A novel isolongifolanone based fluorescent probe with super selectivity and sensitivity for hypochlorite and its application in bio-imaging.

In this study, a novel biocompatible fluorescent probe (DN) capable of detecting ClO- in physiological medium was rationally designed and synthesized from natural and renewable isolongifolanone. This probe underwent a highly specific and sensitive oxidation reaction with ClO- and liberated an isolongifolanone derivative (PA) emitting intensive blue fluorescence. In response to ClO-, the fluorescence emission of DN was obviously enhanced within a short time. The detection limit of DN toward ClO- was found to be as low as 5.86 × 10-9 M. IR, MS and DFT calculation were employed to further confirm the sensing mechanism. Moreover, the test strips coated with DN could easily recognize ClO- from other relevant species through the changes of fluorescence color under 365 nm UV lamp. More importantly, we also successfully demonstrated the potential application of DN for the detection of intracellular hypochloritein living cells.

[1]  Kyoung Chul Ko,et al.  Rationally designed fluorescence turn-on sensors: a new design strategy based on orbital control. , 2010, Inorganic chemistry.

[2]  P. Libby,et al.  Hypochlorous Acid, a Macrophage Product, Induces Endothelial Apoptosis and Tissue Factor Expression: Involvement of Myeloperoxidase-Mediated Oxidant in Plaque Erosion and Thrombogenesis , 2004, Arteriosclerosis, thrombosis, and vascular biology.

[3]  M. Davies,et al.  Absolute rate constants for the reaction of hypochlorous acid with protein side chains and peptide bonds. , 2001, Chemical research in toxicology.

[4]  Lingxin Chen,et al.  A novel dual-ratiometric-response fluorescent probe for SO2/ClO- detection in cells and in vivo and its application in exploring the dichotomous role of SO2 under the ClO- induced oxidative stress. , 2017, Biomaterials.

[5]  E. Hidalgo,et al.  Cytotoxicity mechanisms of sodium hypochlorite in cultured human dermal fibroblasts and its bactericidal effectiveness. , 2002, Chemico-biological interactions.

[6]  B. Zhang,et al.  A water-soluble fluorescent probe for ClO− and Cd2+ under physiological pH and its applications in living cells imaging , 2016 .

[7]  S. Pizzo,et al.  alpha(2)-Macroglobulin from rheumatoid arthritis synovial fluid: functional analysis defines a role for oxidation in inflammation. , 2001, Archives of biochemistry and biophysics.

[8]  Jianbin Chao,et al.  Ratiometric fluorescent probes for ClO− and in vivo applications , 2016 .

[9]  A. Kettle,et al.  Myeloperoxidase: a key regulator of neutrophil oxidant production. , 1997, Redox report : communications in free radical research.

[10]  J. Hua,et al.  A pH-sensitive multifunctional fluorescent probe based on N-annulated perylene for the sensitive and selective detection of hypochlorous acid , 2017 .

[11]  Zhen Li,et al.  A highly sensitive and selective fluorescent probe for hypochlorite in pure water with aggregation induced emission characteristics. , 2017, Faraday discussions.

[12]  R. Stocker,et al.  Presence of hypochlorite-modified proteins in human atherosclerotic lesions. , 1996, The Journal of clinical investigation.

[13]  Kandasamy Ponnuvel,et al.  A new quinoline-based chemosensor for Zn2+ ions and their application in living cell imaging , 2016 .

[14]  A. Levitzki,et al.  ROS, stress‐activated kinases and stress signaling in cancer , 2002, EMBO reports.

[15]  S. Dev,et al.  Hydration of longifolene , 1960 .

[16]  Yanhui Zhang,et al.  A highly sensitive and rapidly responding fluorescent probe based on a rhodol fluorophore for imaging endogenous hypochlorite in living mice. , 2018, Journal of materials chemistry. B.

[17]  Fang Wang,et al.  A highly specific fluorescent probe for hypochlorite based on fluorescein derivative and its endogenous imaging in living cells , 2015 .

[18]  A. Prasanna de Silva,et al.  Luminescent sensors and switches in the early 21st century , 2005 .

[19]  Guang-Jie Song,et al.  A new ratiometric fluorescent probe for sensing HOCl based on TBET in real time , 2018 .

[20]  Hongyan Sun,et al.  A fast-response fluorescent probe for hypochlorous acid detection and its application in exogenous and endogenous HOCl imaging of living cells. , 2017, Chemical communications.

[21]  Wen-Li Wu,et al.  A near-infrared ratiometric fluorescent probe for rapid and selective detection of hypochlorous acid in aqueous solution and living cells , 2018 .

[22]  Xiaomei Yan,et al.  Sensitive and selective off-on rhodamine hydrazide fluorescent chemosensor for hypochlorous acid detection and bioimaging. , 2011, Talanta.

[23]  P. Choyke,et al.  New strategies for fluorescent probe design in medical diagnostic imaging. , 2010, Chemical reviews.

[24]  Yongbin Zhang,et al.  Mono- or di- naphthalimides as fluorophore to detect hypochlorous acid (HOCl) by ratiometric fluorescent signal and their biological application , 2018, Sensors and Actuators B: Chemical.

[25]  Wei Shu,et al.  Highly Specific and Ultrasensitive Two-Photon Fluorescence Imaging of Native HOCl in Lysosomes and Tissues Based on Thiocarbamate Derivatives. , 2016, Analytical chemistry.

[26]  Melek Pamuk Algi.  A highly selective dual channel hypochlorite probe based on fluorescein and 1,10-phenanthroline , 2016 .

[27]  M. Davies,et al.  What are the plasma targets of the oxidant hypochlorous acid? A kinetic modeling approach. , 2009, Chemical research in toxicology.

[28]  Shu-Pao Wu,et al.  A hypochlorous acid turn-on fluorescent probe based on HOCl-promoted oxime oxidation and its application in cell imaging , 2014 .

[29]  Xiaoling Zhang,et al.  A highly specific and ultrasensitive fluorescent probe for basal lysosomal HOCl detection based on chlorination induced by chlorinium ions (Cl+). , 2017, Journal of materials chemistry. B.

[30]  R. Strongin,et al.  Detecting intracellular ClO- with ratiometric fluorescent signal and its application in vivo , 2018, Sensors and Actuators B: Chemical.

[31]  Z. Ziyang,et al.  A fast-response, highly specific fluorescent probe for the detection of picomolar hypochlorous acid and its bioimaging applications , 2018, Sensors and Actuators B: Chemical.

[32]  P. Liu,et al.  Isolongifolanone-based molecular fluorescence marker for imaging endogenous Zn2+ in vivo , 2017 .

[33]  Pan Jia,et al.  A highly specific and ultrasensitive near-infrared fluorescent probe for imaging basal hypochlorite in the mitochondria of living cells. , 2018, Biosensors & bioelectronics.

[34]  Caiqin Qin,et al.  Selective visualization of hypochlorite and its fluctuation in cancer cells by a mitochondria-targeting ratiometric fluorescent probe , 2018 .

[35]  Z. Ziyang,et al.  A highly specific and ultrasensitive fluorescent probe for monitoring hypochlorous acid and its applications in live cells , 2018 .

[36]  Minyong Li,et al.  Bioluminescent probe for detecting endogenous hypochlorite in living mice. , 2018, Organic & biomolecular chemistry.

[37]  Zheng-yin Yang,et al.  Recognition of Al3+ and Zn2+ using a single Schiff-base in aqueous media , 2015 .

[38]  Nam Sang Cheung,et al.  Chlorinative stress: an under appreciated mediator of neurodegeneration? , 2007, Cellular signalling.

[39]  A. Kettle,et al.  Modeling the Reactions of Superoxide and Myeloperoxidase in the Neutrophil Phagosome , 2006, Journal of Biological Chemistry.

[40]  Xu Xu,et al.  A novel hexahydroquinazolin-2-amine-based fluorescence sensor for Cu2+ from isolongifolanone and its biological applications , 2017 .

[41]  S. Hazen,et al.  Myeloperoxidase-generated oxidants and atherosclerosis. , 2000, Free radical biology & medicine.

[42]  Jianxin Chen,et al.  HEPES is not suitable for fluorescence detection of HClO: a novel probe for HClO in absolute PBS. , 2016, Chemical communications.

[43]  F. Cuccurullo,et al.  Hypochlorous acid and its pharmacological antagonism: an update picture. , 1996, General pharmacology.

[44]  Wen-Li Wu,et al.  A mitochondria-targeted fluorescence probe for ratiometric detection of endogenous hypochlorite in the living cells. , 2017, Analytica chimica acta.