Thien-2-yl substituted chlorins as photosensitizers for photodynamic therapy and photodynamic antimicrobial chemotherapy
- Babu, Balaji, Sindelo, Azole, Mack, John, Nyokong, Tebello
- Authors: Babu, Balaji , Sindelo, Azole , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190578 , vital:45007 , xlink:href="https://doi.org/10.1016/j.dyepig.2020.108886"
- Description: The synthesis and characterization of meso-tetra(thien-2-yl)chlorin (1) and meso-tetra(5-bromothien-2-yl)chlorin (2) is reported. These dyes have red-shifted absorption maxima compared to those of the analogous meso-tetraphenylchlorin (3). 1 and 2 have Q bands at 660 and 664 nm, respectively, singlet oxygen quantum yields of 0.60 and 0.64 and exhibit good photostability. The triplet states were found to have lifetimes of 8.6 μs in N2 purged DMF. Time-dependent cellular uptake of chlorins reached a maximum in MCF-7 cancer cells after 12 h. Upon irradiation with a Thorlabs M660L3 LED (280 mW cm−2), 2 exhibited better photocytotoxicity with an IC50 value of 2.7 μM against MCF-7 cells. The 2ʹ,7ʹ-dichlorodihydrofluorescein diacetate (DCFDA) assay provided evidence for intracellular generation of reactive oxygen species. Photodynamic inactivation of bacteria by the chlorins was also studied. 2 exhibits better activity with log reduction values of 7.42 and 8.34 towards Staphylococcus aureus and Escherichia coli, respectively, under illumination for 60 min at 660 nm with a Thorlabs M660L3 LED (280 mW cm−2). These results demonstrate that 2 is a promising candidate for future in vivo experiments and merits further in-depth investigation.
- Full Text:
- Date Issued: 2021
- Authors: Babu, Balaji , Sindelo, Azole , Mack, John , Nyokong, Tebello
- Date: 2021
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/190578 , vital:45007 , xlink:href="https://doi.org/10.1016/j.dyepig.2020.108886"
- Description: The synthesis and characterization of meso-tetra(thien-2-yl)chlorin (1) and meso-tetra(5-bromothien-2-yl)chlorin (2) is reported. These dyes have red-shifted absorption maxima compared to those of the analogous meso-tetraphenylchlorin (3). 1 and 2 have Q bands at 660 and 664 nm, respectively, singlet oxygen quantum yields of 0.60 and 0.64 and exhibit good photostability. The triplet states were found to have lifetimes of 8.6 μs in N2 purged DMF. Time-dependent cellular uptake of chlorins reached a maximum in MCF-7 cancer cells after 12 h. Upon irradiation with a Thorlabs M660L3 LED (280 mW cm−2), 2 exhibited better photocytotoxicity with an IC50 value of 2.7 μM against MCF-7 cells. The 2ʹ,7ʹ-dichlorodihydrofluorescein diacetate (DCFDA) assay provided evidence for intracellular generation of reactive oxygen species. Photodynamic inactivation of bacteria by the chlorins was also studied. 2 exhibits better activity with log reduction values of 7.42 and 8.34 towards Staphylococcus aureus and Escherichia coli, respectively, under illumination for 60 min at 660 nm with a Thorlabs M660L3 LED (280 mW cm−2). These results demonstrate that 2 is a promising candidate for future in vivo experiments and merits further in-depth investigation.
- Full Text:
- Date Issued: 2021
Methodological Survey of Simplified TD-DFT Methods for Fast and Accurate Interpretation of UV−Vis−NIR Spectra of Phthalocyanines
- Martynov, Alexander G, Mack, John, May, Aviwe K, Nyokong, Tebello, Gorbunova, Yulia G, Tsivadze, Aslan Yu
- Authors: Martynov, Alexander G , Mack, John , May, Aviwe K , Nyokong, Tebello , Gorbunova, Yulia G , Tsivadze, Aslan Yu
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186915 , vital:44547 , xlink:href="https://doi.org/10.1021/acsomega.8b03500"
- Description: A methodological survey of density functional theory (DFT) methods for the prediction of UV−visible (vis)−near-infrared (NIR) spectra of phthalocyanines is reported. Four methods, namely, full time-dependent (TD)-DFT and its Tamm−Dancoff approximation (TDA), together with their simplified modifications (sTD-DFT and sTDA, respectively), were tested by using the examples of unsubstituted and alkoxy-substituted metal-free ligands and zinc complexes. The theoretical results were compared with experimental data derived from UV−visible absorption and magnetic circular dichroism spectroscopy. Seven popular exchange-correlation functionals (BP86, B3LYP, TPSSh, M06, CAM-B3LYP, LC-BLYP, and ωB97X) were tested within these four approaches starting at a relatively modest level using 6-31G(d) basis sets and gas-phase BP86/def2-SVP optimized geometries. A gradual augmentation of the computational levels was used to identify the influence of starting geometry, solvation effects, and basis sets on the results of TD-DFT and sTD-DFT calculations. It was found that although these factors do influence the predicted energies of the vertical excitations, they do not affect the trends predicted in the spectral properties across series of structurally related substituted free bases and metallophthalocyanines. The best accuracy for the gas-phase vertical excitations was observed in the lower-energy Q-band region for calculations that made use of range-separated hybrids for both full and simplified TD-DFT approaches. The CAMB3LYP functional provided particularly accurate results in the context of the sTD-DFT approach. The description of the higherenergy B-band region is considerably less accurate, and this demonstrates the need for further advances in the accuracy of theoretical calculations. Together with a general increase in accuracy, the application of simplified TD-DFT methods affords a 2−3 orders of magnitude speedup of the calculations in comparison to the full TD-DFT approach. It is anticipated that this approach will be widely used on desktop computers during the interpretation of UV−vis−NIR spectra of phthalocyanines and related macrocycles in the years ahead.
- Full Text:
- Date Issued: 2019
- Authors: Martynov, Alexander G , Mack, John , May, Aviwe K , Nyokong, Tebello , Gorbunova, Yulia G , Tsivadze, Aslan Yu
- Date: 2019
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/186915 , vital:44547 , xlink:href="https://doi.org/10.1021/acsomega.8b03500"
- Description: A methodological survey of density functional theory (DFT) methods for the prediction of UV−visible (vis)−near-infrared (NIR) spectra of phthalocyanines is reported. Four methods, namely, full time-dependent (TD)-DFT and its Tamm−Dancoff approximation (TDA), together with their simplified modifications (sTD-DFT and sTDA, respectively), were tested by using the examples of unsubstituted and alkoxy-substituted metal-free ligands and zinc complexes. The theoretical results were compared with experimental data derived from UV−visible absorption and magnetic circular dichroism spectroscopy. Seven popular exchange-correlation functionals (BP86, B3LYP, TPSSh, M06, CAM-B3LYP, LC-BLYP, and ωB97X) were tested within these four approaches starting at a relatively modest level using 6-31G(d) basis sets and gas-phase BP86/def2-SVP optimized geometries. A gradual augmentation of the computational levels was used to identify the influence of starting geometry, solvation effects, and basis sets on the results of TD-DFT and sTD-DFT calculations. It was found that although these factors do influence the predicted energies of the vertical excitations, they do not affect the trends predicted in the spectral properties across series of structurally related substituted free bases and metallophthalocyanines. The best accuracy for the gas-phase vertical excitations was observed in the lower-energy Q-band region for calculations that made use of range-separated hybrids for both full and simplified TD-DFT approaches. The CAMB3LYP functional provided particularly accurate results in the context of the sTD-DFT approach. The description of the higherenergy B-band region is considerably less accurate, and this demonstrates the need for further advances in the accuracy of theoretical calculations. Together with a general increase in accuracy, the application of simplified TD-DFT methods affords a 2−3 orders of magnitude speedup of the calculations in comparison to the full TD-DFT approach. It is anticipated that this approach will be widely used on desktop computers during the interpretation of UV−vis−NIR spectra of phthalocyanines and related macrocycles in the years ahead.
- Full Text:
- Date Issued: 2019
Effect of peripheral fused ring substitution on the optical spectroscopy and electronic structure of metal phthalocyanine complexes
- Chidawanyika, Wadzanai J U, Mack, John, Shimizu, Soji, Kobayashi, Nagao, Nyokong, Tebello
- Authors: Chidawanyika, Wadzanai J U , Mack, John , Shimizu, Soji , Kobayashi, Nagao , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263353 , vital:53620 , xlink:href="https://doi.org/10.1142/S1088424609001339"
- Description: In this paper the impact of peripheral substitution with a strongly withdrawing fused ring group on the optical spectroscopy of a metal phthalocyanine complex is analyzed. We report the synthesis of [9 (or 10), 16 (or 17), 23 (or 24)-tri-tert-butylimidophthalocyaninato]zinc(II) (ZnttbIPc), which should eventually prove to be a useful precursor for forming dimeric compounds. The electronic structure is analyzed through a detailed analysis of the UV-visible absorption and magnetic circular dichroism spectra and time-dependent density functional theory calculations. Other than a marked splitting of the Q band, the spectrum is broadly similar to that of ZnPc in terms of the main π → π* electronic bands. The vibrational bands differ markedly in the Q band region when an imido group is added to ligand periphery, relative to what is observed in the case of zinc mononaphthotribenzotetraazaporphyrin (Zn3B1N) with an additional fused benzene ring. The absorption and emission spectra lack mirror symmetry as is the case with ZnPc and thus provide possible evidence for a second set of electronic origins in the Q band region arising from n → π* rather then π → π* transitions.
- Full Text:
- Date Issued: 2009
- Authors: Chidawanyika, Wadzanai J U , Mack, John , Shimizu, Soji , Kobayashi, Nagao , Nyokong, Tebello
- Date: 2009
- Subjects: To be catalogued
- Language: English
- Type: text , article
- Identifier: http://hdl.handle.net/10962/263353 , vital:53620 , xlink:href="https://doi.org/10.1142/S1088424609001339"
- Description: In this paper the impact of peripheral substitution with a strongly withdrawing fused ring group on the optical spectroscopy of a metal phthalocyanine complex is analyzed. We report the synthesis of [9 (or 10), 16 (or 17), 23 (or 24)-tri-tert-butylimidophthalocyaninato]zinc(II) (ZnttbIPc), which should eventually prove to be a useful precursor for forming dimeric compounds. The electronic structure is analyzed through a detailed analysis of the UV-visible absorption and magnetic circular dichroism spectra and time-dependent density functional theory calculations. Other than a marked splitting of the Q band, the spectrum is broadly similar to that of ZnPc in terms of the main π → π* electronic bands. The vibrational bands differ markedly in the Q band region when an imido group is added to ligand periphery, relative to what is observed in the case of zinc mononaphthotribenzotetraazaporphyrin (Zn3B1N) with an additional fused benzene ring. The absorption and emission spectra lack mirror symmetry as is the case with ZnPc and thus provide possible evidence for a second set of electronic origins in the Q band region arising from n → π* rather then π → π* transitions.
- Full Text:
- Date Issued: 2009