Properties of 2,6-diamino-8-azapurine, a highly fluorescent purine analog and its N-alkyl derivatives: Tautomerism and excited-state proton transfer reactions

Wierzchowski, Jacek; Mędza, Grzegorz; Szabelski, Mariusz; Stachelska-Wierzchowska, Alicja

doi:10.1016/j.jphotochem.2013.05.014

Cited by 15 publications

(26 citation statements)

References 37 publications

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“…Its fluorescence, centered at ∼365 nm and showing ∼40% yield is dynamically quenched by buffer ions such as phosphate or acetate, and dual emission can be observed in the nonaqueous media (isopropanol, acetonitrile), in the presence of ∼150 mM triethylamine/acetic acid buffer. [72] In the acidic environment, a clear evidence of "phototautomerism via the cation" is visible (Figure 8), leading to long-wavelength emission at 410 nm, with Stokes' shift ∼11,000 cm −1 (not shown). This 410 nm band is characteristic to the neutral N8-methyl derivative.…”

Section: 6-diamino-8-azapurine and The Corresponding Ribosidesmentioning

confidence: 99%

“…This 410 nm band is characteristic to the neutral N8-methyl derivative. [72] We proposed [72] that the ground-state protonation at the N3 nitrogen shifts the triazole proton from N9 to N8 position, and the electronic excitation of the cationic species lead to a rapid excited-state deprotonation of N(3)H (see Figure 8). This is supported by the emission Fluorescence excitation (left-hand side, solid lines) and emission (broken lines) spectra of N8-ß-Dribofuranosyl-2,6-diamino-8-azapurine (∼2 μM) in aqueous medium.…”

Section: 6-diamino-8-azapurine and The Corresponding Ribosidesmentioning

confidence: 99%

“…[72] Ribosides and deoxyribosides of 8-azaDaPur have been synthesized many years ago, [73,74] but their fluorescence properties were not examined until recently. We have found that enzymatically generated N9-, N8-, and N7-β-d-ribosides of 8-azaDaPur are highly fluorescent, [75] with yields of ca.…”

Section: 6-diamino-8-azapurine and The Corresponding Ribosidesmentioning

confidence: 99%

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Excited-State Proton Transfer and Phototautomerism in Nucleobase and Nucleoside Analogs: A Mini-Review

Wierzchowski¹

2014

Nucleosides, Nucleotides and Nucleic Acids

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Intermolecular excited-state proton transfer (ESPT) has been observed in several fluorescent nucleobase and/or nucleoside analogs. In the present work, some new examples of ESPT in this class of compounds are presented together with a brief recapitulation of the previously published data. The nucleobases, nucleosides, and their analogs contain many basic and acidic centers and therefore their ESPT behavior may be complex. To interpret the complex data, it is usually necessary to determine the microscopic pK* values for each (or most) of the possible ESPT centers. Typical approach to solve this problem is by analysis of the alkyl derivatives, in which the possibility of the ESPT is reduced. Of particular interest are examples of "phototautomerization via the cation," observed in several systems, which in the neutral media do not undergo ESPT. Protonation of the molecule in the ground state facilitates the two-step phototautomerism in several systems, including formycin A and 2-amino-8-azadenine. Fluorescence of the nucleobase and nucleoside analogs undergoing ESPT is usually solvent-, isotope-, and buffer-ion sensitive, and in some systems the ESPT can be promoted by environmental factors, e.g., the presence of buffer ions. This sensitivity to the microenvironment parameters makes the ESPT systems potentially useful for biological applications.

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Section: 6-diamino-8-azapurine and The Corresponding Ribosidesmentioning

confidence: 99%

Section: 6-diamino-8-azapurine and The Corresponding Ribosidesmentioning

confidence: 99%

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Excited-State Proton Transfer and Phototautomerism in Nucleobase and Nucleoside Analogs: A Mini-Review

Wierzchowski¹

2014

Nucleosides, Nucleotides and Nucleic Acids

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“…The ribose source for enzymatic ribosylation, α-d-ribose-1-phosphate (R1P) has been prepared enzymatically as a 100 mM solution from 7-methylguanosine phosphorolysed by calf PNP, as previously described [33,50] and kept frozen.…”

Section: Chemicalsmentioning

confidence: 99%

“…Fluorescence decays were measured and analyzed using a FluoTime 200 lifetime fluorometer (PicoQuant GmbH, Berlin, Germany), equipped with an R3809U-50 microchannel-plate photo-multiplier (MCP-PMT, Hamamatsu, Japan), with 280 nm excitation by sub-nanosecond pulsed LED, as previously described [50].…”

Section: Spectral Measurementsmentioning

confidence: 99%

Tricyclic Nucleobase Analogs and Their Ribosides as Substrates and Inhibitors of Purine-Nucleoside Phosphorylases III. Aminopurine Derivatives

Stachelska-Wierzchowska

Wierzchowski

Górka

et al. 2020

Molecules

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Etheno-derivatives of 2-aminopurine, 2-aminopurine riboside, and 7-deazaadenosine (tubercidine) were prepared and purified using standard methods. 2-Aminopurine reacted with aqueous chloroacetaldehyde to give two products, both exhibiting substrate activity towards bacterial (E. coli) purine-nucleoside phosphorylase (PNP) in the reverse (synthetic) pathway. The major product of the chemical synthesis, identified as 1,N2-etheno-2-aminopurine, reacted slowly, while the second, minor, but highly fluorescent product, reacted rapidly. NMR analysis allowed identification of the minor product as N2,3-etheno-2-aminopurine, and its ribosylation product as N2,3-etheno-2-aminopurine-N2-β-d-riboside. Ribosylation of 1,N2-etheno-2-aminopurine led to analogous N2-β-d-riboside of this base. Both enzymatically produced ribosides were readily phosphorolysed by bacterial PNP to the respective bases. The reaction of 2-aminopurine-N9-β -d-riboside with chloroacetaldehyde gave one major product, clearly distinct from that obtained from the enzymatic synthesis, which was not a substrate for PNP. A tri-cyclic 7-deazaadenosine (tubercidine) derivative was prepared in an analogous way and shown to be an effective inhibitor of the E. coli, but not of the mammalian enzyme. Fluorescent complexes of amino-purine analogs with E. coli PNP were observed.

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2‐Aryl‐2,4‐dihydro‐5H‐[1,2,3]triazolo[4,5‐d]pyrimidin‐5‐ones as a New Platform for the Design and Synthesis of Biosensors and Chemosensors

et al. 2020

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2‐Aryl‐2,4‐dihydro‐5H‐[1,2,3]triazolo[4,5‐d]pyrimidin‐5‐ones (DTPs), which may be considered as analogues of 8‐azapurines, were synthesised. Their structural aspects in the ground and excited states, electronic distributions, and non‐covalent intramolecular interactions were studied using time‐dependent density functional theory. Photophysical investigations demonstrated the variability of the absorption and emission parameters of the DTPs depending on their structure, microenvironment, and external stimuli. The aggregation‐induced emission enhancement effect was confirmed by studying the emission of DTPs in the solid state and by spectral titrations in H2O‐dimethyl sulfoxide (DMSO) and EtOH‐DMSO mixtures. Further investigation revealed the selective sensitivity of DTPs to acids, which strongly depended on their structure. Reversible interactions were found between the DTPs and HCl and subsequently triethylamine, both as vapour stimuli and in solution. Cell imaging experiments showed the potential of the DTPs in fluorescence microscopy bioimaging applications. These findings show that DTPs can be used to fabricate bio‐ and chemosensors.

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Properties of 2,6-diamino-8-azapurine, a highly fluorescent purine analog and its N-alkyl derivatives: Tautomerism and excited-state proton transfer reactions

Cited by 15 publications

References 37 publications

Excited-State Proton Transfer and Phototautomerism in Nucleobase and Nucleoside Analogs: A Mini-Review

Excited-State Proton Transfer and Phototautomerism in Nucleobase and Nucleoside Analogs: A Mini-Review

Tricyclic Nucleobase Analogs and Their Ribosides as Substrates and Inhibitors of Purine-Nucleoside Phosphorylases III. Aminopurine Derivatives

2‐Aryl‐2,4‐dihydro‐5H‐[1,2,3]triazolo[4,5‐d]pyrimidin‐5‐ones as a New Platform for the Design and Synthesis of Biosensors and Chemosensors

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