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This study investigates novel zinc and indium phthalocyanines with Schiff base and sulphur moieties, focusing on their potential for cancer therapy and antimicrobial applications. It explores the effectiveness of photochemical and sono-photochemical methods to enhance singlet oxygen production, which is crucial for photodynamic therapy. The synthesized complexes in this study demonstrated high singlet oxygen quantum yields, with D3 (ZnPc) and D4 (InPc) showing Φ ΔPDT values of 0.71 and 0.75, and Φ ΔSPDT values of 0.91 and 0.94, respectively. Furthermore, the evaluation for biological properties revealed that both D3 and D4 exhibit significant antidiabetic properties, DPPH radical scavenging activity, DNA cleavage, antimicrobial activity, biofilm inhibition, and microbial cell viability impacts, both with and without photodynamic therapy. Notably, D3 and D4 achieved antimicrobial cell viability inhibition rates of 84.67 ± 4.67% and 98.32 ± 5.96%, respectively, showcasing their effectiveness in photodynamic antimicrobial therapy. Overall, the study highlights the potential of these phthalocyanine complexes as advanced photosensitizers, with strong singlet oxygen generation and promising biological activities, paving the way for future therapeutic applications.

Glycosaminoglycans (GAGs) serve as a biomarker for mucopolysaccharidoses disease. In this study, a novel fluorometric method was developed to measure total GAGs in urine. Graphene oxide (GO) and rhodamine B (RhB), a cationic fluorescent dye, were employed in the development of the method. RhB attaches to the GO surface via electrostatic attraction, leading to the quenching of its fluorescence upon the establishment of the RhB-GO complex. However, the presence of GAGs prompts a resurgence of intense fluorescence. The linear range of the method is between 5.00 and 70.00 mg/L. The total GAG levels of urine samples analyzed using the method agree with the results of the biochemistry analysis laboratory (65.85 and 79.18 mg/L; 73.30 ± 1.76 and 72.21 ± 2.21). The method is simple, accurate, and sensitive and may be used for both first-step diagnosis of the mucopolysaccharidoses and detection of individual GAGs for studies of GAG-related research and other biological applications., (© 2024 International Union of Biochemistry and Molecular Biology, Inc.)

Breast cancer is a life-threatening disease that is gaining increasing importance due to its rising incidence, highlighting the need for novel treatment methods with the least disadvantages. Recently, scientists have focused on developing therapeutic treatment modalities for effective cancer treatment. In contrast to conventional cancer treatment methods such as immunotherapy, surgery, chemotherapy, or radiotherapy, photodynamic therapy (PDT) is gaining prominence. Besides, sonodynamic treatment (SDT) is a noninvasive therapeutic approach that uses ultrasound to induce high tissue penetration. In both methods, sensitizers are activated to generate cytotoxic reactive oxygen species such as • OH and 1 O 2 . In particular, the combined use of hybrid and complementary treatment methods has become an important modality in cancer treatment in recent years. Sono-photodynamic therapy (SPDT), which is an important method applied in combination with PDT and SDT, has started to be preferred in terms of reducing potential side effects compared to monotherapy. One of the most important types of sensitizers used in PDT and SDT is known as phthalocyanines (Pcs). Motivated by these facts, this research presents the sono-photochemical, in vitro cytotoxicity, and theoretical evaluation of water-soluble gallium phthalocyanine ( GaPc ). The results indicate that the quantum yield of the generation of singlet oxygen increased in sono-photochemical studies (Φ Δ = 0.94), compared to photochemical studies (Φ Δ = 0.72). In vitro analyses revealed that GaPc did not exhibit significant cytotoxic effects at the specified varying concentration doses (1-20 μM). Furthermore, GaPc -mediated SPDT triggered cell death by inducing reactive oxygen species formation in the breast cancer cell line (MCF-7). The interaction mechanism of the GaPc with EGFR and VEGFR2 target proteins, which are critical regulators of metastasis, proliferation, and angiogenesis, was investigated by molecular docking simulation. GaPc has effective binding affinities against target proteins, and this affinity was found to be the highest against VEGFR2. Molecular docking results showed a good correlation with the obtained biological results. Eventually, this molecular building of the efficient water-soluble phthalocyanine-based sensitizer is a potential therapeutic for PDT, SDT, and SPDT applications.

This study demonstrates the potential of sono-photodynamic therapy as an effective approach for enhancing singlet oxygen generation using the synthesized Schiff-base diaxially substituted silicon phthalocyanines. In photochemical studies, the singlet oxygen quantum yields (Φ ∆ ) were determined as 0.43 for Si1a, 0.94 for Q-Si1a, 0.58 for S-Si1a, and 0.49 for B-Sia1. In sono-photochemical studies, the Φ ∆ values were reached to 0.67 for Si1a, 1.06 for Q-Si1a, 0.65 for S-Si1a, and 0.67 for B-Sia1. In addition, this study demonstrates the therapeutic efficacy of phthalocyanines synthesized as sensitizers on the PC3 prostate cancer cell line through in vitro experiments. The application of these treatment modalities exhibited notable outcomes, leading to a substantial decrease in cell viability within the PC3 prostate cancer cell line. These findings highlight the potential of utilizing these synthesized phthalocyanines as promising therapeutic agents for prostate cancer treatment., (© 2024. The Author(s).)

In the current study, we synthesized and characterized new BODIPY derivatives (1-4) having pyridine or thienyl-pyridine substituents at meso- position and 4-dibenzothienyl or benzo[b]thien-2-yl moieties at 2-,6- positions. We investigated fluorescence properties and the ability to form singlet oxygen. In addition, various biological activities of BODIPYs such as DPPH scavenging, DNA binding/cleavage ability, cell viability inhibition, antimicrobial activity, antimicrobial photodynamic therapy (aPDT) and biofilm inhibition properties were performed. BODIPY derivatives BDPY-3 (3) and BDPY-4 (4) have high fluorescence quantum yields as 0.50 and 0.61 and 1 O 2 quantum yields were calculated as 0.83 for BDPY-1 (1), 0.12 for BDPY-2 (2), 0.11 for BDPY-3 and 0.23 for BDPY-4. BODIPY derivatives BDPY-2, BDPY-3 and BDPY-4 displayed 92.54 ± 5.41%, 94.20 ± 5.50%, and 95.03 ± 5.54% antioxidant ability, respectively. BODIPY compounds showed excellent DNA chemical nuclease activity. BDPY-2, BDPY-3 and BDPY-4 also exhibited 100% APDT activity against E. coli at all tested concentrations. In addition to these, they demonstrated a highly effective biofilm inhibition activity against Staphyloccous aureus and Pseudomans aeruginosa. BDPY-4 showed the most effective antioxidant and DNA cleavage activity, while BDPY-3 exhibited the most effective antimicrobial and antibiofilm activity., (© 2023 American Society for Photobiology.)

To treat a life-threatening disease like cancer, photodynamic therapy (PDT) and sonodynamic therapy (SDT) methods were combined into sono-photodynamic therapy (SPDT) as an effective therapeutic solution. Each day, the usage of phthalocyanine sensitizers increases in the therapeutic applications as they have the ability to produce more reactive oxygen species. In this context, a new diaxially silicon phthalocyanine sensitizer, containing triazole and tert-butyl groups, was synthesized. After elucidating the structure of the complex with elemental analysis, FT-IR, UV-Vis, MALDI-TOF MS and 1 H NMR, its photophysical, photochemical and sono-photochemical properties were examined. When singlet oxygen generation capacity of the new synthesized silicon phthalocyanine complex was determined and compared among photochemical (PDT; Ф Δ  = 0.59 in DMSO, 0.44 in THF, 0.47 in toluene) and sonophotochemical (SPDT; Ф Δ  = 0.88 in dimethyl sulfoxide (DMSO), 0.60 in tetrahydrofuran (THF), 0.65 in toluene) methods, it can be said that the complex is a successful sono-photosensitizer that can be used as a good SPDT agent in vitro or in vivo future studies., (© 2023 The Authors. Photochemistry and Photobiology published by Wiley Periodicals LLC on behalf of American Society for Photobiology.)

A new BODIPY complex (C4) composed of meso- thienyl-pyridine substituted core unit diiodinated from 2- and 6- positions and distyryl moieties at 3- and 5- positions is synthesized. Nano-sized formulation of C4 is prepared by single emulsion method using poly(ε-caprolactone)(PCL) polymer. Encapsulation efficiency and loading capacity values of C4 loaded PCL nanoparticles (C4@PCL-NPs) are calculated and in vitro release profile of C4 is determined. The cytotoxicity and anti-cancer activity are conducted on the L929 and MCF-7 cell lines. Cellular uptake study is performed and interaction between C4@PCL-NPs and MCF-7 cell line is investigated. Anti-cancer activity of C4 is predicted with molecular docking studies and the inhibition property on EGFR, ERα, PR and mTOR are investigated for its anticancer properties. Molecular interactions, binding positions and docking score energies between C4 and EGFR, ERα, PR and mTOR targets are revealed using in silico methods. The druglikeness and pharmacokinetic properties of C4 are evaluated using the SwissADME and its bioavailability and toxicity profiles are assessed using the SwissADME, preADMET and pkCSM servers. In conclusion, the potential use of C4 as an anti-cancer agent is evaluated in vitro and in silico methods. Also, photophysicochemical properties are studied to investigate the potential of using Photodynamic Therapy (PDT). In photochemical studies, the calculated singlet oxygen quantum yield (Φ Δ ) value was 0.73 for C4 and in photopysical studies, the calculated fluorescence quantum yield Φ F value was 0.19 for C4., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

This study presents the synthesis of some metal {M = Zn(II), Lu(III), Si(IV)} phthalocyanines bearing chlorine and 2-(4-methylthiazol-5-yl) ethoxy groups at peripheral or axial positions. The newly synthesized metal phthalocyanines were characterized by applying FT-IR, 1 H NMR, mass, and UV-Vis spectroscopic approaches. Additionally, the surface of gold nanoparticles was modified with zinc(II) and silicon(IV) phthalocyanines. The resultant nanoconjugates were characterized using TEM images. Moreover, the effect of metal ions and position of substituent, and gold nanoparticles on the photochemical and sonophotochemical properties of the studied phthalocyanines was investigated. The highest singlet oxygen quantum yield was obtained for the lutetium phthalocyanine by applying photochemical and sonophotochemical methods. However, the linkage of the zinc(II) and silicon(IV) phthalocyanines to the surface of gold nanoparticles improved significantly their singlet oxygen generation capacities., (© TÜBİTAK.)

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., (© TÜBİTAK.)

Although the sonophotodynamic method has an effective therapeutic outcome for anticancer treatment compared with the photodynamic method, there are not enough related studies in the literature and this study aims to contribute to the development of sonophotodynamic studies. For this purpose, the Schiff base substituted silicon phthalocyanines were designed and synthesized as effective sensitizer candidates and the photophysicochemical and sonophotochemical features of the phthalocyanines were examined to increase singlet oxygen efficiency. The calculated Φ Δ values indicate that the contribution of substituent groups improved the production of singlet oxygen compared with silicon (IV) phthalocyanine dichloride (SiPcCI 2 ) and also the sonophotochemical applications increased the singlet oxygen yields. The Φ Δ values (Φ Δ  = 0.76 for axially bis-{4-[(E)-(pyridin-3-ylimino)methyl]phenol} substituted silicon (IV) phthalocyanine (2a), 0.68 for axially bis-4-[(E)-{[(pyridin-3-yl)methyl]imino}methyl]phenol substituted silicon (IV) phthalocyanine (2b) in photochemical study) reached to Φ Δ  = 0.98 for 2a, 0.94 for 2b in sonophotochemical study. This article will enrich the literature on increasing singlet oxygen yield., (© 2023 The American Society for Photobiology.)

In this study, Schiff base substituted phthalocyanine complexes (Zn1c, Zn2c) and their quaternized derivatives (Q-Zn1c, Q-Zn2c) were synthesized for the first time. Their structures have been characterized by FT-IR, 1 H-NMR, UV-Vis, mass spectrometry and elemental analysis as well as. The photophysicochemical properties (fluorescence, singlet oxygen and photodegradation quantum yield) of these novel complexes were investigated in dimethylsulfoxide (DMSO) for both non-ionic and quaternized cationic phthalocyanine complexes and in aqueous solution for quaternized cationic phthalocyanine complexes. Water soluble cationic phthalocyanine compounds gave good singlet oxygen quantum yield (0.65 for Q-Zn1c, 0.66 for Q-Zn2c in DMSO; 0.65 for Q-Zn2c in aqueous solution). The binding of Q-Zn1c and Q-Zn2c to BSA/DNA was studied by using UV-Vis and fluorescence spectroscopy and these. Studies indicate that the mechanism of BSA quenching by quaternized zinc(II) phthalocyanines was static quenching. Quaternized zinc(II) phthalocyanines interacted with ct-DNA by intercalation. Quaternized zinc(II) phthalocyanines caused a decrease in cell viability and triggered apoptotic cell death after PDT was applied at a concentration that did not have a toxic effect on their own. Q-Zn1c and Q-Zn2c mediated PDT reduced the activity of SOD, CAT, GSH while increased MDA level in the prostate cancer cells. Furthermore, expression of apoptotic proteins after PDT was examined. The results revealed that the synthesized water soluble quaternized zinc(II) phthalocyanine complexes (Q-Zn1c and Q-Zn2c) are promising potential photosensitizers for PDT., (© 2023. The Author(s), under exclusive licence to European Photochemistry Association, European Society for Photobiology.)

Background: Sonophotodynamic therapy (SPDT), a combination of photodynamic therapy (PDT) and sonodynamic therapy (SDT), may offer theraputic advantage. The therapeutic effects of sonodynamic, photodynamic, and sonophotodynamic of 5-(trifluoromethyl)-2-thiopyridine substituted silicon phthalocyanine (gy3) and its quaternized derivative (gy3q) were examined in vitro on prostate cancer using PC3 cells., Methods: The SDT, PDT and SPDT efficiency was determined by using MTT test.Apoptosis mechanism was evaluated by HOPI staining., Results and Discussions: According to MTT results, the phthalocyanines decreased cell viability when compared with a control group. Also, apoptosis measurement data represents that the phthalocyanines would produce much better therapeutic outcomes compare to PDT and SDT by utilizing SPDT. Further studies should be performed to understand the effectiveness of SPDT., Competing Interests: Conflicts of Declaration Interest There are no conflicts to declare., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Sono-photodynamic therapy, which show a very high therapeutic effect compared to photodynamic therapy, is a newer method for anticancer treatments. However, unlike Photodynamic therapy (PDT), the number of studies measuring the efficiency of singlet oxygen for the Sono-photodynamic therapy (SPDT) method is quite insufficient in the literature. Therefore, this study aimed to synthesis novel axially substituted silicon (IV) phthalocyanines containing imine groups with improved photochemical properties and then reported the efficiency of singlet oxygen by both of photochemical and sono-photochemical studies. According to the results, the substituent group increased the singlet oxygen yield of silicon (IV) phthalocyanine dichloride and the sono-photochemical effect increased the singlet oxygen yields (Φ Δ =0.35 for 2a, 0.69 for 2b in photochemical study, 0.78 for 2a, 0.97 for 2b in sono-photochemical study).This article may pave the way to achieve high singlet oxygen efficiency., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper, (Copyright © 2022 Elsevier B.V. All rights reserved.)

In this study, a series of peripherally and non-peripherally tetra-substituted metal-free and zinc(II) phthalocyanines were successfully prepared in good yields by cyclotetramerization of the phthalonitrile derivative bearing a tetraethylene glycol methyl ether group at 3- and 4- positions. All newly synthesized compounds were characterized using spectroscopic methods, such as FT-IR, NMR, mass and UV-Vis spectroscopy. To determine the therapeutic potential of the synthesized phthalocyanines, the effects of the substitution pattern (peripheral and non-peripheral) and central metal atom on the photophysicochemical properties were investigated. When comparing their singlet oxygen generation capabilities ( Φ Δ ), metallo-phthalocyanine derivatives with zinc (0.73 for 1b and 0.70 for 2b) showed higher singlet oxygen yield than metal-free derivatives (0.21 for 1a and 0.12 for 2a) in DMSO. The photodynamic therapy activities of the water-soluble phthalocyanines were tested via in vitro studies using the A253, FaDu (head and neck cancer cell lines), and HT29 (colon cancer) cell lines. The strongest photodynamic activity was found in 1b and 2b molecules with a metal core among the four molecules studied. The results suggested that the non-peripherally tetra-substituted 1b molecule was regarded as a suitable photodynamic therapy agent due to its light cytotoxicity and secondary impact induced by ROS production.

As thiazoles and fluorinated groups are well known as active species of hybrid pharmaceutical agents, this study aimed to evaluate the synergic effect of these groups on the biological features of phthalocyanines for the first time in the hope of discovering efficient pharmaceutical agents. Therefore, a new phthalonitrile derivative namely 4-(2-(4-methylthiazol-5-yl)ethoxy)-5-(4-(trifluoromethoxy)phenoxy)phthalonitrile (1) and its metal-free (2)/metal phthalocyanines (3-5) were prepared and characterized using various spectroscopic techniques. Solubility of new phthalocyanines (2-5) was examined in a series of polar and nonpolar solvents. Additionally, sono/photochemical methods were applied to examine the photophysical and sono/photochemical properties of new zinc phthalocyanine to measure its potential as a probable material for sono/photodynamic therapies. The antioxidant activities of compounds (1-5) were evaluated using the DPPH scavenging activity method and the highest radical scavenging activity was obtained 92.13% (200 mg L -1 ) for manganese phthalocyanine. All the phthalocyanines demonstrated high DNA nuclease activity, as well. The antimicrobial activities of compounds (1-5) were investigated using disk diffusion and microdilution methods. The phthalocyanines exhibited effective microbial cell inhibition activity against Escherichia coli (E. coli). Antimicrobial photodynamic therapy activity was investigated against E. coli by LED irradiation. Compounds (2-5) acted as photosynthesizers. Also, they displayed significant biofilm inhibition activity against Staphylococcus aureus (S. aureus) and Pseudomonas aeruginosa (P. aeruginosa)., (© 2021 American Society for Photobiology.)

The novel pyridine bearing schiff base substituted metal-free ( 9 ), zinc(II) phthalocyanine ( 10 ), and its quaternized derivative ( 11 ) were designed and synthesized. These phthalocyanines were fully characterized by spectroscopic methods (FT-IR, UV-Vis, MALDI-TOF, and 1 H NMR). The photo-physicochemical properties of these phthalocyanines were investigated in both DMSO and DMF for 10 and in both DMSO and aqueous solution for 11 . The addition of pyridine bearing Schiff base groups as peripheral ligands showed an improvement in the photophysical and photochemical properties. In addition, a spectroscopic investigation of the binding behavior of the water-soluble zinc (II) phthalocyanine complex to bovine serum albumin (BSA) was also studied in this work., (© TÜBİTAK.)

Photodynamic therapy (PDT) applications carried out with the assistance of ultrasound have attracted significant attention in recent years. The use of phthalocyanines, which are an important component as photosensitizers in PDT, is becoming more important day by day. In therapeutic applications, phthalocyanines can promote the production of reactive oxygen species. Motivated by this fact, the syntheses of metal-free ( 2 ), gallium ( 3 ), and indium ( 4 ) phthalocyanines have been achieved by substituting 4-(cinnamyloxy)phthalonitrile for the first time to evaluate their therapeutic applications. Additionally, photophysicochemical, sonophotochemical, and in vitro evaluations of phthalocyanines have been reported. To the best of our knowledge, this is the first study of the use of phthalocyanines with different metal ions as potential photosensitizers for sonophotodynamic therapy (SPDT) applications in gastric cancer cell lines. The results show that the quantum yield of the generation of singlet oxygen increased in sonophotochemical studies (Φ Δ = 0.55 ( 2 ), 0.85 ( 3 ), 0.96 ( 4 )), compared to photochemical studies (Φ Δ = 0.22 ( 2 ), 0.61 ( 3 ), 0.78 ( 4 )). The density functional theory (DFT) results are in good agreement with the experimental results and suggest increased reactivity of phthalocyanines 3 and 4 in various redox processes, thus implying their applicability and usefulness as potential therapeutic agents. These phthalocyanines are effective sensitizers for PDT, sonodynamic therapy (SDT), and SPDT against MKN-28 gastric cancer cell line in vitro. All three treatments decreased cell viability and induced apoptosis in the gastric cancer cell line. However, indium phthalocyanine ( 4 )-mediated SPDT was a more effective treatment modality compared to indium phthalocyanine ( 4 )-mediated PDT and SDT. Also, indium phthalocyanine ( 4 ) was found to be a more effective sensitizer to activate apoptosis compared to the other phthalocyanines. To sum up, phthalocyanine-mediated SPDT enhances the cytotoxic effect on gastric cancer cells more than the effect of SDT or PDT alone.

This study presents the preparation of a novel tetra-substituted phthalonitrile (1), namely, 3,6-bis(hexyloxy)-4,5-bis(4-(trifluoromethoxy)phenoxy)phthalonitrile (1) and its metal-free (2)/metal {M = Zn (3), Cu (4), Co (5), Lu(CH 3 COO) (6), Lu (7)} phthalocyanines. A series of various spectroscopic methods (UV-vis, FT-IR, mass, and 1 H NMR spectroscopy) were performed for the characterization of the newly synthesized compounds. The potential of compounds 2, 3, and 6 as photosensitizing materials for photodynamic and sonophotodynamic therapies was evaluated by photophysical, photochemical, and sonochemical methods. The highest singlet quantum yields were obtained for the zinc phthalocyanine derivative 3 by performing photochemical and sonochemical methods. In addition, several biological activities of the new compounds 1-7 were investigated. The newly synthesized phthalocyanines exhibited excellent DPPH scavenging activity and also DNA nuclease activity. The antimicrobial activity of the new compounds was evaluated by the disc diffusion assay. Effective microbial cell viability inhibition was observed with phthalocyanine macromolecules. The photodynamic antimicrobial therapy of the phthalocyanines showed 100% bacterial inhibition when compared to the control. They also exhibited significant biofilm inhibition activity against S. aureus and P. aeruginosa . These results indicate that new phthalocyanines are promising photodynamic antimicrobial therapies for the treatment of infectious diseases.

This study presents the synthesis of a series of new tetra-substituted phthalocyanines bearing 3,5-bis(trifluoromethyl)phenoxy groups at non-peripheral positions. The resulting macromolecules were characterized by performing different spectroscopic methods including 1H NMR, UV-Vis, FT-IR, and mass spectroscopy. In this study, the synergistic effect of phthalocyanines used as colorants in ink formulas with other chemicals available was probed for the first time. The synergistic effect of methyl laurate on the biological and antioxidant activities of the compounds (2-5) was investigated. Moreover, the therapeutic properties of the complexes (3, 6, and 7) were investigated using photochemical methods. Upon comparison, complex 7 (ΦΔ = 0.42) was found to be more effective than complex 6 (ΦΔ = 0.40) and complex 3 (ΦΔ = 0.27) in terms of producing singlet oxygen. The results confirmed that the heavy atom effect improves the therapeutic effects.

This study presents the preparation of a new phthalonitrile derivative namely 3-(4-(trifluoromethoxy)thiophenoxy)phthalonitrile (1) and a series of its metallated phthalocyanines (M = Zn (II) (1a) and In(III) (1b)). In addition, the peripheral analog of the indium phthalocyanine chloride (2b) was newly synthesized. Characterization of the resulting compounds was carried out by utilizing various spectroscopic methods such as FT-IR, 1 H NMR and UV-Vis spectroscopy. The influence of concentration on aggregation properties of compound 1a was investigated at different concentrations of DMSO. The effect of solvent type on aggregation properties of compound 1a was studied, as well. According to the referred procedures, the macrocyclic molecules (2a, 3a-b and 4a-b) were prepared. The effect of some parameters including metal ion, the position of the substituent and the connected atom (oxo or thio) on photochemical and photophysical features of compounds (1a-b, 2a-b, 3a-b, and 4a-b) was studied for evaluation of their potential as a photosensitizer in PDT, comparatively. The highest singlet oxygen quantum yields (Φ Δ  = 0.71 for 1a and 0.80 for 2b) were obtained for complexes 1a and 1b in DMSO. The photophysical and photochemical features of the studied macromolecules are therefore suitable for photodynamic therapy applications., (© 2020 American Society for Photobiology.)

This study reports the 3 new phthalonitrile derivatives, namely 4, 5 Bis-[4-(4-bromophenoxy) phenoxy] phthalonitrile ( 1 ), 4,5 Bis-[4-(4-chlorophenoxy) phenoxy]phthalonitrile ( 2 ), and 4, 5 Bis[4-(4-fluorophenoxy) phenoxy] phthalonitrile ( 3 ). Their octa-substituted zinc phthalocyanines ( 4 , 5 , 6 ) are reported for the first time in this study. The resulting compounds were characterized by utilizing some spectroscopic methods, such as UV-Vis, 1HNMR, FT-IR spectroscopy, as well as mass spectraand elemental analysis. To show photosynthesizer's potential, emission (F F ), singlet oxygen (1O2), and photodegradation quantum yields (F∆, Fd) of octa-peripherally phthalocyanines (Pcs) were performed in the solutions, such as biocompatible solvent DMSO (dimethyl sulfoxide) as well as DMF (dimethylformamide) and THF (tetrahydrofuran). Solvent and octa-peripherally binding effect of the halogen (Br, Cl, F) terminated phenoxy-phenoxy groups on phthalocyanine rings for photophysicochemical properties ( 4 , 5 , and 6 ) were compared with the tetra-peripherally and tetra nonperipherally substituted derivatives. The new dyes ( 4 to 6 ) may be evaluated in photodynamic therapy (PDT) of cancer as photosensitizers due to efficient 1O2 from 0.55 to 0.75., Competing Interests: CONFLICT OF INTEREST: none declared, (Copyright © 2020 The Author(s).)

The new free and nickel phthalocyanine derivatives, tetrakis [(2-formylphenoxy)-phthalocyanine (4), tetrakis [(2-formylphenoxy)-phthalocyaninato]nickel(II) (5) have been synthesized via de-protection of tetra acetal-substituted phthalocyanines in acetic acid/FeCl3 system. The starting phthalocyanines, tetrakis [(2-(1,3-dioxolan-2-yl)phenoxy)-phthalocyanine (2) and tetrakis [(2-(1,3-dioxolan-2-yl)phenoxy)-phthalocyaninato]nickel (3), were prepared by the tetramerization of 4-(2-(1,3-dioxolan-2-yl) phenoxy) phthalonitrile (1). The new compounds have been characterized by the combination of FT-IR, (1)H NMR, UV-Vis, Mass spectra and elemental analysis. Compound 1 crystallizes in the Orthorhombic, space group Pbca with a = 9.2542 (4) Å, b = 13.3299 (5) Å, c = 23.2333 (11) Å, and Z = 8. Compound 1 is built up from two planar groups (phthalonitrile and phenoxy), with a dihedral angle of 69.693(36)° between them and non-planar dioxolane group. We report a combined experimental and theoretical study on molecule 1, as well. Geometric, spectroscopic and electronic properties of compound 1 has been calculated using B3LYP method and 6-311++G(dp) basis set. Fluorescence spectroscopy was applied to record the photoluminescence spectra of the prepared phthalocyanines and the photophysical and photochemical properties were examined in DMSO.

A new highly fluorescent difluoroboradipyrromethene (BODIPY) dye (4) bearing an phthalonitrile group at meso-position of the chromophoric core has been synthesized starting from 4-(4-meso-dipyrromethene-phenoxy)phthalonitrile (3) which was prepared by the oxidation of 4-(2-meso-dipyrromethane-phenoxy)phthalonitrile (2). The structural, electronic and photophysical properties of the prepared dye molecule were investigated. The final product exhibit noticeable spectroscopic properties which were examined by its absorption and fluorescence spectra. The original compounds prepared in the reaction pathway were characterized by the combination of FT-IR, (1)H and (13)C NMR, UV-vis and MS spectral data. It has been calculated; molecular structure, vibrational frequencies, (1)H and (13)C NMR chemical shifts and HOMO and LUMO energies of the title compound by using B3LYP method with 6-311++G(dp) basis set, as well. The final product (4) was obtained as single crystal which crystallized in the triclinic space group P-1 with a = 9.0490 (8) Å, b = 10.5555 (9) Å, c = 11.7650 (9) Å, α = 77.024 (6)°, β = 74.437 (6)°, γ = 65.211 (6)° and Z = 2. The crystal structure has intermolecular C-H···F weak hydrogen bonds. The singlet oxygen generation ability of the dye (4) was also investigated in different solvents to determine of using in photodynamic therapy (PDT).

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 (ΦΔ) and photodegradation quantum yield (Φd)) 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 (ΦΔ=0.41, 0.39)., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Electrochemical and in situ spectroelectrochemical behaviors and electrocatalytic reduction of molecular oxygen with titanyl phthalocyanines (TiPc) bearing 3,4-(methylenedioxy)-phenoxy substituents were performed in aprotic solvents. Multi electrons and metal-based and ring-based redox processes of TiPcs indicate their possible electrocatalytic activity toward many target species. Different numbers and positions of the substituents of the complexes affect the peaks' character and assignment of the processes. The presence of O2 in the electrolyte system influences the electrochemical and spectral responses of TiPcs. Electrochemical and in situ spectroelectrochemical analysis indicates interaction of molecular oxygen with TiPcs and these interaction mechanisms depend on both the substituent environments of the complexes and the electrolyte system. Langmuir-Blodgett films of the complexes also catalyze molecular oxygen in aqueous media, which is a desired property for their practical application.

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, (1)H 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 © 2011 Elsevier B.V. All rights reserved.)