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

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.

scholarly journals Сравнительные исследования фотофизических свойств димегина, фотодитазина и радахлорина

2019 ◽  
Vol 126 (2) ◽  
pp. 162
Author(s):  
И.В. Багров ◽  
А.В. Дадеко ◽  
В.М. Киселев ◽  
Т.Д. Муравьева ◽  
А.М. Стародубцев
Keyword(s):  
Quantum Yield ◽  
Singlet Oxygen ◽  
Fluorescence Quantum Yield ◽  
Photophysical Properties ◽  
Quantum Yields ◽  
Oxygen Generation ◽  
Singlet Oxygen Generation

AbstractThe photophysical properties of three photosensitizers—dimegine, photoditazine, and radachlorin—have been comparatively examined. For dimegine and photoditazine, two techniques have been used to measure the singlet oxygen generation quantum yields and the quenching constants of singlet oxygen by dimegine and photoditazine, as well as the dimegine fluorescence quantum yield.

Photophysical and photochemical properties of novel phthalocyanines bearing non-peripherally substituted mercaptoquinoline moiety

2012 ◽  
Vol 16 (07n08) ◽  
pp. 845-854 ◽  
Author(s):  
Göknur Yaşa ◽  
Ali Erdoğmuş ◽  
Ahmet Lütfi Uğur ◽  
M. Kasım Şener ◽  
Ulvi Avcıata ◽  
...  
Keyword(s):  
Singlet Oxygen ◽  
Electronic Spectroscopy ◽  
Quantum Yields ◽  
Solubility In Water ◽  
Fluorescence Quantum Yields ◽  
H Nmr ◽  
Good Solubility ◽  
Ft Ir ◽  
Photochemical Properties ◽  
First Time

The synthesis, photophysical and photochemical properties of nonperipherally (α) mercaptoquinoline substituted Zn(II) , TiO(IV) and Mg(II) and quaternized Zn(II) phthalocyanines are described for the first time. These complexes (2 to 5) and their precursor are characterized by elemental analysis, FT-IR, 1H NMR, electronic spectroscopy as well as mass spectroscopy. Complexes 2, 4 and 5 have good solubility in organic solvents such as CHCl3 , DCM, DMSO, DMF, THF and toluene and are not aggregated in all solvents within a wide concentration range. Complex 3 showed very good solubility in water as well as DMSO and DMF. General trends are described for singlet oxygen, photodegradation and fluorescence quantum yields of these complexes in DMSO and DMF. While complex 2 has higher singlet oxygen and fluorescence quantum yields than 3, 4 and 5, complex 4 has higher fluorescence quantum yields in DMF and DMSO than 2, 3 and 5. The effect of the solvents and metal on the photophysical and photochemical parameters of the metallophthalocyanines are also reported.

scholarly journals Ruthenium-based PACT agents based on bisquinoline chelates: synthesis, photochemistry, and cytotoxicity

2021 ◽  
Author(s):  
Anja Busemann ◽  
Ingrid Flaspohler ◽  
Xue-Quan Zhou ◽  
Claudia Schmidt ◽  
Sina K. Goetzfried ◽  
...  
Keyword(s):  
Quantum Yield ◽  
Singlet Oxygen ◽  
Cancer Cells ◽  
Cellular Uptake ◽  
Ruthenium Complex ◽  
Human Cancer ◽  
Light Irradiation ◽  
Quantum Yields ◽  
Light Activation ◽  
Human Cancer Cells

AbstractThe known ruthenium complex [Ru(tpy)(bpy)(Hmte)](PF6)2 ([1](PF6)2, where tpy = 2,2’:6’,2″-terpyridine, bpy = 2,2’-bipyridine, Hmte = 2-(methylthio)ethanol) is photosubstitutionally active but non-toxic to cancer cells even upon light irradiation. In this work, the two analogs complexes [Ru(tpy)(NN)(Hmte)](PF6)2, where NN = 3,3'-biisoquinoline (i-biq, [2](PF6)2) and di(isoquinolin-3-yl)amine (i-Hdiqa, [3](PF6)2), were synthesized and their photochemistry and phototoxicity evaluated to assess their suitability as photoactivated chemotherapy (PACT) agents. The increase of the aromatic surface of [2](PF6)2 and [3](PF6)2, compared to [1](PF6)2, leads to higher lipophilicity and higher cellular uptake for the former complexes. Such improved uptake is directly correlated to the cytotoxicity of these compounds in the dark: while [2](PF6)2 and [3](PF6)2 showed low EC50 values in human cancer cells, [1](PF6)2 is not cytotoxic due to poor cellular uptake. While stable in the dark, all complexes substituted the protecting thioether ligand upon light irradiation (520 nm), with the highest photosubstitution quantum yield found for [3](PF6)2 (Φ[3] = 0.070). Compounds [2](PF6)2 and [3](PF6)2 were found both more cytotoxic after light activation than in the dark, with a photo index of 4. Considering the very low singlet oxygen quantum yields of these compounds, and the lack of cytotoxicity of the photoreleased Hmte thioether ligand, it can be concluded that the toxicity observed after light activation is due to the photoreleased aqua complexes [Ru(tpy)(NN)(OH2)]2+, and thus that [2](PF6)2 and [3](PF6)2 are promising PACT candidates. Graphic abstract

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

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.

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

Materials ◽  
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.

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

2019 ◽  
Vol 48 (34) ◽  
pp. 13046-13056 ◽  
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.

Synthesis and QCM gas-sensing properties of 3,4-dialkoxyphenyl tosylamino-substituted phthalocyanines

2020 ◽  
Vol 24 (05n07) ◽  
pp. 830-839 ◽  
Author(s):  
Mika Harbeck ◽  
Zafer Şen ◽  
Dilek D. Erbahar ◽  
Esranur Fidan Çelik ◽  
Gülay Gümüş ◽  
...  
Keyword(s):  
Metal Ion ◽  
Gas Sensing ◽  
Metal Salt ◽  
Chemical Warfare Agent ◽  
Sensing Properties ◽  
Alkyl Chains ◽  
H Nmr ◽  
Gas Sensing Properties ◽  
Ft Ir ◽  
New Compounds

Octa-substituted metallophthalocyanines [M = Ni(II), Zn(II), Co(II), and Cu(II)] carrying 3,4-dialkoxyphenyl tosylamino groups at the peripheral positions have been synthesized from 1,2-dicyano-4,5-bis[(3,4-dialkoxyphenyl-tosylamino)methyl]benzene in the presence of the corresponding anhydrous metal salt. Next to the metal ion center, the length of the alkyl chains in the dialkoxyphenyl moiety ([Formula: see text], 5, 6, and 12) was varied. In total, sixteen soluble phthalocyanines have been characterized by elemental analysis, FT-IR and [Formula: see text]H-NMR spectroscopy as well as mass spectrometry. Furthermore, the gas sensing properties of these new compounds have been studied using quartz crystal microbalance transducers. The sensing properties are described on the basis of sensor responses to nine different test analytes comprising volatile organic compounds, toxic gases, and chemical warfare agent simulants. The influence of the metal ion center and substituents on sensor selectivity and sensitivity is discussed. The compounds show good performance in the gas-sensing experiments with diverse responses to the analytes. Phthalocyanine species with pronounced selectivity for polar analytes, hydrocarbons or amines have been identified among the set of sensors with the help of multivariate data exploration methods. The results reveal that quite a high diversity in terms of selectivity is introduced through the minute variations to the phthalocyanine structure.

Synthesis, characterization, photophysicochemical properties and theoretical study of novel zinc phthalocyanine containing four tetrathia macrocycles

2018 ◽  
Vol 22 (01n03) ◽  
pp. 77-87 ◽  
Author(s):  
Mohamad Albakour ◽  
Gülenay Tunç ◽  
Büşra Akyol ◽  
Sinem Tuncel Kostakoğlu ◽  
Savaş Berber ◽  
...  
Keyword(s):  
Singlet Oxygen ◽  
Zinc Phthalocyanine ◽  
Quantum Yields ◽  
Energy Structure ◽  
Fluorescence Measurement ◽  
Oxygen Generation ◽  
Fluorescence Quantum Yields ◽  
H Nmr ◽  
Ft Ir ◽  
Phthalocyanine Derivative

In this work, Zn(II) phthalocyanine derivative (TTU-Pc) bearing 13-membered tetrathia macrocycles was synthesized, and the novel Zn(II) phthalocyanine derivative was fully characterized by elemental analysis and general spectroscopic methods such as MALDI-TOF mass, FT-IR, UV-vis and [Formula: see text]H-NMR. The synthesized phthalocyanine derivative has quite limited solubility in most of the common organic solvents. Fluorescence measurement was conducted for this Zn(II)phthalocyanine to estimate its fluorescence quantum yields. The singlet oxygen generation ability was also examined to investigate its photosensitizer properties. General trends were described for quantum yields of fluorescence, photodegradation and singlet oxygen quantum yields of this compound. The electrochemical properties of the molecule were investigated by cyclic voltammetry (CV) and square wave voltammetry (SWV). In addition, the lowest energy structure, the electronic structure and frontier molecular orbitals were calculated in DFT and the excitation spectrum was obtained by TDDFT calculations. We found that our computational and experimental results were in agreement.

Synthesis, DNA photocleavage, singlet oxygen photogeneration and two photon absorption properties of ruthenium-phenanthroline porphyrins

2015 ◽  
Vol 19 (09) ◽  
pp. 1046-1052 ◽  
Author(s):  
Ze-Bin Xu ◽  
Fa-Quan Yu ◽  
Fengshou Wu ◽  
Heng Zhang ◽  
Kai Wang ◽  
...  
Keyword(s):  
Singlet Oxygen ◽  
Cross Section ◽  
Therapeutic Agents ◽  
Photon Absorption ◽  
Quantum Yields ◽  
Absorption Properties ◽  
Dna Photocleavage ◽  
Two Photon Absorption ◽  
Two Photon ◽  
Photochemical Properties

Through a new synthetic route, three ruthenium-phenanthroline porphyrins (RPP1, RPP2 and RPP3) were prepared. Their photophysical and photochemical properties, such as DNA photocleavage activity, singlet-oxygen photogeneration and two-photon absorption (2PA) were evaluated. These porphyrins 1–3 had substantial photocleavage activities, with 71%, 74% and 38% observed at 20 μM. The porphyrins with different substituents on phenathroline group had similar singlet oxygen quantum yields, with ΦΔ values at 0.52, 0.47 and 0.41, respectively. The 2PA cross-section (σ(2)) values of RPP 1–3, measured by the Z-scan method, were calculated to be 152, 172 and 135 GM, respectively, which were around 5-fold higher than that of H2TPP . Thus, these porphyrins, with their good photocleavage activities, 1 O 2 quantum yields and high 2PA cross section, suggest great potential as photodynamic therapeutic agents.

Influence of protonation of peripheral substituents on photophysical and photochemical properties of tetrapyrazinoporphyrazines

2010 ◽  
Vol 14 (07) ◽  
pp. 582-591 ◽  
Author(s):  
Veronika Novakova ◽  
Eva H. Mørkved ◽  
Miroslav Miletin ◽  
Petr Zimcik
Keyword(s):  
Charge Transfer ◽  
Sulfuric Acid ◽  
Singlet Oxygen ◽  
Electron Pair ◽  
Intramolecular Charge Transfer ◽  
Quantum Yields ◽  
Considerable Decrease ◽  
Fluorescence Quantum Yields ◽  
Photochemical Properties ◽  
Free Electron Pair

Octasubstituted zinc tetrapyrazinoporphyrazines with four N,N-dimethylaminophenyls and four phenyl or pyridin-3-yl substituents were synthesized and fully characterized. Their fluorescence quantum yields in DMF or pyridine were very low, almost undetectable, as a consequence of ultrafast intramolecular charge transfer. Titration of their DMF solutions with sulfuric acid led to increase of the fluorescence quantum yields by two orders of magnitude when the full protonation of peripheral substituents was achieved. Intramolecular charge transfer is no longer a favorable way of excited-state relaxation at full protonation of N,N-dimethylaminophenyl substituents because of loss of donor centers (free electron pair on its nitrogen). Similarly, singlet oxygen quantum yields also increased by two orders of magnitude when sulfuric acid was added to tetrapyrazinoporphyrazine solutions in DMF. Protonation at azomethine nitrogens of tetrapyrazinoporphyrazine macrocycle was observed at higher acid concentrations and it led to considerable decrease of fluorescence quantum yields. Octaphenyl zinc tetrapyrazinoporphyrazine and octa(pyridin-3-yl) zinc tetrapyrazinoporphyrazine were used as controls without intramolecular charge transfer. Their fluorescence and singlet oxygen quantum yields were high in DMF and decreased at higher concentrations of sulfuric acid due to protonation of azomethine nitrogens. The results suggest that the photophysical and photochemical properties of studied compounds may be controlled by changes of pH of medium.

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