Journal of Chemical Sciences

, 130:133 | Cite as

Synthesis and in vitro photobiological studies of porphyrin capped gold nanoparticles\(^{\S }\)

  • Albish K Paul
  • Dhanya T Jayaram
  • P S Saneesh Babu
  • Nagappanpillai Adarsh
  • Shameel Thurakkal
  • Asha S NairEmail author
  • Danaboyina RamaiahEmail author
Regular Article


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.


Gold nanoparticles porphyrin MTT assay singlet oxygen apoptosis 


Supplementary material

12039_2018_1539_MOESM1_ESM.pdf (470 kb)
Supplementary material 1 (pdf 469 KB)


  1. 1.
    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 2276CrossRefGoogle Scholar
  2. 2.
    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 783CrossRefGoogle Scholar
  3. 3.
    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 672CrossRefGoogle Scholar
  4. 4.
    Zhang P, Steelant W, Kumar M and Scholfield M 2007 Versatile Photosensitizers for Photodynamic Therapy at Infrared Excitation J. Am. Chem. Soc.  129 4526CrossRefGoogle Scholar
  5. 5.
    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 340CrossRefGoogle Scholar
  6. 6.
    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 5110CrossRefGoogle Scholar
  7. 7.
    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 104CrossRefGoogle Scholar
  8. 8.
    Foote C S 1968 Mechanisms of Photosensitized Oxidation Science  162 963CrossRefGoogle Scholar
  9. 9.
    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 3734CrossRefGoogle Scholar
  10. 10.
    Lucky S S, Soo K C and Zhang Y 2015 Nanoparticles in Photodynamic Therapy Chem. Rev.  115 1990CrossRefGoogle Scholar
  11. 11.
    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 1673CrossRefGoogle Scholar
  12. 12.
    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 745CrossRefGoogle Scholar
  13. 13.
    Mineo P, Abbadessa A, Mazzaglia A, Gulino A and Scamporrino E 2017 Gold nanoparticles functionalized with PEGylate uncharged porphyrins Dyes Pigm.  141 225CrossRefGoogle Scholar
  14. 14.
    Quimby D J and Longo F R 1975 Luminescence studies on several tetraarylporphins and their zinc derivatives J. Am. Chem. Soc.  97 5111CrossRefGoogle Scholar
  15. 15.
    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 1368CrossRefGoogle Scholar
  16. 16.
    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 1348CrossRefGoogle Scholar
  17. 17.
    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 6158CrossRefGoogle Scholar
  18. 18.
    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 5528CrossRefGoogle Scholar
  19. 19.
    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 6660CrossRefGoogle Scholar
  20. 20.
    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 9868CrossRefGoogle Scholar
  21. 21.
    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 1010Google Scholar
  22. 22.
    Enustun B V and Turkevich J 1963 Coagulation of Colloidal Gold J. Am. Chem. Soc.  85 3317CrossRefGoogle Scholar
  23. 23.
    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 5825CrossRefGoogle Scholar
  24. 24.
    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 13515CrossRefGoogle Scholar
  25. 25.
    Redmond R W and Gamlin J N 1999 A Compilation of Singlet Oxygen Yields from Biologically Relevant Molecules Photochem. Photobiol.  70 391CrossRefGoogle Scholar
  26. 26.
    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 154CrossRefGoogle Scholar
  27. 27.
    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 307CrossRefGoogle Scholar
  28. 28.
    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 211CrossRefGoogle Scholar
  29. 29.
    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 127CrossRefGoogle Scholar
  30. 30.
    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 628CrossRefGoogle Scholar

Copyright information

© Indian Academy of Sciences 2018

Authors and Affiliations

  1. 1.Photosciences and Photonics Section, Chemical Sciences and Technology DivisionCSIR-National Institute for Interdisciplinary Science and TechnologyThiruvananthapuramIndia
  2. 2.Rajiv Gandhi Centre for BiotechnologyThiruvananthapuramIndia
  3. 3.Academy of Scientific and Innovative Research (AcSIR), CSIR-NIIST CampusThiruvananthapuramIndia
  4. 4.CSIR-North East Institute of Science and TechnologyJorhatIndia

Personalised recommendations