Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2021 May 1;26(9):2657.
doi: 10.3390/molecules26092657.

Nipagin-Functionalized Porphyrazine and Phthalocyanine-Synthesis, Physicochemical Characterization and Toxicity Study after Deposition on Titanium Dioxide Nanoparticles P25

Dariusz T Mlynarczyk  1 , Daniel Ziental  2 , Emil Kolasinski  1 , Lukasz Sobotta  2 , Tomasz Koczorowski  1 , Jadwiga Mielcarek  2 , Tomasz Goslinski  1
Affiliations

Nipagin-Functionalized Porphyrazine and Phthalocyanine-Synthesis, Physicochemical Characterization and Toxicity Study after Deposition on Titanium Dioxide Nanoparticles P25

Dariusz T Mlynarczyk et al. Molecules. .

Abstract

Aza-porphyrinoids exhibit distinct spectral properties in UV-Vis, and they are studied in applications such as photosensitizers in medicine and catalysts in technology. The use of appropriate peripheral substituents allows the modulation of their physicochemical properties. Phthalocyanine and sulfanyl porphyrazine octa-substituted with 4-(butoxycarbonyl)phenyloxy moieties were synthesized and characterized using UV-Vis and NMR spectroscopy, as well as mass spectrometry. A comparison of porphyrazine with phthalocyanine aza-porphyrinoids revealed that phthalocyanine macrocycle exhibits higher singlet oxygen generation quantum yields, reaching the value of 0.29 in DMF. After both macrocycles had been deposited on titanium dioxide nanoparticles P25, the cytotoxicities and photocytotoxicities of the prepared materials were studied using a Microtox® acute toxicity test. The highest cytotoxicity occurred after irradiation with a red light for the material composed of phthalocyanine deposited on titania nanoparticles.

Keywords: Linstead macrocyclization; Microtox; phthalocyanine; porphyrazine; singlet oxygen; titanium dioxide.

PubMed Disclaimer

Conflict of interest statement

The authors declare no conflict of interest. The funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or in the decision to publish the results.

Figures

Scheme 1
Scheme 1
Synthetic route leading to symmetrical phthalocyanine derivative 3: (i) 1,4-dibromobutane, K2CO3, DMF, rt, 72 h; (ii) 3,6-dihydroxybenzene-1,2-dicarbonitrile, K2CO3, DMF, rt, 20 h; (iii) Mg(BuO)2, BuOH, 120 °C, 20 h.
Scheme 2
Scheme 2
Synthetic route leading to sulfanyl porphyrazine: (i) 1,4-dibromobutane, K2CO3, DMF, rt, 72 h; (ii) dimercaptomaleonitrile sodium salt hydrate, K2CO3, DMF, 50 °C, 20 h; (iii) Mg(BuO)2, BuOH, 120 °C, 20 h.
Scheme 3
Scheme 3
Synthetic route leading to novel sulfanyl porphyrazine 7: (i) 1,4-dibromobutane, K2CO3, DMF, rt, 72 h; (ii) dimercaptomaleonitrile sodium salt hydrate, K2CO3, DMF, 50 °C, 20 h; (iii) Mg(BuO)2, BuOH, 120 °C, 20 h.
Scheme 4
Scheme 4
Alternative synthetic route leading to 3: (i) 3,6-dihydroxybenzene-1,2-dicarbonitrile, K2CO3, DMF, rt, 20 h; (ii) Mg(BuO)2, BuOH, 120 °C, 20 h.
Figure 1
Figure 1
Solvatochromic effects observed in the UV-Vis spectra in various solvents for (a) 3; (b) 7; AcOH—acetic acid, DCM—dichloromethane, DMF—N,N-dimethylformamide.
Figure 2
Figure 2
Effect of solvents used on the color of the solution of 3: (a) pyridine, (b) N,N-dimethylformamide, (c) dichloromethane, (d) dichloromethane + 1% of acetic acid, (e) acetone, (f) ethyl acetate.
Figure 3
Figure 3
Chemical structures of macrocycles 3, 7 and 9–12.
Figure 4
Figure 4
Changes in A. fischeri cell viability after 15 min of the experiment when incubated with different materials (P25, 3@P25, 7@P25) or compounds (3, 7). The addition of water served as the control experiment (H2O).
See this image and copyright information in PMC

References

    1. Rodríguez-Morgade M.S., Stuzhin P.A. The chemistry of porphyrazines: An overview. J. Porphyrins Phthalocyanines. 2004;8:1129–1165. doi: 10.1142/S1088424604000490. - DOI
    1. Falkowski M., Rebis T., Piskorz J., Popenda L., Jurga S., Mielcarek J., Milczarek G., Goslinski T. Multiwalled carbon nanotube/sulfanyl porphyrazine hybrids deposited on glassy carbon electrode—Effect of nitro peripheral groups on electrochemical properties. J. Porphyrins Phthalocyanines. 2017;21:295–301. doi: 10.1142/S1088424617500134. - DOI
    1. Olgaç R., Baygu Y., Yıldız B., Gök Y., Köksoy B., Durmuş M. Synthesis, characterization and photochemical properties of metallo porphyrazines substituted with alkyl linked carbazole, benzoazepine and phenothiazine moieties. J. Porphyrins Phthalocyanines. 2017;21:599–610. doi: 10.1142/S1088424617500596. - DOI
    1. Chełminiak-Dudkiewicz D., Ziegler-Borowska M., Stolarska M., Sobotta L., Falkowski M., Mielcarek J., Goslinski T., Kowalonek J., Węgrzynowska-Drzymalska K., Kaczmarek H. The chitosan—Porphyrazine hybrid materials and their photochemical properties. J. Photochemistry Photobiol. B Biol. 2018;181:1–13. doi: 10.1016/j.jphotobiol.2018.02.021. - DOI - PubMed
    1. Yang C., Gao L., Zhang B., Zhang Z., Deng K. Uniform Zinc Thioporphyrazine nanosphere by self-assembly and the photocatalytic performance. J. Porphyrins Phthalocyanines. 2018;22:868–876. doi: 10.1142/S1088424618500487. - DOI

MeSH terms

LinkOut - more resources