Photophysical and Electrochemical Properties and Anticancer 
Activities of Porphyrin-Cored Fluorenodendrimers Synthesized by Click Chemistry

Devaraj Anandkumar; Perumal Rajakumar

doi:10.1055/s-0037-1610218

Synlett, Table of Contents

Synlett 2018; 29(15): 1995-2000
DOI: 10.1055/s-0037-1610218

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Photophysical and Electrochemical Properties and Anticancer Activities of Porphyrin-Cored Fluorenodendrimers Synthesized by Click Chemistry

Devaraj Anandkumar

Department of Organic Chemistry, University of Madras, Guindy Campus, Chennai-600 025, Tamilnadu, India Email: perumalrajakumar@gmail.com

,

Perumal Rajakumar*

Department of Organic Chemistry, University of Madras, Guindy Campus, Chennai-600 025, Tamilnadu, India Email: perumalrajakumar@gmail.com

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Abstract

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Abstract

A new class of porphyrin-cored fluorenodendrimers were synthesized by a convergent approach through click chemistry. The zeroth-, first-, and second-generation porphyrin-cored fluorenodendrimers were characterized by means of ¹H and ¹³C NMR spectroscopy, UV-vis spectroscopy, fluorescent spectroscopy, elemental analysis, and MALDI-TOF mass spectrometry. The UV-vis spectrum of the dendrimers showed an increase in the absorption intensity on increasing the dendrimer generation, and a bathochromic shift was observed for higher-generation dendrimers compared with lower-generation dendrimers. The dendrimers showed emission bands at 317, 604–668, and 617–668 nm, the intensity of which increased with increasing dendrimer generation. All the synthesized dendrimers exhibited a reversible oxidation potential in cyclic voltammetry. The therapeutic efficacy of the porphyrin-cored fluorenodendrimers for the inhibition of a growth tumor cell (PA-1) increased with increasing generation number of the dendrimer.

Key words

dendrimers - fluorenes - click chemistry - porphyrin - anticancer activity

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References

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26 Click Reaction: General Procedure A mixture of the appropriate alkyne (1.0 equiv), the appropriate azide-functionalized compound (1.2 equiv per azide functional unit), CuSO₄·5H₂O (5 mol %), and sodium ascorbate (10 mol%) in 3:1 THF–H₂O was stirred for 10 h at r.t. until the reaction was complete. The residue obtained after evaporation of the solvent was washed thoroughly with H₂O and dissolved in CHCl₃ (150 mL). The organic layer was separated, washed with brine (150 mL), dried (Na₂SO₄), and concentrated to give the crude triazole, which was purified by column chromatography (silica gel, CHCl₃–MeOH) Dendrimer 1 The reaction of dendritic azide 11 (0.091 g, 0.23 mmol, 1.0 equiv.) and porphyrin 22 (0.05 g, 0.06 mmol, 3.1 equiv) according to the general procedure, with elution by 19:1 CHCl₃–MeOH, gave a purple solid; yield: 0.1 g (74%); mp 132 °C. ¹H NMR (300 MHz, CDCl₃): δ = 0.60 (br s, 16 H); 0.76 (t, J = 6.3 Hz, 24 H), 1.04–1.11 (m, 48 H), 1.95 (d, J = 6 Hz, 16 H), 5.19 (s, 8 H), 5.57 (s, 8 H), 7.16–7.33 (m, 28 H), 7.53 (s, 4 H); 7.68 (d, J = 6.9 Hz, 8 H), 8.08 (d, J = 7.8 Hz, 8 H), 8.87 (s, 8 H). ¹³C NMR (75 MHz, CDCl₃ + DMSO-d ₆): δ = 14.0, 22.5, 23.7, 29.6, 31.4, 40.2, 54.6, 55.1, 62.1, 112.6, 119.9, 120.1, 120.2, 122.5, 122.7, 122.9, 126.9, 127.0, 127.5, 131.6, 132.9, 135.5, 136.4, 140.1, 141.9, 150.2, 150.8, 151.8, 157.7. MS (MALDI-TOF): m/z = 2476 [M + Na]⁺. Anal. Calcd For C₁₆₀H₁₇₆N₁₆O₄Zn: C, 78.35; H, 7.23; N, 9.14. Found: C, 78.23; H, 7.11; N, 9.2.

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