Energy Donor Effect on the Sensing Performance for a Series of FRET-Based Two-Photon Fluorescent Hg2+ Probes

Nonlinear optical properties of a series of newly-synthesized molecular fluorescent probes for Hg2+ containing the same acceptor (rhodamine group) are analyzed by using time-dependent density functional theory in combination with analytical response theory. Special emphasis is placed on evolution of the probes’ optical properties in the absence and presence of Hg2+. These compounds show drastic changes in their photoabsorption and photoemission properties when they react with Hg2+, indicating that they are excellent candidates for ratiometric and colorimetric fluorescent chemosensors. Most importantly, the energy donor moiety is found to play a dominant role in sensing performance of these probes. Two-photon absorption cross sections of the compounds are increased with the presence of Hg2+, which theoretically suggests the possibility of the probes to be two-photon fluorescent Hg2+ sensors. Moreover, analysis of molecular orbitals is presented to explore responsive mechanism of the probes, where the fluorescence resonant energy transfer process is theoretically demonstrated. Our results elucidate the available experimental measurements. This work provides guidance for designing efficient two-photon fluorescent probes that are geared towards biological and chemical applications.

[1]  Wei Jiang,et al.  Rational design of a ratiometric fluorescent probe with a large emission shift for the facile detection of Hg2+. , 2012, Chemical communications.

[2]  Zhong Xu,et al.  A theoretical investigation on two latest two-photon pH fluorescent probes , 2014 .

[3]  Kaibo Zheng,et al.  FRET-based small-molecule fluorescent probes: rational design and bioimaging applications. , 2013, Accounts of chemical research.

[4]  Hongmei Wang,et al.  A new coumarin–rhodamine FRET system as an efficient ratiometric fluorescent probe for Hg2+ in aqueous solution and in living cells , 2015 .

[5]  G. Shen,et al.  Efficient fluorescence resonance energy transfer-based ratiometric fluorescent cellular imaging probe for Zn(2+) using a rhodamine spirolactam as a trigger. , 2010, Analytical chemistry.

[6]  Zhicheng Yan,et al.  A turn-on fluorescent probe for Hg2+ detection by using gold nanoparticle-based hybrid microgels , 2016 .

[7]  Jiangli Fan,et al.  Energy transfer cassettes based on organic fluorophores: construction and applications in ratiometric sensing. , 2013, Chemical Society reviews.

[8]  Jing Liu,et al.  A naphthalimide–rhodamine ratiometric fluorescent probe for Hg2+ based on fluorescence resonance energy transfer , 2012 .

[9]  Jing Zhang,et al.  Molecular engineering of a TBET-based two-photon fluorescent probe for ratiometric imaging of living cells and tissues. , 2014, Journal of the American Chemical Society.

[10]  Q. Guo,et al.  Two-photon fluorescent probes for biological Mg(2+) detection based on 7-substituted coumarin. , 2015, The Journal of organic chemistry.

[11]  Zheng-zhong Lin,et al.  Carbon dots-based fluorescent probe for trace Hg2+ detection in water sample , 2016 .

[12]  张秋月,et al.  Responsive mechanism of 2-（2＇-hydroxyphenyl）benzoxazole-based two-photon fluorescent probes for zinc and hydroxide ions , 2015 .

[13]  Yasuhiro Shiraishi,et al.  A coumarin-thiourea conjugate as a fluorescent probe for Hg(II) in aqueous media with a broad pH range 2-12. , 2010, Organic & biomolecular chemistry.

[14]  H. Ågren,et al.  Effects of conjugation length, electron donor and acceptor strengths on two-photon absorption cross sections of asymmetric zinc-porphyrin derivatives. , 2006, The Journal of chemical physics.

[15]  Shogo Iwasaki,et al.  A coumarin-based fluorescent probe for Hg2+ and Ag+ with an N'-acetylthioureido group as a fluorescence switch. , 2011, Chemical communications.

[16]  D. Spring,et al.  A selective and ratiometric Cu2+ fluorescent probe based on naphthalimide excimer-monomer switching. , 2010, Chemical communications.

[17]  Xuanjun Zhang,et al.  Design of turn-on fluorescent probe for effective detection of Hg2+ by combination of AIEE-active fluorophore and binding site , 2015 .

[18]  Jonathan L Sessler,et al.  Small molecule-based ratiometric fluorescence probes for cations, anions, and biomolecules. , 2015, Chemical Society reviews.

[19]  B. Cho,et al.  Two‐Photon Absorption Properties of 2,6‐Bis(styryl)anthracene Derivatives: Effects of Donor–Acceptor Substituents and the π Center , 2005 .

[20]  Zijian Guo,et al.  A highly sensitive ratiometric fluorescent probe for Cd2+ detection in aqueous solution and living cells. , 2010, Chemical communications.

[21]  Bong Rae Cho,et al.  Two-photon fluorescent probes for metal ions in live tissues. , 2014, Inorganic chemistry.

[22]  Th. Förster.  Zwischenmolekulare Energiewanderung und Fluoreszenz , 1948 .

[23]  Ai-Min Ren,et al.  Computational design of a two-photon excited FRET-based ratiometric fluorescent Cu2+ probe for living cell imaging , 2015 .

[24]  Aixia Han,et al.  A phenothiazine–rhodamine ratiometric fluorescent probe for Hg2+ based on FRET and ICT , 2015 .

[25]  P. K. Bharadwaj,et al.  A 2-(2'-hydroxyphenyl)benzothiazole (HBT)-quinoline conjugate: a highly specific fluorescent probe for Hg(2+) based on ESIPT and its application in bioimaging. , 2015, Dalton transactions.

[26]  G. Shen,et al.  An efficient rhodamine thiospirolactam-based fluorescent probe for detection of Hg2+ in aqueous samples. , 2012, The Analyst.

[27]  Q. Liu,et al.  Highly selective two-photon fluorescent probe for imaging of nitric oxide in living cells , 2014 .

[28]  Xiaoling Zhang,et al.  A ratiometric fluorescent probe based on FRET for imaging Hg2+ ions in living cells. , 2008, Angewandte Chemie.

[29]  Mei Chen,et al.  A Novel Hg2+ Selective Ratiometric Fluorescent Chemodosimeter Based on an Intramolecular FRET Mechanism , 2008, Journal of Fluorescence.

[30]  D. Avcı,et al.  Linear and non-linear optical properties of some donor–acceptor oxadiazoles by ab initio Hartree-Fock calculations , 2008 .

[31]  Bong Rae Cho,et al.  Two-photon materials with large two-photon cross sections. Structure-property relationship. , 2009, Chemical communications.

[32]  G. Shen,et al.  Through bond energy transfer: a convenient and universal strategy toward efficient ratiometric fluorescent probe for bioimaging applications. , 2012, Analytical chemistry.

[33]  Amitava Das,et al.  Resonance energy transfer approach and a new ratiometric probe for Hg2+ in aqueous media and living organism. , 2009, Organic letters.

[34]  K. Zhao,et al.  Effects of torsional disorder and position isomerism on two-photon absorption properties of polar chromophore dimers , 2014 .