Poly(oxanorbornene)s bearing triphenylphosphonium and PEGylated zinc(<scp>ii</scp>) phthalocyanine with boosted photobiological activity and singlet oxygen generation

Ahmetali, Erem; Galstyan, Anzhela; Süer, N. Ceren; Eren, Tarık; Şener, M. Kasım

doi:10.1039/d2py01297a

Cited by 4 publications

(2 citation statements)

References 56 publications

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“…The aromatic protons belonging to phthalonitrile group were observed in the range of 8.7-8.1 ppm, as could be expected, while the protons belonging to the Chol group were observed between 5.3 and 0.7 ppm (Figure 3). Further, all relevant bonds are identified in Figure 3, and both the respective positions and integral ratios of the characteristic peaks were in good agreement with previous reports [52][53][54]. Regarding Chol-ZnPc, it was prepared by tetramerization reaction of Chol-phthalonitrile and ZnCl 2 .…”

Section: Resultssupporting

confidence: 88%

Graphene Oxide/Cholesterol-Substituted Zinc Phthalocyanine Composites with Enhanced Photodynamic Therapy Properties

Erden

2023

Materials

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In the present work, cholesterol (Chol)-substituted zinc phthalocyanine (Chol-ZnPc) and its composite with graphene oxide (GO) were prepared for photodynamic therapy (PDT) applications. Briefly, Chol-substituted phthalonitrile (Chol-phthalonitrile) was synthesized first through the substitution of Chol to the phthalonitrile group over the oxygen bridge. Then, Chol-ZnPc was synthesized by a tetramerization reaction of Chol-phthalonitrile with ZnCl2 in a basic medium. Following this, GO was introduced to Chol-ZnPc, and the successful preparation of the samples was verified through FT-IR, UV–Vis, 1H-NMR, MALDI-TOF MS, SEM, and elemental analysis. Regarding PDT properties, we report that Chol-ZnPc exhibited a singlet oxygen quantum yield (Φ∆) of 0.54, which is slightly lower than unsubstituted ZnPc. Upon introduction of GO, the GO/Chol-ZnPc composite exhibited a higher Φ∆, about 0.78, than that of unsubstituted ZnPc. Moreover, this enhancement was realized with a simultaneous improvement in fluorescence quantum yield (ΦF) to 0.36. In addition, DPPH results suggest low antioxidant activity in the composite despite the presence of GO. Overall, GO/Chol-ZnPc might provide combined benefits for PDT, particularly in terms of image guidance and singlet oxygen generation.

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Section: Resultssupporting

confidence: 88%

Graphene Oxide/Cholesterol-Substituted Zinc Phthalocyanine Composites with Enhanced Photodynamic Therapy Properties

Erden

2023

Materials

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“…Among the numerous classes of molecular photosensitizers used in anti-cancer photodynamic therapy (PDT), phthalocyanines have the intrinsic advantage to absorb at far-red wavelengths in the first phototherapeutic window, hence offering a deep penetration of light into biological tissues while avoiding the excitation of endogenous chromophores. Together with their chemical versatility, this makes phthalocyanines ideal photosensitizers for PDT. , To improve phthalocyanines’ biocompatibility, many substitution patterns have been used to make them water soluble, and various drug delivery systems have been developed for poorly water soluble or organosoluble phthalocyanines. , Phthalocyanines can be covalently combined into water-dispersible nanoparticles of various types, such as organosilica nanoparticles, polymeric materials, − and targeting units, such as nanobodies. , …”

Section: Introductionmentioning

confidence: 99%

Comparing PVP and Polymeric Micellar Formulations of a PEGylated Photosensitizing Phthalocyanine by NMR and Optical Techniques

et al. 2023

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Phthalocyanines are ideal candidates as photosensitizers for photodynamic therapy (PDT) of cancer due to their favorable chemical and photophysical properties. However, their tendency to form aggregates in water reduces PDT efficacy and poses challenges in obtaining efficient forms of phthalocyanines for therapeutic applications. In the current work, polyvinylpyrrolidone (PVP) and micellar formulations were compared for encapsulating and monomerizing a water-soluble zinc phthalocyanine bearing four non-peripheral triethylene glycol chains (Pc1). 1H NMR spectroscopy combined with UV–vis absorption and fluorescence spectroscopy revealed that Pc1 exists as a mixture of regioisomers in monomeric form in dimethyl sulfoxide but forms dimers in an aqueous buffer. PVP, polyethylene glycol castor oil (Kolliphor RH40), and three different triblock copolymers with varying proportions of polyethylene and polypropylene glycol units (termed P188, P84, and F127) were tested as micellar carriers for Pc1. 1H NMR chemical shift analysis, diffusion-ordered spectroscopy, and 2D nuclear Overhauser enhancement spectroscopy was applied to monitor the encapsulation and localization of Pc1 at the polymer interface. Kolliphor RH40 and F127 micelles exhibited the highest affinity for encapsulating Pc1 in the micellar core and resulted in intense Pc1 fluorescence emission as well as efficient singlet oxygen formation along with PVP. Among the triblock copolymers, efficiency in binding and dimer dissolution decreased in the order F127 > P84 > P188. PVP was a strong binder for Pc1. However, Pc1 molecules are rather surface-attached and exist as monomer and dimer mixtures. The results demonstrate that NMR combined with optical spectroscopy offer powerful tools to assess parameters like drug binding, localization sites, and dynamic properties that play key roles in achieving high host–guest compatibility. With the corresponding adjustments, polymeric micelles can offer simple and easily accessible drug delivery systems optimizing phthalocyanines’ properties as efficient photosensitizers.

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Zinc Phthalocyanine Core‐First Star Polymers Through Nitroxide Mediated Polymerization and Nitroxide Exchange Reaction

Ahmetali,

Kocaarslan,

Bräse

et al. 2024

Macromol. Rapid Commun.

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Nitroxide‐mediated polymerization (NMP) and nitroxide exchange reaction (NER) are very efficient methodologies that require only suitable alkoxyamine derivatives and create different polymeric architectures in a controlled manner. Herein, the synthesis of star polymers containing TEMPO‐substituted symmetric zinc phthalocyanine (ZnPc) is presented via NMP and NER. Moreover, linear polymer formation is conducted in a single arm on TEMPO‐substituted asymmetric ZnPc to elucidate the properties of star polymers. All linear and star polymers are characterized by FT‐IR, UV–vis, fluorescence, GPC, NMR, and EPR techniques. The results show that the proposed reactions are capable of forming controlled star‐shaped polymers. The increasing arm number (from a single to four arms) results in variable dispersity values (Đ) (1.2–3) due to different arm lengths, especially in NMP. However, this difficulty has been overcome via NER, and star polymers have been successfully synthesized with relatively low molecular weight (30 K > 10 K) and low dispersity (1.2–1.9). The results clearly indicate that while styrene and 4‐vinyl benzyl chloride monomers are introduced to the structure equally, star polymers with phthalocyanine can be synthesized in a controlled manner, and their quarternized derivatives have the potential to be effective as photoactive agents in photodynamic therapy.

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Poly(oxanorbornene)s bearing triphenylphosphonium and PEGylated zinc(ii) phthalocyanine with boosted photobiological activity and singlet oxygen generation

Abstract: Polymers containing suitable photosensitizers are a promising choice for light-guided management of perceived problems associated with microbial infections linked to resistant bacteria and biofilms. Ring-opening metathesis polymerization (ROMP) is an...

Cited by 4 publications

References 56 publications

Graphene Oxide/Cholesterol-Substituted Zinc Phthalocyanine Composites with Enhanced Photodynamic Therapy Properties

Graphene Oxide/Cholesterol-Substituted Zinc Phthalocyanine Composites with Enhanced Photodynamic Therapy Properties

Comparing PVP and Polymeric Micellar Formulations of a PEGylated Photosensitizing Phthalocyanine by NMR and Optical Techniques

Zinc Phthalocyanine Core‐First Star Polymers Through Nitroxide Mediated Polymerization and Nitroxide Exchange Reaction

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