Abstract
We describe the synthesis and characterization of a thiol-functionalized porphyrin derivative 2 and its gold nanoparticle conjugates. The porphyrin 2 exhibited its characteristic intense Soret absorption at 420 nm with a molar extinction coefficient value of \(3.6\times 10^{5}\, \hbox {M}^{-1}\, \hbox {cm}^{-1}\) and good fluorescence in the region of 650–660 nm. The porphyrin-capped gold nanoparticles (POPNPs) were synthesized from the citrate-capped gold nanoparticles by the ligand exchange method and characterized by spectroscopic and morphological analyses (UV–Vis, DLS and TEM). The broadening of the absorption spectrum and quenching of the fluorescence intensity for the porphyrin gold nanoconjugates suggest efficient incorporation of the porphyrin moiety onto the gold surface. The results of DLS and TEM analyses indicate that the nanoconjugate POPNPs are uniformly spherical in shape with a size of ca. \(25 \pm 5\, \hbox {nm}\) and exhibits a negative zeta potential value of \(-\,16.0 \pm 2\, \hbox {mV}\). The singlet oxygen generation efficiency of the porphyrin 2 and POPNPs was calculated and are found to be ca. \(0.53 \pm 0.02\) and \(0.43 \pm 0.03\), respectively. The in vitro photobiological studies revealed that POPNPs exhibited enhanced photodynamic activity compared to their parent porphyrin derivative 2 with an \(\hbox {IC}_{50}\) value of \(5\, \upmu \hbox {M}\) in MDA MB 231 cell lines. The mechanism of the cell destruction was studied by Annexin-FITC and confirmed through TMRM assay. We observed the increase in the percentage of cell population corresponding to the late apoptotic stage ca. 37.7% and 51.2% for 5 and \(10\, \upmu \hbox {M}\) of POPNPs, respectively, thereby demonstrating their apoptotic-mediated cell destruction and use in PDT applications.
Graphical Abstract
Synopsis We synthesized a thiol-functionalized porphyrin-based sensitizer 2 and its gold nanoparticles (POPNPs) and have investigated their photophysical properties, singlet oxygen generation and in vitro photobiological efficacy. Our results demonstrate that the incorporation of the sensitizer onto the surface of nanoparticles not only improved its solubility in the aqueous medium, photophysical and photobiological properties but also its potential as a novel sensitizer for photodynamic therapeutical applications.
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Ogawa K, Hasegawa H, Inaba Y, Kobuke Y, Inouye H, Kanemitsu Y, Kohno E, Hirano T, Ogura S and Okura I 2006 Water-Soluble Bis(imidazolylporphyrin) Self-Assemblies with Large Two-Photon Absorption Cross Sections as Potential Agents for Photodynamic Therapy J. Med. Chem. 49 2276
Ramaiah D, Joy A, Chandrasekhar N, Eldho N V, Das S and George M V 1997 Halogenated Squaraine Dyes as Potential Photochemotherapeutic Agents. Synthesis and Study of Photophysical Properties and Quantum Efficiencies of Singlet Oxygen Generation Photochem. Photobiol. 65 783
Ramaiah D, Eckert I, Arun K T, Weidenfeller L and Epe B 2002 Squaraine Dyes for Photodynamic Therapy: Study of Their Cytotoxicity and Genotoxicity in Bacteria and Mammalian Cells Photochem. Photobiol. 76 672
Zhang P, Steelant W, Kumar M and Scholfield M 2007 Versatile Photosensitizers for Photodynamic Therapy at Infrared Excitation J. Am. Chem. Soc. 129 4526
Ethirajan M, Chen Y, Joshia P and Pandey R K 2011 The role of porphyrin chemistry in tumor imaging and photodynamic therapy Chem. Soc. Rev. 40 340
Thomas A P, Saneesh Babu P S, Asha Nair S, Ramakrishnan S, Ramaiah D, Chandrashekar T K, Srinivasan A and Radhakrishna Pillai M 2012 meso-Tetrakis(p-sulfonatophenyl)N-Confused Porphyrin Tetrasodium Salt: A Potential Sensitizer for Photodynamic Therapy J. Med. Chem. 55 5110
Jayaram D T, Ramos-Romero S, Shankar B H, Garrido C, Rubio N, Sanchez-Cid L, Gómez S B, Blanco J and Ramaiah D 2016 In Vitro and in Vivo Demonstration of Photodynamic Activity and Cytoplasm Imaging through TPE Nanoparticles ACS Chem. Biol. 11 104
Foote C S 1968 Mechanisms of Photosensitized Oxidation Science 162 963
You Y, Gibson S L, Hilf R, Davies S R, Oseroff A R, Roy I, Ohulchanskyy T Y, Bergey E J and Detty M R 2003 Water Soluble, Core-Modified Porphyrins. 3. Synthesis, Photophysical Properties, and in Vitro Studies of Photosensitization, Uptake, and Localization with Carboxylic Acid-Substituted Derivatives J. Med. Chem. 46 3734
Lucky S S, Soo K C and Zhang Y 2015 Nanoparticles in Photodynamic Therapy Chem. Rev. 115 1990
Dinkel R, Braunschweig B and Peukert W 2015 Fast and Slow Ligand Exchange at the Surface of Colloidal Gold Nanoparticles J. Phys. Chem. C 120 1673
Merg A D, Zhou Y, Smith A M, Millstone J E and Rosi N L 2017 Ligand Exchange for Controlling the Surface Chemistry and Properties of Nanoparticle Superstructures ChemNanoMat 3 745
Mineo P, Abbadessa A, Mazzaglia A, Gulino A and Scamporrino E 2017 Gold nanoparticles functionalized with PEGylate uncharged porphyrins Dyes Pigm. 141 225
Quimby D J and Longo F R 1975 Luminescence studies on several tetraarylporphins and their zinc derivatives J. Am. Chem. Soc. 97 5111
Paul A K, Karunakaran S C, Jayaram D T, Adarsh N, Joseph J and Ramaiah D 2016 Selective recognition of cyanide ions by amphiphilic porphyrins in aqueous medium J. Porphyr. Phthalocya. 20 1368
Paul A K, Karunakaran S C, Joseph J and Ramaiah D 2015 Amino Acid–Porphyrin Conjugates: Synthesis and Study of their Photophysical and Metal Ion Recognition Properties Photochem. Photobiol. 91 1348
Girgis O, Isabelle C, Michael J C and David A R 2012 Targeting the Oncofetal Thomsen–Friedenreich Disaccharide Using Jacalin-PEG Phthalocyanine Gold Nanoparticles for Photodynamic Cancer Therapy Angew. Chem. Int. Ed. 51 6158
Zhaowu Z, Jing J, Youqun L, Yanyan M, Jian W and Liping S 2010 Conjugating folic acid to gold nanoparticles through glutathione for targeting and detecting cancer cells Bioorg. Med. Chem. 18 5528
Shiao-Wen T, Jiunn-Woei L, Fu-Yin H, Yi-Yun C, Mei-Jhih L and Ming-His Y 2008 Surface-Modified Gold Nanoparticles with Folic Acid as Optical Probes for Cellular Imaging Sensors 8 6660
Gaiping L, Dan L, Lixue Z Z and Erkang W 2009 One-Step Synthesis of Folic Acid Protected Gold Nanoparticles and Their Receptor-Mediated Intracellular Uptake Chem. Eur. J. 15 9868
Jain S, Bch M B, Hirst D G and O’Sullivan J M 2014 Gold nanoparticles as novel agents for cancer therapy Brit. J. Radiol. 85 1010
Enustun B V and Turkevich J 1963 Coagulation of Colloidal Gold J. Am. Chem. Soc. 85 3317
Nair L V, Nazeer S S, Jayasree R S and Ajayaghosh A 2015 Fluorescence imaging assisted photodynamic therapy using photosensitizer-linked gold quantum clusters ACS Nano 9 5825
Marydasan B, Nair A K and Ramaiah D 2013 Optimization of Triplet Excited State and Singlet Oxygen Quantum Yields of Picolylamine–Porphyrin Conjugates through Zinc Insertion J. Phys. Chem. B 117 13515
Redmond R W and Gamlin J N 1999 A Compilation of Singlet Oxygen Yields from Biologically Relevant Molecules Photochem. Photobiol. 70 391
Wang H M, Jiang J Q, Xiao J H, Gao R L, Lin F Y and Liu X Y 2008 Porphyrin with amino acid moieties: A tumor photosensitizer Chem.- Biol. Interact. 172 154
Ronn A M, Nbouri M, Abrahmson A L and Pecci L 1999 Evaluation of the Third Generation Photosensitiser SC102 in Two Animal Models Lasers Med. Sci. 14 307
Rovers J P, Saarnack A E, de Jode M, Sterenborg H J, Terpstra O T and Grahn M F 2007 Biodistribution and Bioactivity of Tetra-pegylated Meta-tetra(hydroxyphenyl)chlorin Compared to Native Meta-tetra(hydroxyphenyl)chlorin in a Rat Liver Tumor Model Photochem. Photobiol. 71 211
Karunakaran S C, Saneesh Babu P S, Madhuri B, Marydasan B, Paul A K, Nair S A, Rao K S, Srinivasan A, Chandrashekar T K, Rao Ch M, Pillai R and Ramaiah D 2012 In Vitro Demonstration of Apoptosis Mediated Photodynamic Activity and NIR Nucleus Imaging through a Novel Porphyrin ACS Chem. Biol. 8 127
Prasanth C S, Karunakaran S C, Paul A K, Kussovski V, Mantareva V, Ramaiah D, Selvaraj L, Angelov I, Avramov L, Nandakumar K and Subhash N 2014 Antimicrobial Photodynamic Efficiency of Novel Cationic Porphyrins towards Periodontal Gram-positive and Gram-negative Pathogenic Bacteria Photochem. Photobiol. 90 628
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$$^{\S }$$ § Dedicated to Professor M V George on the occasion of his $$90^\mathrm{th}$$ 90 th Birth Anniversary.
Special Issue on Photochemistry, Photophysics and Photobiology
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Paul, A.K., Jayaram, D.T., Babu, P.S.S. et al. Synthesis and in vitro photobiological studies of porphyrin capped gold nanoparticles\(^{\S }\). J Chem Sci 130, 133 (2018). https://doi.org/10.1007/s12039-018-1539-8
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DOI: https://doi.org/10.1007/s12039-018-1539-8