fluorescent, and in this work the protonation reaction was measured by monitoring steady-state and time-resolved fluorescence. The rate of protonation of pyrene-COO- by acetic, chloroacetic, lactic, and cacodylic acids is a function of ΓpK, as predicted by Marcus theory. The rate of proton transfer from these acids saturates at high concentration, as expected for the existence of an encounter complex. Trihydrogen-phosphate is a much better proton donor than dihydrogen- and monohydrogen-phosphate, as can be seen by the pH dependence. The proton-donating ability of phosphate does not saturate at high concentrations, but increases with increasing phosphate concentration. We suggest that enhanced rate of proton transfer at high phosphate concentrations may be due to the dual proton donating and accepting nature of phosphate, in analogy to the Grotthuss mechanism for proton transfer in water. It is suggested that in molecular structures containing multiple phosphates, such as membrane surfaces and DNA, proton transfer rates will be enhanced by this mechanism.",
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Protonation of excited state pyrene-1-carboxylate by phosphate and organic acids in aqueous solution studied by fluorescence spectroscopy. / Zelent, Bogumil; Vanderkooi, Jane M.; Coleman, Ryan G.; Gryczynski, Ignacy; Gryczynski, Zygmunt.

In: Biophysical Journal, Vol. 91, No. 10, 11.2006, p. 3864-3871.

Research output: Contribution to journalArticle

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AU - Zelent, Bogumil

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AU - Gryczynski, Zygmunt

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