Abstract
Novel probes represented connection of pyrene as chromophore and sterically hindered amine stabilizers (HAS) in the form of esters of 2-(1-pyrenyl)acrylic acid were synthesized. HAS was in the form of parent amine (PAP) as well as stable nitroxyl radical form (PAP-NO.). Photophysics of these probes were compared with their precursor as 2-(1-pyrenyl)acrylic acid (PAA) and its methyl ester (PAM). The fluorescence spectrum of PAA strongly depends on the acidity of the solution. The spectrum in neutral methanol indicates that it originates from the anionic form –COO−. Changes of acidity or basicity of methanol solution resulted in the changes of shape, position as well as the intensity of fluorescence band. This is due to the presence of protolytic equilibria, either in the ground state or in the singlet excited state, leading to the formation of molecular form –COOH and the cationic form –COOH2+. The ester analogues did not show any changes in various pH conditions. Fluorescence of all probes depends on the polarity of solvents and the presence of oxygen. Intermolecular quenching was studied with external quenchers TEMPO and oxygen and the data were compared with the intramolecular quenching using 1′-oxo-2′,2′,6′,6′-tetramethyl-4′-piperidinyl-2-(1-pyrenyl)acrylate (PAP-NO.).
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
W. Rettig and R. Lapoyade (1994). in J. R. Lakowicz (Ed.), Topics in Fluorescence Spectroscopy Probe Design and Chemical Sensing, Vol. 4. Plenum Press, New York, p. 109.
J. K. Thomas (1993). Physical aspects of photochemistry and radiation chemistry of molecules adsorbed on silica, gamma-alumina, zeolites, and clays. Chem. Rev. 93, 301–320.
K. Kalyanasundaran and J. K. Thomas (1977). Environmental effects on vibronic band intensities in pyrene monomer fluorescence and their application in studies of micellar systems. J. Am. Chem. Soc. 99, 2039–2044.
F. M. Winnik and S. T. A. Regismond (1996). Fluorescence methods in the study of the interaction of surfactants with polymer. Colloids Surf. A 118, 1–39.
P. Hrdloviĉ and I. Lukáĉ (2000). Monosubstituted derivatives of pyrene: Comparison of their spectral behaviour in solution and in polymer matrices. J. Photochem. Photobiol. A: Chem. 133, 73–82.
M. Nowakowska and J. E. Guillet (1991). Studies of the antenna effect in polymer systems. 18. Photochemical reactions of styrene solubilized in an aqueous solution of poly(sodium styrenesulfonate-co-2-vinylnaphthalene). Macromolecules 24, 474–478.
M. Danko, P. Hrdlović, and E. Borsig (2003). Monitoring of swelling of interpenetrating polymer network of polyethylene/poly(styrene-co-butylmethacrylate) (PE/P(S-co-BMA)) in toluene and cyclohexane using fluorescence spectroscopy. Polymer 44, 389–396.
S. Pankasem, M. Biscoglio, and J. K. Thomas (2000). Photophysics of pyrenyl acrylic acid and its methyl ester. A spectroscopic method to monitor polymerization and surface properties. Langmuir 16, 3620–3625.
E. N. Step, N. J. Turro, P. P. Klemchuk, and M. E. Gande (1995). Model studies on the mechanism of HALS stabilization. Angew. Makromol. Chem. 232, 65.
A. R. Watkins (1980). Solvent effects on triplet state quenching by tetramethylpiperidine-N-oxide. Chem. Phys. Lett. 70, 262–265.
J. A. Green and L. A. Singer (1974). Di-tert-butyl nitroxide as a convenient probe for excited singlet states. Pyrene luminescence. J. Am. Chem. Soc. 96, 2730–2733.
V. A. Kuzmin and A. S. Tatikolov (1977). Formation of triplets of aromatic hydrocarbons on quenching of excited singlet states by nitroxyl radicals. Chem. Phys. Lett. 51, 45–47.
A. S. Green, D. J. Simpson, G. Zhou, P. S. Ho, and N. V. Blough (1990). Intramolecular quenching of excited singlet states by stable nitroxyl radicals. J. Am. Chem. Soc. 112, 7337–7346.
S. Jockusch, G. Dedola, G. Lem, and N. J. Turro (1999). Electron spin polarization by intramolecular triplet quenching of a nitroxyl radical labeled thioxanthonedioxide. J. Phys. Chem. B 103, 9126–9129.
P. Hrdloviĉ and Ŝ. Chmela (1998). Spectral characteristics of multifunctional probes based on pyrene in solution and in polymer matrices. J. Photochem. Photobiol. A: Chem. 105, 83–88.
P. Hrdloviĉ, Ŝ. Chmela, M. Sarakha, and J. Lacoste (2001). Transient absorption spectra of bifunctional probes of a chromophore-sterically hindered amine type in solution; study of the triplet route to deactivation. J. Photochem. Photobiol. A: Chem. 138, 95– 109.
L’. Búcsiová, A. Búcsi, P. Hrdloviĉ, and Ŝ. Chmela (2002). Characterization of stable nitroxide radicals on the basis of adduct chromophore-hindered amine utilizing EPR spectroscopy in solution and polymer matrix. Chem. Pap. 56, 275–281.
L’. Búcsiová, P. Hrdloviĉ, and Ŝ. Chmela (2001). Spectral characteristics of fluorescence probes based on pyrene in solution and in polymer matrix. J. Photochem. Photobiol. A: Chem. 143, 59– 68.
E. Bosch, P. Bou, H. Alleman, and M. Marti Roses (1996). Retention of ionizable compounds on HPLC. pH scale in methanol–water and the pK and pH values of buffers. Anal. Chem. 68, 3651– 3657.
S. Rondinini, P. R. Mussini, T. Mussini, and A. Vertova (1998). pH measurements in non-aqueous and mixed solvents: Predicting pH (PS) of potasium hydrogen phthalate for alcohol–water mixtures. Pure Appl. Chem. 70(7), 1419–1422.
B. H. Milosavljevic and J. K. Thomas (1988). Solvent effects on the photophysical properties of pyrene-3-carboxylic acid. J. Phys. Chem. 92, 2997–3001.
S. Murow, I. Carnichack, G. L. Hund, and Marcel Decker (1993). Handbook of Photochemistry, 2nd ed.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Chmela, Š., Kollár, J., Hrdlovič, P. et al. Preparation and Photophysics of 2-(1-Pyrenyl)acrylic Acid and Its Methyl and 2′,2′,6′,6′-Tetramethyl-4′-Piperidyl Esters. J Fluoresc 15, 243–253 (2005). https://doi.org/10.1007/s10895-005-2624-1
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/s10895-005-2624-1