Asymmetric zinc phthalocyanines substituted with a single carboxyl and triethyleneoxysulfonyl groups: synthesis, characterization and validation for photodynamic therapy

This work describes modular pathway towards the synthesis of new specific unsymmetrically (AB3) zinc phthalocyanines that contains three polyoxy ethylene and monocarboxylic acid groups as photosensitizers. Their photophysical and photochemical properties are studied. General trends are described for quantum yields of fluorescence, photodegradation and singlet oxygen quantum yields of these compounds. Therefore, these novel phthalocyanines could potentially be good photosensitizers for photodynamic therapy.

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New peripherally substituted lutetium mono and bis phthalocyanines: Synthesis and comparative photophysical and photochemical properties

Journal of Porphyrins and Phthalocyanines ◽

10.1142/s1088424619501840 ◽

2019 ◽

Vol 23 (11n12) ◽

pp. 1542-1550

Author(s):

Nagihan Kocaağa ◽

Öznur Dülger Kutlu ◽

Ali Erdoğmuş

Keyword(s):

Mass Spectrometry ◽

Photodynamic Therapy ◽

Singlet Oxygen ◽

Photophysical Properties ◽

Quantum Yields ◽

Synthesis And Characterization ◽

Type Ii ◽

H Nmr ◽

Photochemical Properties

In this study, the synthesis and characterization of mono-(phthalocyaninato) lutetium(III) (1-Cl and 1-F) [Lu[Formula: see text](AcO)(Pc)] (Pc [Formula: see text] phthalocyaninato, AcO [Formula: see text] acetate) and bis-(phthalocyaninato) lutetium(III) (2-Cl and 2-Br) [Lu[Formula: see text]Pc[Formula: see text]] bearing halogenated (F, Cl and Br) phenoxy–phenoxy groups are described and verified by IR, [Formula: see text]H-NMR, UV-vis and mass spectrometry. Photochemical and photophysical properties of 1-F, 1-Cl 2-Cl and 2-Br in DMSO are also presented. A comparison between photophysical and photochemical parameters of mono and bis derivatives showed that mono phthalocyanines are better photosensitizers than bis phthalocyanines. Photophysical and photochemical properties of phthalocyanines are very useful for photodynamic therapy applications. Singlet oxygen quantum yields [Formula: see text] give an indication of the potential of the complexes as photosensitizers in photodynamic therapy applications. The chloro, fluoro, bromo-phenoxy–phenoxy substituted mono-(phthalocyaninato) lutetium(III) complexes (1-Cl and 1-F) gave good singlet oxygen quantum yields (from 0.86 to 0.80) in DMSO. Thus, these complexes show potential as Type II photosensitizers for PDT of cancer.

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Bis-indole substituted phthalocyanines: Photophysical and photochemical properties

Journal of Porphyrins and Phthalocyanines ◽

10.1142/s1088424620500522 ◽

2020 ◽

Vol 25 (01) ◽

pp. 66-74

Author(s):

Kevser Harmandar ◽

Esra N. Kaya ◽

Mehmet F. Saglam ◽

Ibrahim F. Sengul ◽

Devrim Atilla

Keyword(s):

Photodynamic Therapy ◽

Singlet Oxygen ◽

Spectral Data ◽

Quantum Yields ◽

Oxygen Generation ◽

Fluorescence Quantum Yields ◽

H Nmr ◽

Singlet Oxygen Generation ◽

Photochemical Properties ◽

C Nmr

Tetra substituted peripheral and non-peripheral Zn(II) phthalocyanines were successfully synthesized employing 4-(bis(3-methyl-1H-indol-2-yl)methyl)phenol as a starting material. The structure of these synthesized compounds was confirmed using 1H NMR, [Formula: see text]C NMR, infrared (IR), UV-vis, and MALDI-TOF spectral data. The photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen generation) properties of all synthesized peripheral and non-peripheral compounds were investigated in order to determine the potential of these compounds for application in photodynamic therapy.

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Photophysical and photochemical properties of newly synthesized zinc(II) and chloroindium(III) phthalocyanines substituted with 3,5-bis (trifluoromethyl)phenoxy groups

Journal of Porphyrins and Phthalocyanines ◽

10.1142/s108842461950055x ◽

2019 ◽

Vol 23 (07n08) ◽

pp. 960-968 ◽

Cited By ~ 9

Author(s):

Erem Ahmetali ◽

Göknur Yaşa Atmaca ◽

Hande Pekbelgin Karaoğlu ◽

Ali Erdoğmuş ◽

Makbule Burkut Koçak

Keyword(s):

Photodynamic Therapy ◽

Photophysical Properties ◽

Quantum Yields ◽

Fluorescence Quantum Yields ◽

Zinc Phthalocyanines ◽

Photochemical Properties ◽

Photocatalytic Applications

4,5-bis(3,5-bis(trifluoromethyl)phenoxy)phthalonitrile (1) and its complexes, namely 2,3,9,10,16,17,23,24-octakis[3,5-bis(trifluoromethyl)phenoxy] phthalocyaninato zinc(II) (2) and 2,3,9,-10,16,17,23,24-octakis[3,5-bis(trifluoromethyl)phenoxy]phthalocyaninato indium(III) (3) are synthesized and characterized. Aggregation of the phthalocyanines was studied in tetrahydrofuran in different concentrations. Photochemical and photophysical properties of 2 and 3 in THF were investigated. A comparison between the photophysicochemical parameters of 2 and 3 yielded that 3 is a better photosensitizer than 2. The fluorescence quantum yields (ΦF) and 1O2 formation ([Formula: see text] for compound 3 are 0.016 and 0.84, respectively. The values for compound 2 are 0.135 and 0.54, respectively. The values of indium and zinc phthalocyanines (2 and 3) could be classified as photosensitizers in the photocatalytic applications such as photodynamic therapy (PDT) of cancer.

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Photodynamically active phthalocyanine building blocks for click chemistry

Journal of Porphyrins and Phthalocyanines ◽

10.1142/s1088424611003987 ◽

2011 ◽

Vol 15 (09n10) ◽

pp. 1062-1069 ◽

Cited By ~ 7

Author(s):

Veronika Novakova ◽

Kamil Kopecky ◽

Miroslav Miletin ◽

Jana Ivincova ◽

Petr Zimcik

Keyword(s):

Photodynamic Therapy ◽

Singlet Oxygen ◽

Click Chemistry ◽

Building Blocks ◽

Quantum Yields ◽

Dipolar Cycloaddition ◽

Chromatographic Technique ◽

Simple Modification ◽

Fluorescence Quantum Yields ◽

Zinc Phthalocyanines

Synthesis of symmetrical and unsymmetrical zinc phthalocyanines from two different precursors 4,5-bis(tert-butylsulfanyl)phthalonitrile (A) and N-(3-azidopropyl)-2,3-dicyanoquinoxaline-6-carboxamide (B) is described. Congeners of AAAA, AAAB, ABAB and AABB type were isolated by a chromatographic technique, however, the congener of BBBB type had to be prepared in a separate reaction. The adjacent and opposite isomers were also separated and fully characterized. Isolated phthalocyanines contained different number of azide groups, a substrate for highly efficient Cu(I) -catalyzed azide-alkyne 1,3-dipolar cycloaddition ("click chemistry"). All phthalocyanines absorbed strongly (ε over 150 000 M-1.cm-1) over 700 nm. Their singlet oxygen quantum yields were determined in DMF and ranged from 0.63 to 0.79, fluorescence quantum yields in DMF were considerably lower in the range 0.03–0.06. All these properties make them suitable building blocks for a simple modification and a synthesis of phthalocyanines with better tuned properties for photodynamic therapy.

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Photophysical, Photochemical, and BQ Quenching Properties of Zinc Phthalocyanines with Fused or Interrupted Extended Conjugation

Journal of Chemistry ◽

10.1155/2014/435834 ◽

2014 ◽

Vol 2014 ◽

pp. 1-11 ◽

Cited By ~ 9

Author(s):

Gülşah Gümrükçü ◽

Gülnur Keser Karaoğlan ◽

Ali Erdoğmuş ◽

Ahmet Gül ◽

Ulvi Avcıata

Keyword(s):

Singlet Oxygen ◽

Quantum Yields ◽

Schiff’S Base ◽

Fluorescence Quantum Yields ◽

Zinc Phthalocyanines ◽

Peripheral Position ◽

Photochemical Properties ◽

Group Effects

The effects of substituents and solvents on the photophysical and photochemical parameters of zinc(II) phthalocyanines containing four Schiff’s base substituents attached directly and through phenyleneoxy-bridges on peripheral positions are reported. The group effects on peripheral position and the continual and intermittent conjugation of the phthalocyanine molecules on the photophysical and photochemical properties are also investigated. General trends are described for photodegradation, singlet oxygen, and fluorescence quantum yields of these compounds in dimethylsulfoxide (DMSO), dimethylformamide (DMF), and tetrahydrofurane (THF). Among the different substituents, phthalocyanines with cinnamaldimine moieties (1cand2c) have the highest singlet oxygen quantum yields (ΦΔ) and those with nitro groups (1aand2a) have the highest fluorescence quantum yields in all the solvents used. The fluorescence of the substituted zinc(II) phthalocyanine complexes is effectively quenched by 1,4-benzoquinone (BQ) in these solvents.

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New soluble 4-(4-formyl-2,6-dimethoxyphenoxy) substituted phthalocyanines: Synthesis, characterization, photophysical and photochemical properties

Main Group Chemistry ◽

10.3233/mgc-210123 ◽

2021 ◽

pp. 1-10

Author(s):

Ibrahim Erden ◽

Betül Karadoğan ◽

Fatma Aytan Kılıçarslan ◽

Göknur Yaşa Atmaca ◽

Ali Erdoğmuş

Keyword(s):

Quantum Yield ◽

Singlet Oxygen ◽

Fluorescence Quantum Yield ◽

Metal Ion ◽

Mass Spectra ◽

Quantum Yields ◽

Therapeutic Outcomes ◽

Ft Ir ◽

Photochemical Properties ◽

New Compounds

This work describes the synthesis, spectral and fluorescence properties of bis 4-(4-formyl-2,6-dimethoxyphenoxy) substituted zinc (ZnPc) and magnesium (MgPc) phthalocyanines. The new compounds have been characterized by elemental analysis, UV-Vis, FT-IR, 1H-NMR and mass spectra. Afterward, the effects of including metal ion on the photophysicochemical properties of the complexes were studied in biocompatible solvent DMSO to analyze their potential to use as a photosensitizer in photodynamic therapy (PDT). The fluorescence and singlet oxygen quantum yields were calculated as 0.04–0.15 and 0.70–0.52 for ZnPc and MgPc, respectively. According to the results, MgPc has higher fluorescence quantum yield than ZnPc, while ZnPc has higher singlet oxygen quantum yield than MgPc. The results show that the synthesized complexes can have therapeutic outcomes for cancer treatment.

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Red and Near-Infrared Absorbing Dicyanomethylene Squaraine Cyanine Dyes: Photophysicochemical Properties and Anti-Tumor Photosensitizing Effects

Materials ◽

10.3390/ma13092083 ◽

2020 ◽

Vol 13 (9) ◽

pp. 2083

Author(s):

Tiago D. Martins ◽

Eurico Lima ◽

Renato E. Boto ◽

Diana Ferreira ◽

José R. Fernandes ◽

...

Keyword(s):

Singlet Oxygen ◽

Near Infrared ◽

Cyanine Dyes ◽

Quantum Yields ◽

Squaraine Dyes ◽

Photodynamic Activity ◽

Photochemical Properties ◽

Radiation Treatments ◽

Species Production

Photodynamic therapy is a medical modality developed for the treatment of several diseases of oncological and non-oncological etiology that requires the presence of a photosensitizer, light and molecular oxygen, which combined will trigger physicochemical reactions responsible for reactive oxygen species production. Given the scarcity of photosensitizers that exhibit desirable characteristics for its potential application in this therapeutic strategy, the main aims of this work were the study of the photophysical and photochemical properties and the photobiological activity of several dicyanomethylene squaraine cyanine dyes. Thus, herein, the study of their aggregation character, photobleaching and singlet oxygen production ability, and the further application of the previously synthesized dyes in Caco-2 and HepG2 cancer cell lines, to evaluate their phototherapeutic effects, are described. Dicyanomethylene squaraine dyes exhibited moderate light-stability and, despite the low singlet oxygen quantum yields, were a core of dyes that exhibited relevant in vitro photodynamic activity, as there was an evident increase in the toxicity of some of the tested dyes exclusive to radiation treatments.

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Synthesis and characterization of novel 7-oxy-3-ethyl-6-hexyl-4-methylcoumarin substituted metallo phthalocyanines and investigation of their photophysical and photochemical properties

Dalton Transactions ◽

10.1039/c9dt02687h ◽

2019 ◽

Vol 48 (34) ◽

pp. 13046-13056 ◽

Cited By ~ 8

Author(s):

Mücahit Özdemir ◽

Begümhan Karapınar ◽

Bahattin Yalçın ◽

Ümit Salan ◽

Mahmut Durmuş ◽

...

Keyword(s):

Singlet Oxygen ◽

Quantum Yields ◽

Synthesis And Characterization ◽

Photochemical Properties ◽

Lipophilic Groups

Coumarin functionalized metallo phthalocyanines shows increased singlet oxygen quantum yields when included lipophilic groups.

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3-Methylindole-substituted zinc phthalocyanines for photodynamic cancer therapy

Journal of Porphyrins and Phthalocyanines ◽

10.1142/s1088424619501426 ◽

2019 ◽

Vol 23 (11n12) ◽

pp. 1371-1379 ◽

Cited By ~ 3

Author(s):

Sami Ayari ◽

Mehmet F. Saglam ◽

Elif Şenkuytu ◽

Pelin B. Erçin ◽

Yunus Zorlu ◽

...

Keyword(s):

Photodynamic Therapy ◽

Cancer Treatment ◽

Cancer Cell Line ◽

Zinc Phthalocyanine ◽

Quantum Yields ◽

Light Conditions ◽

Suitable Candidate ◽

Zinc Phthalocyanines ◽

Invasive Human Breast Cancer

Novel peripherally and non-peripherally 3-methylindole-substituted zinc phthalocyanine derivatives were synthesized as photosensitizers for photodynamic therapy in cancer treatment. The photophysical, photochemical and photobiological properties of targeted phthalocyanines were also investigated. For this purpose, the fluorescence and singlet oxygen quantum yields, and fluorescence lifetime values of the final compounds were determined in DMF solutions. The phototoxicity and cytotoxicity of the phthalocyanine complexes were tested against the invasive human breast cancer cell line (MDA-MB-231) for determination of their photosensitizing ability in the area of photodynamic therapy. It was revealed that while peripherally 3-methylindole-substituted phthalocyanine was found to be toxic for cells in both dark and light conditions, its non-peripherally substituted phthalocyanine analogue significantly caused cell death following light irradiation. A preliminary assay suggested that the non-peripherally linked phthalocyanine could be a suitable candidate for cancer treatment via photodynamic therapy techniques.

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