Abstract
Fluorescence and singlet molecular oxygen (1O2) quantum yields for phloxine B loaded poly(2-hydroxyethyl methacrylate) thin films are determined at dye concentrations from 0.015 to 22 wt%. Fluorescence self-quenching and the fall off of the 1O2 quantum yield observed above 0.1 wt% are attributed to very weakly interacting close-lying dye molecules acting as energy traps arising from molecular confinement. The maximum singlet oxygen generation efficiency (quantum yield × absorption factor) lies at concentrations around 2 wt%, where fluorescence self quenching amounts to more than 80%. Data are fitted quantitatively by using a quenching radius model involving energy migration and trapping with rQ = 1.2 nm. The present results constitute a proof of concept for the rational design of heterogeneous photosensitizers in general and, particularly, for applications in which the antimicrobial activity of singlet oxygen is central.
Similar content being viewed by others
References
F. Baldini, A. N. Chester, J. Homola and S. Martellucci, Optical Chemical Sensors, Springer, Dordrecht, 2006.
Y. Huang, S.-T. Wu, Multi-Wavelength Laser from Dye-Doped Cholesteric Polymer Films, Opt. Express, 2010, 18, 27697–27702.
S. Kawata and Y. Kawata, Three-Dimensional Optical Data Storage Using Photochromic Materials, Chem. Rev., 2000, 100, 1777–1788.
R. Waning and S. Muke, Authentication Means. PCT Int. Pat., WO2004087430, 2004.
H. Dotan, O. Kfir, E. Sharlin, O. Blank, M. Gross, I. Dumchin, G. Ankonina and A. Rothschild, Resonant Light Trapping in Ultrathin Films for Water Splitting, Nat. Mater., 2013, 12, 158–164.
M. Nowakowska, M. Kepczynski and K. Szczubialka, New Polymeric Photosensitizers, Pure Appl. Chem., 2001, 73, 491–495.
A. Priimagi, S. Cattaneo, R. H. A. Ras, S. Valkama, O. Ikkala and M. Kauranen, Polymer-Dye Complexes: A Facile Method for High Doping Level and Aggregation Control of Dye Molecules, Chem. Mater., 2005, 17, 5798–5802.
S. G. López, G. Worringer, H. B. Rodríguez, E. San Román, Trapping of Rhodamine 6G Excitation Energy on Cellulose Microparticles, Phys. Chem. Chem. Phys., 2010, 12, 2246–2253.
M. Mirenda, C. A. Strassert, L. E. Dicelio, E. San Román, Dye-Polyelectrolyte Layer-by-Layer Self-Assembled Materials: Molecular Aggregation, Structural Stability, and Singlet Oxygen Photogeneration, ACS Appl. Mater. Interfaces, 2010, 2, 1556–1560.
A. Opdahl, S. H. Kim, T. S. Koffas, C. Marmo and G. A. Somorjai, Surface Mechanical Properties of pHEMA Contact Lenses: Viscoelastic and Adhesive Property Changes on Exposure to Controlled Humidity, J. Biomed. Mater. Res., Part A, 2003, 67, 350–356.
C. Maldonado-Codina and N. Efron, Dynamic Wettability of pHEMA-Based Hydrogel Contact Lenses, Ophthal. Physiol. Opt., 2006, 26, 408–418.
E. Gandin, Y. Lion, A. Van de Vorst, Quantum Yield of Singlet Oxygen Production by Xanthene Derivatives, Photochem. Photobiol., 1983, 37, 271–278.
P. Duarte, D. P. Ferreira, I. Ferreira Machado, L. F. Vieira Ferreira, H. B. Rodríguez, E. San Román, Phloxine B as a Probe for Entrapment in Microcrystalline Cellulose, Molecules, 2012, 17, 1602–1616.
A. Rasooly and A. Weisz, In Vitro Antibacterial Activities of Phloxine B and Other Halogenated Fluoresceins Against Methicillin-Resistant Staphylococcus aureus, Antimicrob. Agents Chemother., 2002, 46, 3650–3653.
R. Rasooly, Expanding the Bactericidal Action of the Food Color Additive Phloxine B to Gram-Negative Bacteria, FEMS Immunol. Med. Microbiol., 2005, 45, 239–244.
D. S. Moreno, H. Celedonio, R. L. Mangan, J. L. Zavala and P. Montoya, Field Evaluation of a Phototoxic Dye, Phloxine B, Against Three Species of Fruit Flies (Diptera: Tephritidae), J. Econ. Entomol., 2001, 94, 1419–1427.
H. Qi, H. Takano, Y. Kato, Q. Wu, C. Ogata, B. Zhu, Y. Murata and Y. Nakamura, Hydrogen Peroxide-Dependent Photocytotoxicity by Phloxine B, a Xanthene-Type Food Colorant, Biochim. Biophys. Acta, 2011, 1810, 704–712.
H. Qi, B. Zhu, N. Abe, Y. Shin, Y. Murata and Y. Nakamura, Involvement of Intracellular Oxidative Stress-Sensitive Pathway in Phloxine B-Induced Photocytotoxicity in Human T Lymphocytic Leukemia Cells, Food Chem. Toxicol., 2012, 50, 1841–1847.
C. P. McCoy, R. A. Craig, S. M. McGlinchey, L. Carson, D. S. Jones and S. P. Gorman, Surface Localisation of Photosensitisers on Intraocular Lens Biomaterials for Prevention of Infectious Endophthalmitis and Retinal Protection, Biomaterials, 2012, 33, 7952–7958.
R. F. Loring, H. C. Andersen and M. D. Fayer, Electronic Excited State Transport and Trapping in Solution, J. Chem. Phys., 1982, 76, 2015–2027.
L. Kulak and C. Bojarski, Forward and Reverse Electronic Energy Transport and Trapping in Solution. II. Numerical Results and Monte Carlo Simulations, Chem. Phys., 1995, 191, 67–86.
Y. Usui, Determination of Quantum Yield of Singlet Oxygen Formation by Photosensitization, Chem. Lett., 1973, 2, 743–744.
M. Nowakowska, Solvent Effect on the Quantum Yield of the Self-Sensitized Photoperoxidation of 1,3-Diphenilisobenzofuran, J. Chem. Soc., Faraday Trans. 1, 1984, 80, 2119–2126.
A. De Girolamo Del Mauro, A. I. Grimaldi, V. La Ferrara, E. Massera, M. L. Miglietta, T. Polichetti, G. Di Francia, A Simple Optical Model for the Swelling Evaluation in Polymer Nanocomposites, J. Sens., 2009, 703206.
J. W. Parker and M. E. Cox, Mass Transfer of Oxygen in Poly(2-Hydroxyethyl Methacrylate), J. Polym. Sci., Part A: Polym. Chem., 1988, 26, 1179–1188.
J. F. Rabek, Photodegradation of Polymers: Physical Characteristics and Applications, Springer Verlag, Berlin, 2012, p. 87.
G. R. Fleming, A. W. E. Knight, J. M. Morris, R. J. S. Morrison and G. W. Robinson, Picosecond Fluorescence Studies of Xanthene Dyes, J. Am. Chem. Soc., 1977, 99, 4306–4311.
Y. Tian, B. R. Shumway, W. Gao, C. Youngbull, M. R. Holl, R. H. Johnson and D. R. Meldrum, Influence of Matrices on Oxygen Sensing of Three Sensing Films with Chemically Conjugated Platinum Porphyrin Probes and Preliminary Application for Monitoring of Oxygen Consumption of Escherichia coli (E. coli), Sens. Actuators, B, 2010, 150, 579–587.
O. Valdez-Aguilera and D. C. Neckers, Aggregation Phenomena in Xanthene Dyes, Acc. Chem. Res., 1989, 22, 171–177.
H. B. Rodríguez, E. San Román, P. Duarte, I. Ferreira Machado, L. F. Vieira Ferreira, Eosin Y Triplet State as a Probe of Spatial Heterogeneity in Microcrystalline Cellulose, Photochem. Photobiol., 2012, 88, 831–839.
Author information
Authors and Affiliations
Corresponding authors
Rights and permissions
About this article
Cite this article
Litman, Y., Rodríguez, H.B. & San Román, E. Tuning the concentration of dye loaded polymer films for maximum photosensitization efficiency: phloxine B in poly(2-hydroxyethyl methacrylate). Photochem Photobiol Sci 15, 80–85 (2016). https://doi.org/10.1039/c5pp00360a
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1039/c5pp00360a