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The term sonophotodynamic therapy (SPDT) refers to a combination of sonodynamic therapy (SDT) and photodynamic therapy (PDT), in which the efficacy of the treatment is boosted by utilizing the proper amount of a sensitizer that is responsive to both light and ultrasound. Although it has been proven in photophysicochemical studies that SPDT enhances singlet oxygen production, related studies in the literature are very limited. Considering this situation, this study aims to investigate the efficacy of synthesized phthalocyanines in terms of PDT and SPDT. The singlet oxygen quantum values calculated as 0.13 for 5, 0.44 for 6, and 0.61 for 7 in photochemical (PDT) application increased to 0.18, 0.86, and 0.92, respectively, with sonophotochemical (SPDT) application. According to the results, singlet oxygen production was more efficient with SPDT. This work will add to the body of knowledge on employing the SPDT approach to increase singlet oxygen generation. [ABSTRACT FROM AUTHOR]

The aim of this paper is to explore the therapeutic contribution of graphene oxide (GO) to new sono/photosensitizers through sono/photochemical studies for the first time. For this purpose, new zinc (II) phthalocyanine bearing 3‐chloro‐4‐fluorophenoxy 2 was synthesized and then its GO‐based composites were prepared by non‐covalently coating ZnPc 2 on the graphene oxide surface. The photoactivity of these materials was compared and discussed in terms of their potential ability to be used in photosensitizer in photodynamic therapy (PDT) and sono‐photodynamic therapy (SPDT). In these application areas, GO can serve as photosensitizer carrier, while ZnPc 2 can be acting as PDT/SPDT agent. Therefore, phthalocyanine composites containing different percentages of graphene oxide by weight (wt.% GO) were prepared. SEM (scanning electron microscopy) results supported the interaction between GO and ZnPc 2. In the sono‐photochemical study, both ZnPc 2 and its composites gave very higher ΦΔ values than the photochemical study. The sono‐photochemical ΦΔ values were found to be 0.928 for 0 wt.% GO, 0.869 for 0.25 wt.% GO, 0.891 for 0.50 wt.% GO, 0.868 for 1 wt.% GO, 0.908 for 3 wt.% GO, 0.845 for 5 wt.% GO and 0.851 for 10 wt.% GO, respectively. According to obtained results, these materials could be promise as good photosensitizers for both the photochemical study and the sono‐photochemical study due to their very high singlet oxygen generation. [ABSTRACT FROM AUTHOR]

Phthalocyanines (Pcs) are an important group of substances with interesting chemical and physical properties with many different application areas. The use of Pc compounds in photodynamic therapy (PDT), especially in the treatment of cancer, has gained great importance in recent years. In this study, the spectral and electronic properties of new PDT active anticancer non-peripheral tetrakis [2-mercaptoquinoline]phthalocyanine and metal complexes were examined by using Density Functional Theory (DFT). Their properties were computed in DMSO and water phases. The UV absorption spectrum study results show that the main transition responsible for the Q band of the molecular spectrum is from π to π ∗ . The presence of the heavier atom in the Pc cavity has the effect of enhancing the fluorescence quantum yield. In addition, photochemical singlet oxygen production of newly synthesized phthalocyanine and metal complexes was also investigated. The calculated spectral (UV, IR, NMR) and singlet oxygen yield results were compared with the experimental ones and they were in good agreement. The spectral and electronic properties of non-peripheral tetrakis [2-mercaptoquinoline]-substituted magnesium, oxotitanium, zinc phthalocyanines were examined with DFT. The HOMO-LUMO energies, global descriptors, molecular electrostatic potential (MEP) surfaces, and spectral (UV-vis, IR, Raman, and NMR) properties of MPcs were calculated. ZnPc, MgPc and TiOPc can be preferred as photosensitizers in PDT applications. [ABSTRACT FROM AUTHOR]

This study reports synthesis of three new metallophthalocyanines namely 1(4),8(11),15(18),22(25)‐tetrakis‐(4‐(trifluoromethoxy)phenoxy) phthalocyaninato} Gallium chloride (1‐Ga), {2(3),9(10),16(17),23(24)‐tetrakis‐(4‐(trifluoromethoxy)phenoxy)phthalocyaninato} Gallium chloride (2‐Ga), and {2,3,9,10,17,18,23,24‐octakis‐(4‐(trifluoromethoxy)phenoxy)phthalocyaninato} Gallium chloride (3‐Ga). The newly synthesized macromolecules were characterized using different spectroscopic approaches, such as Fourier‐transform infrared (FT‐IR), ultraviolet–visible (UV–vis), and mass (MS) spectroscopy. Aggregation properties of the resulting compounds were studied at different concentrations ranging from 4 × 10−6 to 14 × 10−6 M. Density functional theory level computations were conducted to shed light on their electronic properties. The effect of the number and position of the substituent on photophysicochemical properties of the gallium chloride complexes (1‐Ga, 2‐Ga, and 3‐Ga) was studied for the examination of their performance as photosensitizer candidates in photodynamic therapy (PDT), comparatively. The complex 3‐Ga shows up the highest singlet oxygen quantum yield (ΦΔ = 0.87). The photophysical and photochemical features of the stated compounds are useful for PDT applications. [ABSTRACT FROM AUTHOR]

A new phthalonitrile precursor with tyrosine substituent and the zinc phthalocyanine derived from it were synthesized and their interaction with diphenylborinic acid was studied. The new compounds were characterized by using elemental analysis, IR, 1 H and 11 B-NMR and UV-VIS spectral data. 11 B-NMR data demonstrated that boron atom attached to the phthalonitrile precursor is in a bulky tetra-coordinated state with the formation of a coordinative N-B bond while completely planar phthalocyanine moieties with high aggregation tendencies at the concentrations used in NMR measurements lead the borinic ester side of the molecule into a planar tri-coordinated form. Moreover, the consequences of the presence of diphenylborinic ester groups on the spectral, photophysical and photochemical properties of the new zinc phthalocyanine are investigated in detail. [ABSTRACT FROM AUTHOR]

• Successfully synthesis and characterization of new phthalocyanines having Schiff base. • Photophysical and photochemical properties were investigated. • Determined their singlet oxygen generation efficiencies. • The bovine serum albumin (BSA) and DNA binding behaviours were determined in aqua solutions. In the present work, the synthesis, characterization, photophysicochemical and DNA/BSA binding activity of peripherally tetra-substituted metal-free (3a), Zn(II) (3b), and water soluble Zn(II) (3c) phthalocyanines containing tetra 4-(4-methoxybenzylidene)quinolin-3-imine moieties were reported. The new compounds 3a-3c were characterized spectroscopically. The aggregation behaviors of the synthesized phthalocyanines were examined in DMSO, DMF (3a and 3b) and aqueous medium (3c) at different concentrations. The fluorescence (Ф F), singlet oxygen (Ф Δ) and photodegradation quantum (Ф d) yields were investigated in DMSO, DMF (3a and 3b) and aqueous media (3c) to determine the suitability of novel phthalocyanines as photosensitizers. Besides, the effects of the presence of Zn+2 ion and the Schiff base substituent containing quinoline groups on the photophysicochemical properties were also researched. According to photochemical study, the presence of the metal ion and the Schiff base substituent containing the quinoline group on the pheriphery side of the phthalocyanine ring increases the singlet oxygen production. In addition, a spectroscopic investigation of the binding activity of the water-soluble zinc (II) (3c) complex to bovine serum albumin (BSA) and deoxyribo nucleic acid (DNA) were also studied in this work. All of these results suggest that 3c has a high-quality photosensitiser agent for photodynamic therapy to that of 3c due to DNA and BSA photocleavage properties. [ABSTRACT FROM AUTHOR]

4-[4-(Thiophen-3-yl)phenoxy]phthalonitrile and 4,5-bis[4-(thiophen-3-yl)phenoxy]phthalonitrile and their corresponding tetra- and octa-substituted metal-free and Lu(III) phthalocyanine derivatives have been synthesised. The aggregation behaviour of the phthalocyanine compounds has been investigated in different solvents and concentrations and the effects of the substituent and the lutetium on their photophysical properties are reported. [ABSTRACT FROM AUTHOR]

The synthesis of a 4-(2,2-diphenylethoxy)phthalonitrile (1) and its organosoluble free base (2), zinc(II) (3), nickel(II) (4), and cobalt(II) (5) phthalocyanine derivatives is presented in this work. The novel complexes were characterized by elemental analyses and spectral data such as infrared, nuclear magnetic resonance, ultraviolet visible, and mass data. General tendencies were described for photophysics (fluorescence) and photochemistry (photodegradation and singlet oxygen quantum yields) of the free base and zinc(II) phthalocyanine derivatives in dimethylformamide. The quantum yield values of fluorescence (ΦF), singlet oxygen formation (ΦΔ), and photodegradation (Φd) for the zinc phthalocyanine were found to be 0.37, 0.48, and 9.12 x 10-4, respectively. The photophysicochemical properties of the phthalocyanines (2 and 3) clearly reveal that these phthalocyanines could be used in singlet oxygen applications such as photodynamic therapy. [ABSTRACT FROM AUTHOR]

Abstract: The synthesis of a new 3,4-(dimethoxyphenylthio) substituted phthalonitrile (1) and its soluble metal free (2), zinc (II) (3), oxo-titanium (IV) (4) and nickel (II) (5) phthalocyanine derivatives are reported for the first time. The new compounds have been characterized by elemental analysis, FT-IR, 1H NMR, UV–Vis, fluorescence spectroscopies and mass spectra. General trends are described for fluorescence, photodegradation and singlet oxygen quantum yields and fluorescence lifetimes of oxo-titanium (IV) and zinc (II) phthalocyanine compounds in dimethylsulfoxide (DMSO). The effects of the metal ion on the photophysical and photochemical parameters for these phthalocyanines (3 and 4) are also reported. [Copyright &y& Elsevier]

Abstract: The synthesis, photophysical and photochemical properties of soluble 3,4-(methylendioxy)-phenoxy substituted oxo-titanium(IV) phthalocyanines (4–6) are reported for the first time. The new compounds have been characterized by elemental analysis, FT-IR, 1H NMR spectroscopy, electronic spectroscopy and mass spectra. General trends are described for fluorescence lifetimes and fluorescence, photodegradation and singlet oxygen quantum yields, of these compounds in dimethylsulfoxide (DMSO) and toluene. The effects of the position of the substituents and solvent effect on the photophysical and photochemical parameters of the oxo-titanium(IV) phthalocyanines (4–6) are also reported. The fluorescence of the substituted oxo-titanium(IV) phthalocyanine complexes (4–6) is effectively quenched by 1,4-benzoquinone (BQ) in both DMSO and toluene. [Copyright &y& Elsevier]

Abstract: The syntheses and spectral, photophysical and photochemical properties of some zinc phthalocyanine derivatives – {2, (3)-tetra(quinoxalinyl)phthalocyaninato zinc(II), (β-ZnPc) and 1, (4)-tetra(quinoxalinyl)phthalocyaninato zinc(II), (α-ZnPc)} – are presented. The β-substituted complex is more fluorescent and exhibits lower tendencies to undergo intersystem crossing than its α-substituted counterpart, as judged by the former''s higher fluorescence quantum yield (Φ F ) and lower triplet quantum yield (Φ T ) than the latter''s in three solvents (DMSO, DMF and toluene). Singlet oxygen quantum yield (Φ Δ ) values show the same trends as Φ T values. The differences in the spectral and photophysical properties of α-ZnPc and β-ZnPc are partly attributed to greater molecular distortions in the former. Studies of the interaction of the triplet states of α-ZnPc and β-ZnPc with triplet oxygen showed that α-ZnPc is more vulnerable to oxygen quenching than β-ZnPc. Also, the smallest quenching rate constants were observed in DMSO, which is attributed to the higher viscosity of DMSO than DMF and toluene. [Copyright &y& Elsevier]

[Display omitted] The singlet oxygen quantum yield is a valuable parameter for assessing the ability of a photosensitizer to generate radical oxygen. This value is influenced by the photo-physicochemical characteristics of the sensitizer molecule. Phthalocyanines are among these complexes and as the central metal atoms and substituent groups on the phthalocyanine ring are modified, the therapeutic effects required for photodynamic therapy (PDT) can be enhanced. For this purpose, 5-bromo-2-hydroxypyridine substituted zinc phthalocyanine and its biocompatible quaternized structure are synthesized and shown to exhibit singlet oxygen efficiency with Φ Δ values reaching 0.65 in DMSO and 0.39 in water in photochemical studies. The obtained fluorescence quantum yields (Φ F) for the compounds are 0.17 in DMSO and 0.06 in water, while the photodegradation (Φ d) values are 9.1 x 10-3 in DMSO and 5.3 x 10-3 in water. This research offers valuable insights into developing water-soluble and targeted photodynamic therapies for combating cancer using photochemical applications. [ABSTRACT FROM AUTHOR]

In this study, the three new phthalonitriles (1 , 2 , 3) and their non-peripherally tetra substituted zinc phthalocyanines (3)-Tetra [bromophenoxy] phthalocyaninato zinc (II) (np4), (3)-Tetra [chlorophenoxy] phthalocyaninato zinc (II) (np5) and (3)-Tetra [fluorophenoxy] phthalocyaninato zinc(II) (np6) are reported for the first time. All phthalonitriles and their phthalocyanines have been characterized by using spectroscopic methods, FT-IR, 1H NMR, electronic spectroscopy and mass spectra as well as elemental analysis. To investigate photosynthesizer's properties; fluorescence, singlet oxygen and photodegradation quantum yields of non-peripherally Pcs were measured in dimethylsulfoxide (DMSO), dimethylformamide (DMF) and tetrahydrofuran (THF) solutions. Non-peripherally position and solvent effect on the photophysical and photochemical parameters of the chloro, fluoro, bromo phenoxy-phenoxy substituted phthalocyanines (np4 , np5 and np6) are also compared with the corresponding tetra-peripherally substituted analogues. The values of non-peripherally zinc phthalocyanines (np4 to np6) could be classified as photosensitizers in the photocatalytic applications such as photodynamic therapy (PDT) of cancer due to having good singlet oxygen yields (ranging from 0.52 to 0.85). • Synthesis of novel non-peripherally phthalocyanines with improved photophysicochemical properties. • Substituents and Solvent effects on the photophysicochemical parameters of phthalocyanines. • Singlet oxygen generation and photodegradation. • Photodynamic therapy properties. [ABSTRACT FROM AUTHOR]

In this study, a new type of Zn-phthalocyanine compound (2) peripherally substituted with 4-Hydroxy-7-methoxyquinoline was synthesized and characterized, and its photodynamic and sono-photodynamic activities were examined both experimentally and theoretically. [Display omitted] In recent years cancer has become a global problem and burden to the health system. Photodynamic therapy (PDT) and sonodynamic therapy (SDT) are promising alternatives for cancer treatment. It is very important to use phthalocyanines as sensitizers in such treatments. In this study, a new type of Zn-phthalocyanine compound (2) peripherally substituted with 4-Hydroxy-7-methoxyquinoline was synthesized and characterized, and its photodynamic and sono-photodynamic efficiencies were examined. Additionally, the electronic and spectroscopic properties of the compounds were calculated theoretically using Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT) methods. The effect of the solvent on the reactivity of the compounds was examined by the Conductive-Like Polarizable Continuum Model (CPCM). The results have indicated that singlet oxygen quantum yield has increased in the sono-photochemical study (Φ Δ =0.98) compare to the photodynamic study (Φ Δ =0.70). Experimental and theoretical study results show that the reactivity of the new ligand increases with Zn metal. [ABSTRACT FROM AUTHOR]

Abstract: The three new phthalocyanine precursors, 4-[4-(bromo phenoxy)phenoxy]phthalonitrile, 4-[4-(chlorophenoxy)phenoxy]phthalonitrile, 4-[4-(flourophenoxy)phenoxy]phthalonitrile (1, 2 and 3) were synthesized and characterized. The photochemical properties (singlet oxygen quantum yields and photodegradation quantum yields) and photophysical properties (fluorescence quantum yields and fluorescence behavior) of their peripherally tetra substituted zinc phthalocyanines (4)-tetra[bromo phenoxy]phthalocyaninato zinc(II), (4)-tetra[chlorophenoxy]phthalocyaninato zinc(II), (4)-Tetra [flourophenoxy]phthalocyaninato zinc(II) (4, 5 and 6) were reported for the first time. The new compounds (1–6) were characterized by using spectroscopic methods, FT-IR, 1H NMR spectroscopy, electronic spectroscopy and mass spectra as well as elemental analysis. General trends focus on fluorescence, photodegradation and singlet oxygen quantum yields of these compounds in dimethylsulfoxide (DMSO), dimethylformamide (DMF) and tetrahydrofuran (THF). The nature of the substituent and solvent effects on the photophysical and photochemical parameters of the chloro, fluoro, bromo-phenoxy-phenoxy substituted phthalocyanines (4, 5 and 6) was also reported. [Copyright &y& Elsevier]

Abstract In this study, ligand (1) was prepared by a nucleophilic displacement reaction of (4-bromophenyl)methanethiol with 4-nitrophthalonitrile according to literature and its novel type peripheral substituted tetra phthalocyanines [CuPc (2), ZnPc (3) and GaPc (4) ] were prepared. The phthalocyanines obtained from compound (1) were characterized by FT-IR, 1H NMR, UV–Vis spectral data, elemental analysis, and MALDI-TOF. The novel phthalocyanines [CuPc (2), ZnPc (3) and GaPc (4)] were highly soluble in common organic solvents such as CHCl 3 , THF, CH 2 Cl 2 , DMSO and DMF. The effect of Pd2+ ions on the fluorescence emission and UV–Vis spectra were performed with addition of increasing amounts of Pd2+ ions. This functional phthalocyanines exhibited H-type aggregation versus Pd2+ ions due to special chemical structures, which can be used as a selective chemosensor for Pd2+ ions. Also, the molecular reactivity of the ligand (1) and related metallo phthalocyanines [CuPc (2), ZnPc (3) and GaPc (4)] were investigated and compared with the analysis of frontier molecular orbitals. In addition, photochemical and photophysical properties of these new phthalocyanines (fluorescence quantum yields, fluorescence behavior, singlet oxygen and photodegradation quantum yields) were studied in DMSO. Graphical abstract Image 1 Highlights • The synthesis of novel-type phthlocyanines bearing "(4-bromophenyl)methanethiol" as functional groups at peripheral positions. • Selective chemosensor for Pd2+ ions. • The investigation of photophysical and photochemical parameters. • The analysis of frontier molecular orbitals. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • The synthesis of tetra substituted phthalocyanines. • The crystallographic molecular structure of the ligand (1). • The optimized structures of the ligand (1) and the phthalocyanines (2–5). • The good singlet-oxygen yield. Abstract This work presents the synthesis of 4-(2-(ethyl(m-tolyl) amino) ethoxy) phthalonitrile (1) as ligand and its peripherally tetrasubstituted metal-free (2) and metallophthalocyanines (3–5) derivatives. Synthesized compounds were characterized by standart spectroscopy methods. The molecular structure of the ligand (1) was confirmed by single-crystal X-ray diffraction experiment. The crystallographic information file (cif) was uploaded to the data center with CCDC number 1,853,485. The optimized structure of the ligand (1) and the phthalocyanines (2–5) were obtained by using different metods such as B3lyp, HF and m062x method 3–21 g, 6–31 g, sdd basis set. In b3lyp/6–31++g(d,p) basis set, 1H and 13C NMR chemical shifts, IR spectrum and UV–vis spectrum were measured in gas, chloroform and dimethylsulfoxide phase by means of the obtained optimized structure. Besides, the photophysical and photochemical properties of newly synthesized phthalocyanines (2–5) were investigated in DMSO, comparatively. Singlet oxygen quantum yields of the phthalocyanines (2–5) are ranging from 0.28 to 0.70. [ABSTRACT FROM AUTHOR]

Graphical abstract This work presents the synthesis of peripherally and non-peripherally tetra-substituted metallophthalocyanines. The quantum chemical parameters of the ligands, such as the HOMO, LUMO and chemical hardness were calculated by the B3lyp, HF and M062x methods. The Δ G value of the phthalocyanine compunds were calculated with the obtained results. In addition, the photophysical and photochemical properties of the newly synthesized phthalocyanines were investigated in DMSO solutions, comparatively. Abstract This work presents the synthesis of peripherally and non-peripherally tetra-substituted metallophthalocyanines (6 – 14) containing the 2-(3,4-dimethoxyphenyl)ethanol group. The synthesized compounds were characterized by standard spectroscopy methods. The ligands of the metallophthalocyanines were investigated by quantum chemical calculations. The quantum chemical parameters of these ligands (1 and 2) such as the HOMO, LUMO and chemical hardness were calculated by the B3lyp, HF and M062x methods. The Δ G value of the metal complexes of the ligands were calculated with the obtained results. In addition, photophysical (fluorescence quantum yields) and photochemical (singlet oxygen generation and photodegradation under light irradiation) properties of newly synthesized phthalocyanines were investigated in DMSO solutions, comparatively. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Novel zinc and indium phthalocyanines (MPcs) with furan-2-ylmethoxy groups were prepared. • Photophysical and photochemical properties of these phthalocyanines were investigated. • MPcs bearing furan-2-ylmethoxy indicated a high singlet oxygen quantum yield. • Antioxidant and antimicrobial properties of the complexes investigated and compared. Abstract The synthesis, characterization, aggregation, photophysical, antioxidant and antimicrobial properties of furan-2-ylmethoxy substituted zinc (2) and chloroindium (3) phthalocyanine complexes are reported for the first time. The novel compounds have been characterized by using elemental analysis, UV–vis, FT-IR, 1H-NMR and MS spectroscopic data. In photophysical studies, the effect of the central metal ion on the UV–vis and photophysical properties of the metallophthalocyanines are reported. These results suggest that the metal in the core of the phthalocyanine plays essential role in the fluorescence quantum yields (Φ F) of the synthesized complexes. In addition, high quantum yields of singlet oxygen generation (Φ Δ ranging from 0.58 to 0.69 in THF) were obtained. Antioxidant activities of the complexes were determined by using three different methods. In all experiments performed, complex 3 showed better antioxidant activity than complex 2. Complex 3 showed 59.01 ± 1.23% inhibition of DPPH (1,1-diphenyl-2-picrylhydrazyl) free radicals and 84.16 ± 0.13% ferrous metal chelating activity both at 500 mg/L concentration and the highest reducing power activity were measured at 0.397 nm with 80 mg/L concentration. Inhibition zone of complex 3 was found as 11 mm for Escherichia coli , 7.5 mm for Bacillus subtilis, 13 mm for Bacillus cereus and 9 mm for Pseudomonas aeruginosa. Inhibition zone of complex 2 was found 8 mm for Staphylococcus aureus and Bacillus subtilis (ATCC 6051). In addition, MIC (Minimum Inhibitory Concentrations) values varied in the range of 2.0–64 μg/mL. [ABSTRACT FROM AUTHOR]

This paper reports on the synthesis and characterization of non-peripherally and peripherally tetrasubstituted metal-free and zinc(II) phthalocyanines functionalized with the phenolic compound “4-hydroxybenzyl methyl ether (HBME)”. Synthesized compounds have been characterized by elemental analysis, FT-IR, 1 H NMR, 13 C NMR, MALDI-MS and UV–Vis spectral data. Besides, spectral, photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen generation and photodegradation under light irradiation) properties of newly synthesized phthalocyanines were investigated in DMF solution. We obtained very high singlet oxygen quantum yields as 0.86, 0.91, suggesting its potential as photosensitizer in PDT treatment. [ABSTRACT FROM AUTHOR]

This work reports on the synthesis and characterization of phthalocyanines (M = Ga(III) and In(III)) which is peripherally tetra-substituted with 4-(4-hydroxyphenyl)butan-2-one and also with 1-(4-hydroxyphenyl)propan-1-one. Confirmation of the synthesized phthalocyanine structures performed with a combination of elemental analysis, FTIR, 1 H NMR, 13 C NMR, UV–vis and MALDI-MS spectral data. Also, investigated and discussed the effects of peripherally tetra-substitution with different ketones which contain reactive carbonyl groups on the photochemical (Singlet oxygen quantum yields and photodegradation quantum yields) and photophysical properties (Fluorescence quantum yields and fluorescence behavior) which is very important for biological cell studies on PDT. The singlet oxygen quantum yields give an indication of the efficiency of potential photosensitizers in photodynamic therapy (PDT). That's why the high results (Φ Δ; 0.90, 0.88, 0.60 and 0.80 in DMSO) of spectral measurements showed that all of the complexes can have potential to be used as sensitizers. [ABSTRACT FROM AUTHOR]

Peripherally electron withdrawing thiadiazole substituted phthalocyanine Zn(II), Ga(III) and axially disubstituted Si(IV) complexes have been synthesized for the first time. These new phthalocyanine compounds have been characterized by spectral methods such as FT-IR, 1 H NMR, UV–vis spectra, Mass spectra and elemental analyses. In this study, the ground state electronic absorption spectra and the nature of the metal ion on the photophysical and photochemical parameters of the phthalocyanines are also presented. The closed shell and diamagnetic ions (Zn(II), Ga(III) and Si(IV)) gave high quantum yields of singlet oxygen ( Φ Δ , 0.49, 0.81 and 0.86 in DMSO), which makes them potential photosensitizer for use in photodynamic therapy (PDT) of cancer. [ABSTRACT FROM AUTHOR]

As cancer is one of the leading causes of death globally, it is highly desirable to explore the therapeutic potential of new sensitizers in photodynamic therapy (PDT). In recent years, PDT applications performed with the help of ultrasound have attracted attention. Also, the importance of phthalocyanines, which are used as sensitizers in photodynamic and/or sonodynamic therapy (SDT), is increasing. The most important properties of phthalocyanines for therapeutic applications are their ability to generate reactive oxygen species (ROS) at the appropriate wavelength. To improve ROS production by phthalocyanines applying ultrasounds seems to be the reasonable pathway of development for this treatment method. In this context, to evaluate potentials for sonophotodynamic therapy (SPDT), the syntheses of highly soluble non-peripherally substituted metal-free (2), gallium (3), and indium (4) phthalocyanines were completed by substituting 3-methoxybenzyloxy groups. All prepared compounds were elucidated using many different spectroscopic approaches encompassing Fourier transform infrared (FT-IR), ultraviolet–visible (UV–Vis), 1H NMR, and matrix-assisted laser deionization/ionization time-of-flight mass spectroscopy (MALDI-TOF MS) techniques. Additionally, photophysical, photochemical, and sono-photochemical evaluations of the novel phthalocyanines are presented. The combination of ultrasound and light had an enhancing effect on singlet oxygen production in all phthalocyanine derivatives (2 – 4). Singlet oxygen quantum yields increased between 50% and 80% for metal-free, gallium, and indium phthalocyanines. Density Functional Theory (DFT) and time-dependent (TD-DFT) were used for the description of optical and electronic properties of metal-free, gallium, and indium phthalocyanines. The Spin Orbital Coupling Constant (SOCC) for these molecules was also calculated through the quasi-degenerate perturbation theory method. Considering the singlet and triplet states of lower energy, we have calculated the most probable intersystem spin crossing (ISC) pathways. Our results suggest that all the phthalocyanines have potential application in PDT, however, indium phthalocyanine has greater applicability in PDT. [Display omitted] • Syntheses of highly soluble phthalocyanines were completed by substituting 3-methoxybenzyloxy groups. • Photophysical, photochemical, and sono-photochemical properties of the novel phthalocyanines are presented. • Combination of ultrasound and light had an enhancing effect on singlet oxygen production in all phthalocyanine derivatives. • The Spin Orbital Coupling Constant (SOCC) and most probable intersystem spin crossing (ISC) pathways are calculated. • 3-methoxybenzyloxy substituted indium phthalocyanine has great applicability in photodynamic purposes. [ABSTRACT FROM AUTHOR]

The novel axially dicarborane substituted silicon (IV) ( SiPc-DC ) phthalocyanine was synthesized by treating silicon phthalocyanine dichloride SiPc(Cl) 2 ( SiPc ) with o -Carborane monool. The compound was characterized by mass spectrometry, UV–Vis, FT-IR, 1 H and 11 B Nuclear Magnetic Resonance Spectroscopy (NMR). Spectral, photophysical (fluorescence quantum yield) and photochemical (singlet oxygen ( Φ Δ ) and photodegradation quantum yield ( Φ d )) properties of the complex were reported in different solutions (Dimethyl sulfoxide (DMSO), Dimethylformamide (DMF) and Toluene). The results of spectral measurements showed that both SiPc and carborane cage can have potential to be used as sensitizers in photodynamic therapy (PDT) and boron neutron capture therapy (BNCT) by their singlet oxygen efficiencies ( Φ Δ = 0.41, 0.39). [ABSTRACT FROM AUTHOR]

A novel zinc(II) phthalocyanine substituted with four diphenylborinic ester units was synthesized by the reaction of 2,9,16,23-tetra (salicylaldimino)-phthtalocyaninatozinc(II) and triphenylborane in THF at reflux condition. The novel zinc phthalocyanine was characterized by using elemental analysis, IR, 1 H and 11 B-NMR and UV–Vis spectral data. 11 B-NMR data demonstrated that the boron atom is in tetracoordinated state and diphenylborinate substituents have a cyclic structure with a coordinative N–B bond enhancing the stability of this borinated phthalocyanine derivative. Moreover, the consequences of the presence of diphenylborinic ester groups on the spectral, photophysical and photochemical properties of the new zinc phthalocyanine are investigated in detail. [ABSTRACT FROM AUTHOR]

Photodynamic therapy (PDT) is an alternative way to treat the cancer non-surgically with minimum harm, in which a specific light and light sensitive photosensitizer (PS) is used. This study deals with the utilization of zinc photosensitizers (λ max ∼700 nm) from the group of phthalocyanines in photodynamic therapy. The photosensitizers differed in bearing either tetra- or octa-mercaptopropionic acid groups. The phthalocyanines (L1ZnPc and DipZnPc) were tested in cancer cell line, HeLa cell (epitheloid cervix carcinoma), by dark and light cytotoxicity. The photophysico-chemical properties of the resulting zinc photosensitizers were analyzed and to investigate the singlet oxygen's efficiency, photochemical properties were determined. For L1ZnPc, the singlet oxygen quantum yield was Φ Δ = 0.41 and for DipZnPc, the value was Φ Δ = 0.27. In addition to the experimental outcomes, this study handles detailed calculations of the absorbed light dose by the photosensitizer at a specific wavelength. In the light of this study, the researchers could get the insight of the precise amount of energy delivered to the cells by a laser beam for critical applications. The absorbed dose of the laser irradiation was calculated within a true wavelength range that is the most detailed explanation in literature. This study deals with the utilization of zinc phthalocyanine photosensitizers (λ max ∼700 nm) in photodynamic therapy. The phthalocyanines were tested in cancer cell line, HeLa cell (epitheloid cervix carcinoma), by dark and light cytotoxicity. The photophysico-chemical properties of the resulting zinc photosensitizers were analyzed to investigate the singlet oxygen efficiency and photochemical properties were determined. In the light of this study, also the researchers could get the insight of the precise amount of energy delivered to the cells by a laser beam for critical applications. [Display omitted] • Zinc phthalocyanine photosensitizers (λ max ∼700 nm) were studied in photodynamic therapy (PDT). • Synthesized photosensitizers offer an effective PDT for epitheloid cervix carcinoma cells. • Their photochemical properties were analyzed to see the singlet oxygen generation efficiencies. • The absorbed dose of the laser was calculated within a true wavelength range for the first time in PDT. [ABSTRACT FROM AUTHOR]

• Single crystal x-ray diffraction measurements of 4-(1-methyl-1H-imidazole-2-thiol) phthalonitrile. • Synthesis of novel water-soluble phthalocyanine hydrochloride bearing imidazole derivative. • Investigation of photo-physicochemical, anti-α-glygosidase, anti-cholinesterases properties. • Antibacterial properties: gram-negative and gram-positive bacteria. In this work, we have reported on the synthesis and characterization of water-soluble hydrochloride forms (2a-4a) based on novel peripherally [ M = metal-free (2) , zinc (II) (3) , gallium (III) chloride (4) ] phthalocyanines bearing 1-methyl-1H-imidazole-2-thiol substituents. Characterization of all compounds used was supported by a series of spectroscopic techniques such as UV–Vis, FT-IR 1H NMR, 13C NMR and MALDI-MS, etc. The confirmation of the molecular structure of 4-(1-methyl-1H-imidazole-2-thiol) phthalonitrile (1) by single crystal x-ray diffraction experiment was performed for the first time in this work. Besides, the intra/inter-molecular interactions inside the obtained crystal structure have been investigated. Afterward, the effects of the central metal atoms and solvents on the photophysicochemical properties of the phthalocyanines were analyzed to investigate their potential to use as a photosensitizer in photodynamic theraphy (PDT). The obtained results show that the phthalocyanines have therapeutic outcomes for cancer treatment. It has been seen that all compounds have a better ability to inhibit compared to existing tried inhibitors. Among these, the best inhibitors against acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) enzymes are (4) (Ki 47.71±9.14 µM and IC 50 68.22) and (3a) (Ki 20.12±3.75 µM and IC 50 19.24), respectively. Also, against α-Glycosidase, (4) showed the highest effect (Ki 9.13±1.05 µM and IC 50 11.22). Phthalocyanines were performed to gram-negative and gram-positive bacteria using minimum inhibition concentration (MIC) assay and indicated an antibacterial effect. [Display omitted] [ABSTRACT FROM AUTHOR]

In this study, novel silicon phthalocyanines complexes have been synthesized, characterized and compared their antitumor efficiency of photodynamic, sonodynamic, sonophotodynamic on prostate cancer cells. Sonophotodynamic therapy (SPDT), a combination of photodynamic therapy (PDT) and sonodynamic therapy (SDT), is a new and promising method for the treatment of cancer cells. Although it is known that SPDT therapy has improved potential therapeutic result, the development of this method by working with different sensitizers has been lacking in the literature. To the best of our knowledge, this paper is the first study in the literature to calculate the photochemical properties of synthesized molecules and compare the results of photodynamic, sonodynamic and sonophotodynamic therapies on prostate cancer cells. In this study, new water soluble sensitizers with the different properties of linker heteroatom (O or S) were synthesized, characterized and analyzed their photophysicochemical properties. Then, the effects of sonodynamic, photodynamic and sonophotodynamic on these sensitizers were examined in vitro on prostate cancer using PC3 cells. For this purpose, the cells were incubated with various concentrations of chemicals and subjected to ultrasound and/or light irradiation. According to MTT results, the sensitizers were showed quite efficiency for sonodynamic, photodynamic and sonophotodynamic therapies and decreased cell viability when compared with control group. Also apoptosis measurement data shows that the sensitizers (1a , 1b) would produce much better effects by combination sonodynamic and photodynamic therapies, especially the measurement of apoptotic cells in complex 2a reached 95% after SPDT therapy. As a result, it is seen that SPDT is a combination which has enhanced the therapeutic outcome. Image 1 • The novel water soluble silicon (VI) phthalocyanines bearing quinolone moieties. • The photochemical and photophysical properties of these phthalocyanines were investigated. • Compared their antitumor efficiency of photodynamic, sonodynamic and sonophotodynamic on prostate cancer cells. • Apoptotic cell were observed in 95% in SPDT studies for 2a. [ABSTRACT FROM AUTHOR]

• Synthesis of water-soluble tetra-substituted phthalocyanines containing sodium 2-mercaptoethanesulfonate substituents. • Photo-physicochemical and biological properties. • The effective inhibitor for the α-glycosidase, human carbonic anhydrase I and II isoforms, and cholinesterase enzymes. • Antidiabetic, anticancer and anticholinergic potentials. In this study, we have reported on the synthesis and characterization of water-soluble phthalocyanines [M=2H (2) , Zn(II) (3) , Ga(III)Cl (4) , containing sodium 2-mercaptoethanesulfonate substituents at the non-peripheral positions. All compounds were characterized by UV–vis, FT-IR and NMR spectroscopies, and MALDI-TOF mass spectra. Besides, spectral, photophysical (fluorescence quantum yields) and photochemical (singlet oxygen generation and photodegradation under light irradiation) properties of newly synthesized phthalocyanines were investigated in DMSO. These synthesized phthalocyanines [M=2H (2) , Zn(II) (3) , Ga(III)Cl (4) were found to be effective inhibitor compounds for the α-glycosidase, human carbonic anhydrase I and II (cytosolic, ubiquitous isozymes), hCA IX (transmembrane, cancerassociated isozyme), and cholinesterase enzymes with Ki values in the range of 0.66±0.08–2.31±0.24 μM for α-glycosidase, 8.54±1.63−14.93±2.05 μM for hCA I, 10.77±1.55−13.74±0.97 μM for hCA II, 10.55±0.98−15.96±1.54 μM for hCA IX, 102.77±16.04–158.43±26.95 μM for BChE, and 114.75±15.05–174.31±35.43 μM for AChE, respectively. Additionally, this work is also the first example of cancer-associated isozyme hCA IX inhibition by these novel phthalocyanines. [ABSTRACT FROM AUTHOR]