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Two-Photon Semiconducting Polymer Dots with Dual-Emission for Ratiometric Fluorescent Sensing and Bioimaging of Tyrosinase Activity Junyong Sun, Han Mei, Sufan Wang, and Feng Gao Anal. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.analchem.6b01929 • Publication Date (Web): 20 Jun 2016 Downloaded from http://pubs.acs.org on June 26, 2016
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Analytical Chemistry
Two-Photon Semiconducting Polymer Dots with Dual-Emission for Ratiometric Fluorescent Sensing and Bioimaging of Tyrosinase Activity Junyong Sun, Han Mei, Sufan Wang, and Feng Gao* Laboratory of Functionalized Molecular Solids, Ministry of Education, Anhui Key Laboratory of Chemo/Biosensing, Laboratory of Optical Probes and Bioelectrocatalysis (LOPAB), College of Chemistry and Materials Science, Anhui Normal University, Wuhu 241000, P. R. China
*
Corresponding author. Tel. +86-553-3937137; Fax: +86-553-3869302
E-mail:
[email protected]. 1
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Analytical Chemistry
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ABSTRACT
Semiconducting polymer dots (Pdots) with one-, two-photon excitation and dual-emission have been
synthesized
by
co-precipitation
of
two
poly(9,9-dioctylfluorenyl-2,7-diyl)
conjugated
polymers
including
(PFO)
and
poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-(1-cyanovinylene-1,4-phenylene)] (CN-PPV) and have been further functionalized with L-tyrosine methyl ester (Tyr-OMe) via electrostatic assembly for ratiometric fluorescent sensing and bioimaging of tyrosinase activity. Tyrosinase-catalyzed oxidation
of
Tyr-OMe
effectively
modulate
the
dual-emission
fluorescence
of
PFO/CN-PPV@Tyr-OMe Pdots from orange to blue through a selective photo-induced electron transfer (PET) process. A two-photon ratiometric sensor at almost zero-background interfering and bioimaging of tyrosinase activity have been demonstrated, suggesting the potential biomedical applications of the prepared functionalized Pdots.
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Analytical Chemistry
INTRODUCTION Tyrosinase (TR), an important polyphenol oxidase, initiates the aerobic oxidation of tyrosine for the production of melanin biopolymer and plays significant roles in melanin biosynthesis. The disordering of tyrosinase in human body might cause Parkinson's disease1 and also tyrosinase has been regarded as an important biomarker for melanoma owing to the overexpression level.
2
Therefore, the detection of tyrosinase activity is of great value in ascertaining Parkinson's disease and melanoma. Among the variously developed TR sensors, fluorescence-based assays are promising methods due to their high sensitivity and noninvasive imaging.
1,3-5
However, the
fluorescent probes based on the fluorescence quenching (turn-off ) or enhancing (turn-on) effects at a certain wavelength generally suffer from the unavoidable disturbance induced by intensity fluctuations ascribed to the instrumental or environmental factors.6,7 Very recently, the ratiometric TR sensing mechanisms by measuring the relative fluorescence varies at two wavelengths of a fluorescent probe, coupling with the TR-catalyzed oxidation of TR substrate, dopamine, have been expected to overcome the above-mentioned concern. 8,9 Unfortunately, dopamine is air-unstable and sensitive to pH, which may induce the instability of the analytical system and therefore limit its further biological applications. In addition, the overwhelming majority of the developed fluorescent probes for TR sensors are excited with short wavelength (usually in UV region), leading to some defects such as auto-fluorescence interferences from tissues, limited penetration depth (
