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Studies of photochemical properties of azidopurine nucleosides in the context of their potential use as photocrosslinking agents in double-stranded oligonucleotides systems

Krzysztof Komodziński

Abstract

A series of azidopurine nulcoesides have been synthesized and their photochemistry examined under the conditions of aerobic and anaerobic irradiation with near UV light (λ > 300 nm) in aqueous solutions. The major photoproducts were isolated using the high performance liquid chromatography (HPLC) and their structures established based on the measurements of 1H and 13C NMR and HR ESI-TOF MS spectra. Based on the results obtained it has been shown that dominant phototransformation in the case of 6-azidonebularine involves purine ring expansion to give a novel imidazole-fused 1,3,5-triazepinone nucleoside, independent on the presence or absence of oxygen, whereas the photochemistry of remaining azidopurine derivatives depends on the position of the azido group and the presence of additional substituents in the purine ring, as well as the presence of oxygen. Thus, depending on the photoirradiation conditions (aerobic or anaerobic), the major photoreactions of 2-azidoadenosine and 2-amino-6-azidonebularine were found to undergo either photoreduction or photooxidation to respective amino or nitro analogs, and no purine ring expansion product could be detected in both cases. Photochemical reactions of 6-azidopurine in the model oligonucleotides have been also examined. It was shown that in the single stranded oligonucleotide this derivative undergoes purine ring expansion photoreaction, whereas in the case of irradiation in the double stranded oligonucleotides it undergoes photoaddition to one of the adenine residues in the complementary strand leading to efficient (75-80%), covalent bonding of the two strands.
Record ID
UAMe486f2fa71284bf39ad3273da4f514f7
Diploma type
Doctor of Philosophy
Author
Title in Polish
Badania właściwości fotochemicznych azydonukleozydów purynowych w kontekście ich potencjalnego wykorzystania jako czynników fotozszywających w dwuniciowych układach oligonukleotydowych
Title in English
Studies of photochemical properties of azidopurine nucleosides in the context of their potential use as photocrosslinking agents in double-stranded oligonucleotides systems
Language
pol (pl) Polish
Certifying Unit
Faculty of Chemistry (SNŚ/WC/FoC)
Discipline
chemistry / (chemical sciences domain) / (physical sciences)
Scientific discipline (2.0)
6.5 chemical sciences
Status
Finished
Defense Date
03-06-2014
Title date
03-06-2014
Supervisor
URL
http://hdl.handle.net/10593/10892 Opening in a new tab
Keywords in English
azidonucleosides, photochemistry, photocrosslinking
Abstract in English
A series of azidopurine nulcoesides have been synthesized and their photochemistry examined under the conditions of aerobic and anaerobic irradiation with near UV light (λ > 300 nm) in aqueous solutions. The major photoproducts were isolated using the high performance liquid chromatography (HPLC) and their structures established based on the measurements of 1H and 13C NMR and HR ESI-TOF MS spectra. Based on the results obtained it has been shown that dominant phototransformation in the case of 6-azidonebularine involves purine ring expansion to give a novel imidazole-fused 1,3,5-triazepinone nucleoside, independent on the presence or absence of oxygen, whereas the photochemistry of remaining azidopurine derivatives depends on the position of the azido group and the presence of additional substituents in the purine ring, as well as the presence of oxygen. Thus, depending on the photoirradiation conditions (aerobic or anaerobic), the major photoreactions of 2-azidoadenosine and 2-amino-6-azidonebularine were found to undergo either photoreduction or photooxidation to respective amino or nitro analogs, and no purine ring expansion product could be detected in both cases. Photochemical reactions of 6-azidopurine in the model oligonucleotides have been also examined. It was shown that in the single stranded oligonucleotide this derivative undergoes purine ring expansion photoreaction, whereas in the case of irradiation in the double stranded oligonucleotides it undergoes photoaddition to one of the adenine residues in the complementary strand leading to efficient (75-80%), covalent bonding of the two strands.

Uniform Resource Identifier
https://researchportal.amu.edu.pl/info/phd/UAMe486f2fa71284bf39ad3273da4f514f7/
URN
urn:amu-prod:UAMe486f2fa71284bf39ad3273da4f514f7

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