Journal of Porphyrins and Phthalocyanines

Two fluorinated meso-C₆F₅-corroles (5,15-bis(pentafluorophenyl)-10-(phenyl)corrole and 5,15-bis(pentafluorophenyl)-10-(1-pyrenyl)corrole) were biologically evaluated in terms of binding affinity to human serum albumin (HSA) and calf-thymus DNA (CT-DNA) via multiple spectroscopic techniques under physiological conditions combined with molecular docking calculations. The HSA:corrole interaction is spontaneous and moderate via static binding, disturbing both secondary and tertiary albumin structures at high fluorinated corrole concentrations. The competitive binding studies indicated positive cooperativity or allosteric activation, while molecular docking calculations suggested that both fluorinated corroles bind preferentially inside subdomains IIA and IB (sites I and III, respectively). The experimental CT-DNA binding assays indicated that fluorinated corroles interact spontaneously by non-classical modes in the minor groove of the CT-DNA strands via static fluorescence quenching mechanism. Molecular docking results also showed the minor groove as the main binding site for CT-DNA. Overall, the pyrene moiety increased the interaction with HSA and CT-DNA, which is probably due to the planarity and volume that favors the pyrene unit to be buried inside the biomacromolecule pockets.

The development of synthetic strategies for functional building units plays a central role in supramolecular chemistry. Both porphyrin and crown ethers have attracted the attention of researchers worldwide owing to their unique properties. It is envisioned that the integration of the two molecules will result in hybrid materials with potential applications in many fields. In the present study, a new porphyrin derivative 3 appended with four 18-crown-6 (18C6) ether moieties was synthesized through the Suzuki-Miyaura coupling of boronic ester porphyrin 1 and 4-bromobenzo-18-crown-6 2 in 80% yield. Porphyrin 3 was fully characterized by ¹H/${}^{13}$C NMR spectroscopy and high resolution mass spectrometry. The tendency of the 18C6 to form host-guest complexes with ammonium cations was exploited to assemble cation responsive hybrid material of porphyrin 3 and ammonium immobilized mesoporous silica nanoparticles (MSNs). Furthermore, the potential application of the 3/MSNs conjugate as a cation-responsive drug delivery vehicle was investigated in solution by UV-vis and fluorescence spectroscopies.

The main challenge in the cancer treatment is the on-target drug delivery to the affected cells. Various therapies have been designed to target the affected cells efficiently but still the success is awaited. An iron and cobalt nanocomposite for the effective drug delivery to target cells was designed. The photodynamic effect of anticancer drugs loaded with iron oxide and cobalt ferrite nanomaterials coated with polyvinyl alcohol (PVA) was studied. The iron oxide nanoparticles (IONPs) and cobalt ferrite (CF) NPs without the loaded drugs were characterized by UV, XRD, FTIR, SEM and EDX techniques. The photodynamic effect of the photosensitizer, doxorubicin, and dacarbazine loaded nanomaterials were screened against human rhabdomyosarcoma (RMS) cells after incubation for 3 h, 24 h, and 48 h using MTT assay. The combination of photodynamic therapy (PDT) with chemo drugs is studied over different doses. When RMS cells were exposed to nanomaterials loaded with chemo drugs and PDT alone, it resulted in less cell killing compared to chemo drugs followed by PDT. These results revealed that in the case of combined treatment (combination therapy) the cell viability decreases as compared to individual treatment (monotherapy). The in vitro studies showed positive results which give a new pathway for the in vivo studies.

TEG-Pc, a Zn(II) phthalocyanine tetra substituted in non-peripheral position by tetraethylene glycol chains, proved to have good efficiency during in vitro photodynamic experiments. Its in vivo phototoxic effects have been investigated in tumor-bearing Wistar albino rats at an enzymatic level. The evolution of different oxidative markers are reviewed 6 h after the treatment.

Magnesium diethynylporphyrin derivatives with strong near-infrared absorption were obtained. These derivatives possess electron rich units directly introduced to the porphyrin core. The electron rich units caused strong absorption on the near-infrared region due to an intramolecular charge transfer. Theoretical calculation also proved that the derivatives showed large oscillator strength at the Q band. As a donor material, such large absorption coefficient in the range of long wavelength region is a desirable characteristic for organic solar cells. Organic photovoltaic devices using these diethynylporphyrin derivatives gave a PCE of 2.91% in optimal conditions.

In the present work, a number of chlorophyll $a$ derivatives were synthetized with galactose fragments with an ester bond between macrocycle and carbohydrate fragments. It showed that synthesized compounds fluoresce intensely inside HeLa cells, which enable these compounds to be considered as potential diagnostic agents and indicates their ability to remain in the cell in an unassociated photoactive state — a necessary condition for the realization of a photodynamic action. It was determined that while all conjugates had comparable photoinduced toxicities, the conjugate with phorbin macrocycle fragment had a much lower dark toxicity, which corresponds to the trends noted earlier. In terms of a therapeutic window, conjugate significantly exceeds similar derivatives of chlorin $e_6$ and is the most promising for further research.

The interaction of meso-tetra-($N$-methyl-3-pyridyl)bacteriochlorin tetra 4-methylbenzenesulfonate, meso-tetra-($N$-methyl-4-pyridyl)porphine tetraiodide and meso-tetra-($N$-methyl-3-pyridyl)porphine tetraiodide with protein was studied. The localization of macrocycles in the protein and their influence on the processes of protein aggregation were established. The aggregation process is initiated by the transition of alpha structures into beta folds, caused by the binding of porphyrins at the sites of protein IB and IIA. The complexes were irradiated with blue and green light. The data obtained showed that by varying the intensity of the light exposure, one can influence the shift of the aggregation equilibrium, obtaining predominantly monomeric or aggregated structures. Thus, photoexposure can be used as an alternative method of treating diseases caused by amyloidosis and for regulating the state of the protein in the pharmacological preparations.

In this study, zinc phthalocyanine (ZnPc) was encapsulated in liposomes (Phosphatidylcholine (PC) from soybean lecithin (95% phosphatidylcholine, 5% lysophosphatidylcholine), and phosphatidic acid) obtained by a reverse-phase evaporation method. Liposomes were characterized and cytotoxicity and phototoxicity assays were performed using mouse embryo fibroblast (NIH3T3) and human breast cancer (MDAMB231), respectively. ZnPc was successfully encapsulated in liposomes ($>$80%), presenting single populations with sizes of $\sim$300 nm and negative zeta potential (-35 to -40 mV). The release profile at different pH presented a biphasic release controlled by the Fickian diffusion mechanism. The cytotoxicity assays carried out on NIH3T3 cells showed that the liposomes provided good protection for ZnPc, and did not affect the viability of non-cancerous cells. In contrast, free ZnPc significantly reduced non-cancerous cell viability at higher concentrations. ZnPc loaded in liposomes ensured a higher phototoxic effect on the MDAMB231 cells at all concentrations tested when exposed to low light dose.

An approach for the possible production of novel bimetallic self-doped porphyrin-based compounds of potential interest in material science is reported. Heating Cu(II)tetraphenylporphyrin (TPPCu) with chromocene at 120°C in benzonitrile affords the crystalline multimetal porphyrin system TPPCu/TPPCr in good yield. The X-ray single crystal structural analysis reveals a random distribution of TPPCu and TPPCr, with a Cu:Cr ratio of 71(2):29(2)%. Exploratory DFT calculations of TPPCu/TPPCr indicate little if any electron transfer. In contrast, calculations of a hypothetical cationic TPPCu/TPPRu system indicates the possibility of self-doping.

This article has been retracted. For details, please refer to the Retraction Notice published in Vol.25, No.2 (2021).

This article has been retracted. For details, please refer to the Retraction Notice published in Vol.25, No.2 (2021).