Conjugated polyene fatty acids on fluorescent probes

Spectroscopic characterization

Larry A. Sklar, Bruce S Hudson, Marianne Petersen, James Diamond

Research output: Contribution to journalArticle

215 Citations (Scopus)

Abstract

This paper is the first in a series which extends introductory studies of parinaric acid and its phospholipid derivatives as membrane probes (Sklar, L. A., Hudson, B., and Simoni, R. D. (1975), Proc. Natl. Acad. Sci. U.S.A. 72, 1649; (1976), J. Supramol. Struct. 4, 449). Parinaric acid has a conjugated tetraene chromophore and exhibits many spectroscopic properties common to linear polyenes. Its absorption spectrum is characterized by a strong near-ultraviolet transition with vibronic structure, which is strongly affected by solvent polarizability. The fluorescence emission occurs at considerably lower energy than the absorption and the wave-length of the emission is nearly independent of the solvent. The fluorescence quantum yield and lifetime are strongly affected by temperature and solvent. These spectral features are interpreted in terms of an excited electronic-state order such that a weak transition occurs at longer wavelengths than the strongly allowed transition which dominates the absorption. The sensitivity of the fluorescence quantum yield and lifetime to environment is shown to be due primarily to variations in the nonradiative rate, although changes in the radiative rate constant are also observed and interpreted. The absorption spectrum (εmax > 65 000) is in the 300-320-nm range, a region relatively free of absorption due to intrinsic biological chromophores. Shifts of several nanometers are characteristic of different environments. These shifts are compared to similar effects observed for a series of diphenylpolyenes for which new data are given and are correlated using a simple but adequate theory of solvent shifts. The intrinsic (or radiative) fluorescence lifetime is near 100 ns in a wide variety of environments. This is much longer than the intrinsic lifetime calculated from the absorption spectrum and strongly supports the proposed excited-state order.

Original languageEnglish (US)
Pages (from-to)813-819
Number of pages7
JournalBiochemistry
Volume16
Issue number5
StatePublished - 1977
Externally publishedYes

Fingerprint

Polyenes
Fluorescent Dyes
Fatty Acids
Fluorescence
Absorption spectra
Quantum yield
Chromophores
Wavelength
Electronic states
Excited states
Rate constants
Phospholipids
Derivatives
Membranes
Temperature
parinaric acid

ASJC Scopus subject areas

  • Biochemistry

Cite this

Sklar, L. A., Hudson, B. S., Petersen, M., & Diamond, J. (1977). Conjugated polyene fatty acids on fluorescent probes: Spectroscopic characterization. Biochemistry, 16(5), 813-819.

Conjugated polyene fatty acids on fluorescent probes : Spectroscopic characterization. / Sklar, Larry A.; Hudson, Bruce S; Petersen, Marianne; Diamond, James.

In: Biochemistry, Vol. 16, No. 5, 1977, p. 813-819.

Research output: Contribution to journalArticle

Sklar, LA, Hudson, BS, Petersen, M & Diamond, J 1977, 'Conjugated polyene fatty acids on fluorescent probes: Spectroscopic characterization', Biochemistry, vol. 16, no. 5, pp. 813-819.
Sklar LA, Hudson BS, Petersen M, Diamond J. Conjugated polyene fatty acids on fluorescent probes: Spectroscopic characterization. Biochemistry. 1977;16(5):813-819.
Sklar, Larry A. ; Hudson, Bruce S ; Petersen, Marianne ; Diamond, James. / Conjugated polyene fatty acids on fluorescent probes : Spectroscopic characterization. In: Biochemistry. 1977 ; Vol. 16, No. 5. pp. 813-819.
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