Photocontrolled DNA minor groove interactions of imidazole/pyrrole polyamides
Uloženo v:
| Název: | Photocontrolled DNA minor groove interactions of imidazole/pyrrole polyamides |
|---|---|
| Autoři: | Sabrina Müller, Jannik Paulus, Jochen Mattay, Heiko Ihmels, Veronica I Dodero, Norbert Sewald |
| Zdroj: | Beilstein J Org Chem Beilstein Journal of Organic Chemistry, Vol 16, Iss 1, Pp 60-70 (2020) |
| Informace o vydavateli: | Beilstein Institut, 2020. |
| Rok vydání: | 2020 |
| Témata: | DNA minor groove, polyamide, Science, Organic chemistry, n-methylpyrrole, 01 natural sciences, dna minor groove, Full Research Paper, photoswitches, 0104 chemical sciences, 3. Good health, azobenzene, QD241-441, 13. Climate action, n-methylimidazole, N-methylimidazole, N-methylpyrrole |
| Popis: | Azobenzenes are photoswitchable molecules capable of generating significant structural changes upon E-to-Z photoisomerization in peptides or small molecules, thereby controlling geometry and functionality. E-to-Z photoisomerization usually is achieved upon irradiation at 350 nm (π–π* transition), while the Z-to-E isomerization proceeds photochemically upon irradiation at >400 nm (n–π* transition) or thermally. Photoswitchable compounds have frequently been employed as modules, e.g., to control protein–DNA interactions. However, their use in conjunction with minor groove-binding imidazole/pyrrole (Im/Py) polyamides is yet unprecedented. Dervan-type Im/Py polyamides were equipped with an azobenzene unit, i.e., 3-(3-(aminomethyl)phenyl)azophenylacetic acid, as the linker between two Im/Py polyamide strands. Only the (Z)-azobenzene-containing polyamides bound to the minor groove of double-stranded DNA hairpins. Photoisomerization was exemplarily evaluated by 1H NMR experiments, while minor groove binding of the (Z)-azobenzene derivatives was proven by CD titration experiments. The resulting induced circular dichroism (ICD) bands of the bound ligands, together with the photometric determination of the dsDNA melting temperature, revealed a significant stabilization of the DNA upon association with the ligand. The (Z)-azobenzene acted as a building block inducing a reverse turn, which favored hydrogen bonds between the pyrrole/imidazole amide and the DNA bases. In contrast, the E-configured polyamides did not induce any ICD characteristic for minor groove binding. The incorporation of the photoswitchable azobenzene unit is a promising strategy to obtain photoswitchable Im/Py hairpin polyamides capable of interacting with the dsDNA minor groove only in the Z-configuration. |
| Druh dokumentu: | Article Other literature type |
| Jazyk: | English |
| ISSN: | 1860-5397 |
| DOI: | 10.3762/bjoc.16.8 |
| Přístupová URL adresa: | https://www.beilstein-journals.org/bjoc/content/pdf/1860-5397-16-8.pdf https://pubmed.ncbi.nlm.nih.gov/31976017 https://doaj.org/article/f52b142f86394ca88d262a96eaf95e45 https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6964667 https://europepmc.org/article/MED/31976017 https://pubmed.ncbi.nlm.nih.gov/31976017/ https://www.beilstein-journals.org/bjoc/articles/16/8 https://www.ncbi.nlm.nih.gov/pubmed/31976017 https://www.beilstein-journals.org/bjoc/content/pdf/1860-5397-16-8.pdf |
| Rights: | CC BY "In Copyright" Rights Statement URL: http://creativecommons.org/licenses/by/4.0http://www.beilstein-journals.org/bjoc/termsThis is an Open Access article under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0). Please note that the reuse, redistribution and reproduction in particular requires that the authors and source are credited. The license is subject to the Beilstein Journal of Organic Chemistry terms and conditions: (http://www.beilstein-journals.org/bjoc/terms) |
| Přístupové číslo: | edsair.doi.dedup.....ec403fb22c50f2405bc86548fa3b054c |
| Databáze: | OpenAIRE |
Full Text 
Full Text Finder 
Nájsť tento článok vo Web of Science | Abstrakt: | Azobenzenes are photoswitchable molecules capable of generating significant structural changes upon E-to-Z photoisomerization in peptides or small molecules, thereby controlling geometry and functionality. E-to-Z photoisomerization usually is achieved upon irradiation at 350 nm (π–π* transition), while the Z-to-E isomerization proceeds photochemically upon irradiation at >400 nm (n–π* transition) or thermally. Photoswitchable compounds have frequently been employed as modules, e.g., to control protein–DNA interactions. However, their use in conjunction with minor groove-binding imidazole/pyrrole (Im/Py) polyamides is yet unprecedented. Dervan-type Im/Py polyamides were equipped with an azobenzene unit, i.e., 3-(3-(aminomethyl)phenyl)azophenylacetic acid, as the linker between two Im/Py polyamide strands. Only the (Z)-azobenzene-containing polyamides bound to the minor groove of double-stranded DNA hairpins. Photoisomerization was exemplarily evaluated by 1H NMR experiments, while minor groove binding of the (Z)-azobenzene derivatives was proven by CD titration experiments. The resulting induced circular dichroism (ICD) bands of the bound ligands, together with the photometric determination of the dsDNA melting temperature, revealed a significant stabilization of the DNA upon association with the ligand. The (Z)-azobenzene acted as a building block inducing a reverse turn, which favored hydrogen bonds between the pyrrole/imidazole amide and the DNA bases. In contrast, the E-configured polyamides did not induce any ICD characteristic for minor groove binding. The incorporation of the photoswitchable azobenzene unit is a promising strategy to obtain photoswitchable Im/Py hairpin polyamides capable of interacting with the dsDNA minor groove only in the Z-configuration. |
|---|---|
| ISSN: | 18605397 |
| DOI: | 10.3762/bjoc.16.8 |