Ultrasmall Phosphorescent Polymer Dots for Ratiometric Oxygen Sensing and Photodynamic Cancer Therapy

A series of semiconducting polymer dots (Pdots) composed of phosphorescent Ir(III) complexes and polyfluorene units in the main polymer chains are designed, synthesized, and applied in ratiometric oxygen sensing and photodynamic cancer therapy. The ultrasmall Pdots with particle size less than 10 nm are fabricated in aqueous solution on account of amphiphilic nature of the polymers. The Pdots possess fine photostability, biocompatibility, and efficient energy transfer from the polymer main chain to the Ir(III) complex. By utilizing the excited-state energy transfer from phosphorescent Pdots to the ground state molecular oxygen, these Pdots are applied in the optical sensing of oxygen with ratiometric and naked-eye detection as well as high sensitivity in aqueous solution. The Pdots also show low cytotoxicity and can pass across the cell membrane to enter into the cytoplasm. The singlet oxygen photo-generated from the Pdots under irradiation at 488 nm can effectively induce the apoptosis and death of tumor cells for photodynamic cancer therapy in vitro.

[1]  G. Bazan,et al.  Design Guidelines For Conjugated Polymers With Light‐Activated Anticancer Activity , 2011 .

[2]  Changfeng Wu,et al.  Stark fluoreszierende halbleitende Polymerpunkte für Biologie und Medizin , 2013 .

[3]  Qiang Zhao,et al.  Rational design of an "OFF-ON" phosphorescent chemodosimeter based on an iridium(III) complex and its application for time-resolved luminescent detection and bioimaging of cysteine and homocysteine. , 2013, Chemistry.

[4]  Yanli Zhao,et al.  Spacer intercalated disassembly and photodynamic activity of zinc phthalocyanine inside nanochannels of mesoporous silica nanoparticles. , 2013, ACS applied materials & interfaces.

[5]  Daniel T Chiu,et al.  Highly fluorescent semiconducting polymer dots for biology and medicine. , 2013, Angewandte Chemie.

[6]  Devrim Atilla,et al.  A set of highly water-soluble tetraethyleneglycol-substituted Zn(II) phthalocyanines: synthesis, photochemical and photophysical properties, interaction with plasma proteins and in vitro phototoxicity. , 2011, Dalton transactions.

[7]  Hui Jiang,et al.  Konjugierte Polyelektrolyte: Synthese, Photophysik und Anwendungen , 2009 .

[8]  D. Chiu,et al.  Hybrid semiconducting polymer dot-quantum dot with narrow-band emission, near-infrared fluorescence, and high brightness. , 2012, Journal of the American Chemical Society.

[9]  Qiang Zhao,et al.  Hyper-branched phosphorescent conjugated polyelectrolytes for time-resolved heparin sensing. , 2013, ACS applied materials & interfaces.

[10]  Perry G. Schiro,et al.  Bioconjugation of ultrabright semiconducting polymer dots for specific cellular targeting. , 2010, Journal of the American Chemical Society.

[11]  Qiang Zhao,et al.  Simple conjugated polymers with on-chain phosphorescent iridium(III) complexes: toward ratiometric chemodosimeters for detecting trace amounts of mercury(II). , 2010, Chemistry.

[12]  Qiang Zhao,et al.  Phosphorescent heavy-metal complexes for bioimaging. , 2011, Chemical Society reviews.

[13]  Chunlei Zhu,et al.  Chemical molecule-induced light-activated system for anticancer and antifungal activities. , 2012, Journal of the American Chemical Society.

[14]  K. Schanze,et al.  Conjugated polyelectrolytes: synthesis, photophysics, and applications. , 2009, Angewandte Chemie.

[15]  Cheuk‐Lam Ho,et al.  Charge and energy transfers in functional metallophosphors and metallopolyynes , 2013 .

[16]  S. Mecking,et al.  Nanoparticles of conjugated polymers. , 2010, Chemical reviews.

[17]  B. Howerton,et al.  Strained ruthenium complexes are potent light-activated anticancer agents. , 2012, Journal of the American Chemical Society.

[18]  B. Liu,et al.  Recent Advances in Conjugated Polyelectrolytes for Emerging Optoelectronic Applications , 2011 .

[19]  Shaojuan Zhang,et al.  Phosphorescent light-emitting iridium complexes serve as a hypoxia-sensing probe for tumor imaging in living animals. , 2010, Cancer research.

[20]  Fuyou Li,et al.  Phosphorescent chemosensors based on heavy-metal complexes. , 2010, Chemical Society reviews.

[21]  Qiong Yang,et al.  Water-soluble conjugated polymers for imaging, diagnosis, and therapy. , 2012, Chemical reviews.

[22]  K. Ohkubo,et al.  Phosphorescent sensor for biological mobile zinc. , 2011, Journal of the American Chemical Society.

[23]  M. Dewhirst,et al.  A dual-emissive-materials design concept enables tumour hypoxia imaging. , 2009, Nature materials.

[24]  Jianzhang Zhao,et al.  Triplet photosensitizers: from molecular design to applications. , 2013, Chemical Society reviews.

[25]  B. Liu,et al.  Fluorescent Conjugated Polyelectrolytes for Bioimaging , 2011 .

[26]  Bin Liu,et al.  Polymer encapsulated conjugated polymer nanoparticles for fluorescence bioimaging , 2012 .

[27]  Jesse V. Jokerst,et al.  Semiconducting Polymer Nanoparticles as Photoacoustic Molecular Imaging Probes in Living Mice , 2014, Nature nanotechnology.

[28]  Michael J. Hall,et al.  Supramolecular photonic therapeutic agents. , 2005, Journal of the American Chemical Society.

[29]  T. Nyokong,et al.  Generation of singlet oxygen via the composites of water-soluble thiol-capped CdTe quantum dots-sulfonated aluminum phthalocyanines. , 2008, The journal of physical chemistry. B.

[30]  Robie A. Hennigar,et al.  Exploitation of long-lived 3IL excited states for metal-organic photodynamic therapy: verification in a metastatic melanoma model. , 2013, Journal of the American Chemical Society.

[31]  M. O. Wolf,et al.  Template approaches to conjugated polymer micro- and nanoparticles. , 2010, Chemical Society reviews.

[32]  Xing-jie Liang,et al.  Ultrabright and Multicolorful Fluorescence of Amphiphilic Polyethyleneimine Polymer Dots for Efficiently Combined Imaging and Therapy , 2013, Scientific Reports.

[33]  Yuji Yamaguchi,et al.  Ratiometric molecular sensor for monitoring oxygen levels in living cells. , 2012, Angewandte Chemie.

[34]  Changfeng Wu,et al.  Ratiometric single-nanoparticle oxygen sensors for biological imaging. , 2009, Angewandte Chemie.

[35]  Wei Feng,et al.  Cationic Polyfluorenes with Phosphorescent Iridium(III) Complexes for Time‐Resolved Luminescent Biosensing and Fluorescence Lifetime Imaging , 2013 .