Implantable Tin Porphyrin-PEG Hydrogels with pH-Responsive Fluorescence.

Tetracarboxy porphyrins can be polymerized with polyethylene glycol (PEG) diamines to generate hydrogels with intense, near-infrared, and transdermal fluorescence following subcutaneous implantation. Here, we show that the high density porphyrins of the preformed polymer can be chelated with tin via simple incubation. Tin porphyrin hydrogels exhibited increasing emission intensities, ratios, and lifetimes from pH 1 to 10. Tin porphyrin hydrogel emission was strongly reversible and pH responsiveness was observed in the physiological range between pH 6 and pH 8. pH-sensitive emission was detected via noninvasive transdermal fluorescence imaging in vivo following subcutaneous implantation in mice.

[1]  R. Grigg,et al.  The proton-controlled fluorescence of aminomethyltetraphenylporphyrin-tin(IV) derivatives , 1992 .

[2]  Guanying Chen,et al.  Pd‐Porphyrin‐Cross‐Linked Implantable Hydrogels with Oxygen‐Responsive Phosphorescence , 2014, Advanced healthcare materials.

[3]  Ian D. Williams,et al.  Fluorescent pH sensor constructed from a heteroatom-containing luminogen with tunable AIE and ICT characteristics , 2013 .

[4]  R. J. Johnson,et al.  Non-age related differences in thrombin responses by platelets from male patients with advanced Alzheimer's disease. , 1993, Biochemical and biophysical research communications.

[5]  Heinz Rüdel,et al.  Case study: bioavailability of tin and tin compounds. , 2003, Ecotoxicology and environmental safety.

[6]  Haotian Sun,et al.  A porphyrin-PEG polymer with rapid renal clearance. , 2016, Biomaterials.

[7]  Stephan Schreml.  Luminescent dual sensors reveal extracellular pH-gradients and hypoxia on chronic wounds that disrupt epidermal repair , 2015 .

[8]  J. Xia,et al.  Axial PEGylation of Tin Octabutoxy Naphthalocyanine Extends Blood Circulation for Photoacoustic Vascular Imaging. , 2016, Bioconjugate chemistry.

[9]  Colette McDonagh,et al.  Optical chemical pH sensors. , 2014, Analytical chemistry.

[10]  Michael Landthaler,et al.  The impact of the pH value on skin integrity and cutaneous wound healing , 2010, Journal of the European Academy of Dermatology and Venereology : JEADV.

[11]  Jens Lienig,et al.  Review on Hydrogel-based pH Sensors and Microsensors , 2008, Sensors.

[12]  J. Lovell,et al.  Recent applications of phthalocyanines and naphthalocyanines for imaging and therapy. , 2017, Wiley interdisciplinary reviews. Nanomedicine and nanobiotechnology.

[13]  D. Delmarre,et al.  Spectroscopic properties of Sn(IV) tetrapyridyl and tetramethylpyridinium porphyrins in solution and in sol–gel matrices , 1999 .

[14]  Shoji Takeuchi,et al.  Long-term in vivo glucose monitoring using fluorescent hydrogel fibers , 2011, Proceedings of the National Academy of Sciences.

[15]  D. Meldrum,et al.  A dual sensor for real-time monitoring of glucose and oxygen. , 2013, Biomaterials.

[16]  P. Krulevitch,et al.  In vitro and in vivo measurements of fiber optic and electrochemical sensors to monitor brain tissue pH , 2001 .

[17]  M. Meyerhoff,et al.  Salicylate-selective membrane electrode based on tin(IV) tetraphenylporphyrin. , 1989, Analytical chemistry.

[18]  Christophe Detrembleur,et al.  A novel pH sensitive water soluble fluorescent nanomicellar sensor for potential biomedical applications. , 2013, Bioorganic & medicinal chemistry.

[19]  Jonathan F. Lovell,et al.  Emerging applications of porphyrins in photomedicine , 2015, Front. Phys..

[20]  D. Ding,et al.  Biocompatible fluorescent supramolecular nanofibrous hydrogel for long-term cell tracking and tumor imaging applications , 2015, Scientific Reports.

[21]  Jishan Wu,et al.  Far-red and near infrared BODIPY dyes: synthesis and applications for fluorescent pH probes and bio-imaging. , 2014, Organic & biomolecular chemistry.

[22]  Jae Ho Shin,et al.  Biocompatible materials for continuous glucose monitoring devices. , 2013, Chemical reviews.

[23]  Michael Landthaler,et al.  A sprayable luminescent pH sensor and its use for wound imaging in vivo , 2012, Experimental dermatology.

[24]  J. Lovell,et al.  Advanced Functional Nanomaterials for Theranostics , 2017, Advanced functional materials.

[25]  R. Dacosta,et al.  Porphyrin-cross-linked hydrogel for fluorescence-guided monitoring and surgical resection. , 2011, Biomacromolecules.

[26]  Ross W. Boyle,et al.  Photodynamic Therapy and the Development of Metal-Based Photosensitisers , 2008, Metal-based drugs.

[27]  Nicholas A Peppas,et al.  Hydrogel-based biosensors and sensing devices for drug delivery. , 2016, Journal of controlled release : official journal of the Controlled Release Society.

[28]  Philipp Kurz,et al.  A water-soluble tin(IV) porphyrin as a bioinspired photosensitiser for light-driven proton-reduction. , 2014, Physical chemistry chemical physics : PCCP.

[29]  C. Bai,et al.  Continuous intra-arterial blood pH monitoring in rabbits with acid–base disorders , 2011, Respiratory Physiology & Neurobiology.

[30]  Shoji Takeuchi,et al.  Injectable hydrogel microbeads for fluorescence-based in vivo continuous glucose monitoring , 2010, Proceedings of the National Academy of Sciences.

[31]  T. Nyokong,et al.  Spectroscopic studies of nanostructures of negatively charged free base porphyrin and positively charged tin porphyrins , 2010 .

[32]  Jonathan F. Lovell,et al.  Porphyrins as Theranostic Agents from Prehistoric to Modern Times , 2012, Theranostics.

[33]  H. Luo,et al.  Highly sensitive fluorescent and colorimetric pH sensor based on polyethylenimine-capped silver nanoclusters. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[34]  A. Hoffman.  Hydrogels for Biomedical Applications , 2001, Advanced drug delivery reviews.

[35]  R. Kumar,et al.  Two-color probe to monitor a wide range of pH values in cells. , 2013, Angewandte Chemie.

[36]  J. Hardcastle,et al.  Measurement of gastrointestinal pH profiles in normal ambulant human subjects. , 1988, Gut.