Novel type ketone-substituted metallophthalocyanines: synthesis, spectral, structural, computational and anticancer studies

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Cancer is one of the diseases with the highest mortality rate worldwide. Although PDT has recently produced encouraging outcomes, there are still many areas that need to be improved. The first of these is the negative consequences faced by patients treated with the PDT method when exposed to sunlight. For this reason, a new PDT method has been developed in recent years, and it is aimed at using photosensitizer molecules that can be active in acidic conditions. Since the pH values of tumor tissues are more acidic than normal tissues, preparing molecules that act effectively in acidic conditions will allow for more effective results in treating cancer with PDT. In this context, within the scope of this study, 3‐(4‐propionylphenoxy)phthalonitrile (1) and its non‐peripheral tetra‐substituted phthalocyanine derivatives [(2), (3), and (4)] were prepared. With these phthalocyanine derivatives, the novel compounds (5), (6), and (7) were synthesized for the first time. The aggregation tendencies of newly synthesized phthalocyanines (5–7) were investigated in solvent media. The effects of pH changes upon UV–Vis and fluorescence spectra were performed. The electronic and emission spectra of synthesized phthalocyanine derivatives are highly sensitive to pH changes. Formation constant (LogK) values of mono‐ and di‐protonated phthalocyanine forms were calculated by the Henderson–Hasselback equation. The mono‐ and di‐protonated species' equilibrium constants (logK1 and logK2) were calculated as ~5.0. This value may be promising for pH‐sensitizing photosensitizers. Also, the photophysical and photochemical properties of synthesized metallophthalocyanine derivatives (2) and (5) were studied at different pH values. The singlet oxygen quantum yield of (2) and (5) was calculated to be 0.78 and 0.81 in DMSO, respectively. When pH = 6.4, that is, tumor‐pH‐values, this value for (5) has increased to 0.92. The newly synthesized phthalocyanines are suitable photosensitizers for PDT applications, especially with high singlet oxygen quantum yield at pH 6.4.

Section: Introductionmentioning

confidence: 84%

Tumor‐pH‐value responsive non‐peripheral substituted phthalocyanines: Synthesis, investigation of photophysical and photochemical properties

Genc Bilgicli,

Bilgiçli,

Alagöz

et al. 2023

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“…The HOMO and LUMO values of the molecules were used to explain the molecular activity. The chemical reactivity parameters of the molecules, such as Energy of the Highest Occupied Molecular Orbital ( E HOMO ), Energy of the Lowest Unoccupied Molecular Orbital (E LUMO ), Δ E (HOMO – LUMO energy gap), electronegativity ( χ ), chemical potential ( μ ), chemical hardness ( η ), electrophilicity ( ω ), nucleophilicity ( ε ), global softness ( σ ), and proton affinity (PA) were used to obtain information about the activities of the molecules:

μ = - χ = {(\frac{\partial E}{\partial N})}_{υ ((), r)}

η = \frac{1}{2} {(\frac{\partial^{2} E}{\partial N^{2}})}_{υ ((), r)} = \frac{1}{2} ((), \frac{\partial μ}{\partial N})

…”

Section: Methodsmentioning

confidence: 99%

Turn‐on fluorescent probe for Zn²⁺ ions based on thiazolidine derivative

Bilgiçli

Günsel

et al. 2020

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In this study, simple on–off fluorescent/UV–visible (UV–Vis) probes were easily prepared using 2‐(2‐hydroxyphenyl)thiazolidine‐4‐carboxylic acid (Sen‐1) and/or 2‐(2‐hydroxy‐5‐nitrophenyl)thiazolidine‐4‐carboxylic acid (Sen‐2) for fast detection of Zn2+ ions. Their sensing properties towards common metal ions were investigated using UV–Vis and fluorescence spectroscopies. Sen‐1 and Sen‐2 displayed a significant change with the addition of Zn2+ ions in the UV–Vis spectra. The addition of Zn2+ ions induced a 104 nm bathochromic shift for Sen‐1. The binding ratio towards Zn2+ metal ions was determined to be 1:1 by using Job plot analysis and fluorescence spectroscopy. The association constant and free energy (ΔG) of Sen‐1 and Sen‐2 towards Zn2+ ions were calculated by the Benesi–Hildebrand equation. The limit of detection of Sen‐1 towards Zn2+ ions is 3.73 × 10−8 M, which is about 1/100 of the value recommended by the World Health Organization for drinking water. Sen‐1 was successfully applied to detect Zn2+ ions in water samples and the fluorescence test strip was prepared for visual detection of Zn2+ ions. Finally, the quantum chemical parameters of Sen‐1 and Sen‐2, such as highest occupied molecular orbital, lowest unoccupied molecular orbital, and chemical hardness, were investigated by the Becke, three‐parameter, Lee–Yang–Parr, Hartree–Fock, and M062x methods.

“…[22] It is well known that the substitution of bulky groups in the peripheral/nonperipheral positions of phthalocyanines increases their solubility in common organic solvents. Phthalocyanines containing 1-(4-hydroxyphenyl) propane-1-one groups previously synthesized by our group have been found to have very high solubility in many organic solvents such as CHCl 3 , CH 2 Cl 2 , THF, toluene, DMF, and DMSO, [23,24] and within the scope of this study, it was found that the electronic spectra of novel octa-substituted phthalocyanine derivatives bearing 1-(4-hydroxyphenyl)propane-1-one are highly dependent on acid concentration. The green color of phthalocyanines was changed to pale green in the presence of HCl, which can be observed even with the naked eye.…”

Section: Introductionmentioning

confidence: 99%

Octa‐substituted Zinc(II), Cu(II), and Co(II) phthalocyanines with 1‐(4‐hydroxyphenyl)propane‐1‐one: Synthesis, sensitive protonation behaviors, Ag(I) induced H‐type aggregation properties, antibacterial–antioxidant activity, and molecular docking studies

Bilgiçli

Kandemir

Tüzün

et al. 2021

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This study shows the synthesis and characterization of 4,5-bis(4-propionylphenoxy)phthalonitrile (2) and its octa-substituted phthalocyanine derivatives [ZnPc(3), CuPc(4), and CoPc(5)]. A combination of standard spectroscopic techniques has characterized the newly synthesized phthalonitrile derivative and phthalocyanines. The aggregation behaviors of new octa-substituted phthalocyanines have been evaluated by ultravioletvisible (UV-vis) spectroscopy. The metal ion-sensitive behaviors of new octa-substituted phthalocyanines in the presence of soft metal ions have been performed by UV-vis and fluorescence spectrophotometer. The quenching efficiency (K sv ) of Ag + ions against ZnPc(3) was found using the Stern-Volmer equation. The binding constant (K a ) and binding stoichiometry (n) of ZnPc(3) with Ag + ions were calculated using the modified Benesi-Hildebrand equation. Sensitive protonation behaviors of octa-substituted phthalocyanines have been investigated by titration experiments as well as computational calculations. The ZnPc(3) and CuPc(4) were exhibited H-type aggregation behaviors toward Ag + ions. However, the protonation of octa-substituted zinc and copper phthalocyanine during the titration with HCl caused J-type selfaggregation properties. In vitro antioxidant properties of the new compounds were investigated by the radical scavenging ability of 1,1-diphenyl-2-picrylhydrazyl (DPPH), chelating ability to ferrous ions, and reducing power methods. Additionally, in vitro antibacterial activities of the octa-substituted phthalocyanines were determined. Finally, optimized structures of novel compounds [(2), ZnPc(3), CuPc(4), and CoPc(5)] were obtained on the HF (Hartree-Fock), B3LYP (Becke, 3-parameter, Lee-Yang-Parr), M06-2X methods with 3-21 g, 6-31 g and SDD basis set. Then, biological activities of