Microwave-assisted synthesis, electrochemistry and spectroelectrochemistry of phthalocyanines bearing tetra terminal-alkynyl functionalities and click approach

Koyun, Ozge; Gördük, Semih; Keskin, Bahadır; Çetinkaya, Ahmet; Koca, Atıf; Avcıata, Ulvi

doi:10.1016/j.poly.2016.03.019

Cited by 27 publications

(10 citation statements)

References 59 publications

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“…Especially phthalocyanines (Pc), second- and third-generation photosensitizers, have a lot of advantages in PDT applications because of their superior absorption in the phototherapeutic window . In addition, their chemical structure is easily modified by replacing central metals and adding peripheral and nonperipheral substituents. − These changes allow to easily adjust chemical and physical properties, pharmacokinetics, and biodistributions of phthalocyanines …”

Section: Introductionmentioning

confidence: 99%

Ultrasound versus Light: Exploring Photophysicochemical and Sonochemical Properties of Phthalocyanine-Based Therapeutics, Theoretical Study, and In Vitro Evaluations

Güzel

Atmaca

Kuznetsov

et al. 2022

ACS Appl. Bio Mater.

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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.

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Section: Introductionmentioning

confidence: 99%

Ultrasound versus Light: Exploring Photophysicochemical and Sonochemical Properties of Phthalocyanine-Based Therapeutics, Theoretical Study, and In Vitro Evaluations

Güzel

Atmaca

Kuznetsov

et al. 2022

ACS Appl. Bio Mater.

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“…Nevertheless, it still often requires an organic base, commonly 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU), to catalyze the reagent tetramerization and reaction media such as alkyl alcohols (pentanol, hexanol), dimethylaminoethanol (DMAE) nitrobenzene, chlorobenzene, quinoline and α-chloronaphthalene [ 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 ], most of which are non-environmentally friendly. Given their extreme technological importance, many unconventional synthetic approaches have been studied and developed in parallel with their applications to increase their yields and sustainability while reducing their production cost, such as (i) microwave-assisted [ 22 ] and UV-assisted [ 23 , 24 ] processes, which are usually much faster and cleaner than their “standard” counterparts but requiring specific instrumentation and lacking scalability, and (ii) room-temperature reactions promoted by strong organic bases such as lithium diisopropylamide (LDA) [ 25 ] and pre-formed lithium alcoholate solutions [ 26 ]. With a view to increase the sustainability of the phthalocyanine synthesis on the lab scale, we systematically studied the effect of solvent and base replacement on the yield and cost of the macrocyclization reaction of phthalonitrile and 4- tert -butylphthalonitile templated by three first-transition metal ions: Co(II), Cu(II) and Zn(II).…”

Section: Introductionmentioning

confidence: 99%

Sustainable Approaches to the Synthesis of Metallophthalocyanines in Solution

et al. 2021

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This work aims to investigate more sustainable reaction conditions for the synthesis of metallophthalocyanines. Anisole, glycerol and their mixtures have been investigated as reaction media for the tetramerization of phthalonitriles. Acetates of three divalent first-transition metal cations, Co(II), Cu(II) and Zn(II), were used and several bases were tested, depending on the chosen substrates and reaction conditions, with a view to making the whole process more sustainable while ensuring its scalability. Unsubstituted phthalocyanines were synthesized to analyze the behavior of the different metal ions in terms of reactivity in the new reaction media, resulting in a general Cu > Co > Zn trend, while the nonpolar tetra-tert-butyl substitution was investigated to evaluate the synthesis of soluble derivatives in the new conditions. Furthermore, the potassium hydroxide (KOH)-aided statistical synthesis of the unsymmetrical 9(10), 16(17), 23(24)-tri-tert-butyl-2-iodophthalocyaninato zinc(II), starting from 4-tert-butylphthalonitrile and 4-iodophthalonitrile in a glycerol/anisole mixture, proceeded with a satisfactory 26% yield. Our results provide insights into the investigation of new reaction environments and the understanding of their strengths and weaknesses, with a view to further increasing the sustainability of the synthesis of metallomacrocycles with high added value while lowering their production cost.

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“…UV-Vis spectroscopy is thought to be the basic method to verify the formation of phthalocyanines. The phthalocyanine compounds show two main electronic transitions named as Q band (600-700 nm in the visible region), assigned to the - * transition from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO) of the Pc ring, and B band (300-350 nm in the UV region), resulting from the deeper - * transitions [20][21][22]. The UV spectra of the metallophthalocyanines ( -) display intense Q band at 675 nm for , 663 nm for , 671 nm for , Journal of Chemistry and 675 nm for in THF.…”

Section: Synthesis and Characterization Ofmentioning

confidence: 99%

Synthesis of Peripherally Tetrasubstituted Phthalocyanines and Their Applications in Schottky Barrier Diodes

Gördük

Koyun

Avcıata

et al. 2017

Journal of Chemistry

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New metal-free and metallophthalocyanine compounds (Zn, Co, Ni, and Cu) were synthesized using 2-hydroxymethyl-1,4-benzodioxan and 4-nitrophthalonitrile compounds. All newly synthesized compounds were characterized by elemental analysis, FT-IR, UV-Vis, 1 H-NMR, MALDI-TOF MS, and GC-MS techniques. The applications of synthesized compounds in Schottky barrier diodes were investigated. Ag/Pc/p-Si structures were fabricated and charge transport mechanism in these devices was investigated using dc technique. It was observed from the analysis of the experimental results that the charge transport can be described by Ohmic conduction at low values of the reverse bias. On the other hand, the voltage dependence of the measured current for high values of the applied reverse bias indicated that space charge limited conduction is the dominant mechanism responsible for dc conduction. From the observed voltage dependence of the current density under forward bias conditions, it has been concluded that the charge transport is dominated by Poole-Frenkel emission.

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Microwave-assisted synthesis, electrochemistry and spectroelectrochemistry of phthalocyanines bearing tetra terminal-alkynyl functionalities and click approach

Cited by 27 publications

References 59 publications

Ultrasound versus Light: Exploring Photophysicochemical and Sonochemical Properties of Phthalocyanine-Based Therapeutics, Theoretical Study, and In Vitro Evaluations

Ultrasound versus Light: Exploring Photophysicochemical and Sonochemical Properties of Phthalocyanine-Based Therapeutics, Theoretical Study, and In Vitro Evaluations

Sustainable Approaches to the Synthesis of Metallophthalocyanines in Solution

Synthesis of Peripherally Tetrasubstituted Phthalocyanines and Their Applications in Schottky Barrier Diodes

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