The Peculiarities of the RNA Luminescence

Kudrya, Vladislav Yu.; Yashchuk, Valeriy M.; Levchenko, Svitlana M.; Mel'nik, V. I.; Zaika, L. A.; Govorun, D. M.

doi:10.1080/15421400802458670

Cited by 9 publications

(15 citation statements)

References 5 publications

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“…On the other hand, guanine and cytosine, having a much lower spectroscopic 1 (ππ*) singlet excited state below the nπ*-type states, are not expected to display the nπ*-mediated ISC mechanisms in regions close to the main MEP and may have only efficient ISC funnels at low energies, close to the singlet CI, a feature common to all nucleobases. The present results explain the fact that guanine and cytosine contribute much less to the phosphorescence of DNA, as it has been established. − It is noteworthy to indicate that the phosphorescence spectrum of RNA was also reported, and it was shown, first, to be determined mainly by the individual properties of the ribonucleotides’ π-electron systems, and second, to be composed by triplet signals of adenosine groups and centers of an unknown nature with structureless long-wavelength phosphorescence different from that in DNA. The present results would indicate that adenine and, in this case, uracil nucleobases should be preferably considered as sources of phosphorescence in RNA, as adenine and thymine are in DNA.…”

Section: Discussionsupporting

confidence: 75%

“…It is clear that the present results for the isolated systems cannot be directly extrapolated to polymeric DNA/RNA. As already explained before, the described properties should be, however, considered intrinsic features of the nucleobases that, even if they may change in condensed phases or, in general, in the biological environment for the single monomers, are expected to maintain their basic characteristics, as occurs for the singlet states properties and it seems also for triplet states …”

Section: Discussionmentioning

confidence: 99%

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Singlet−Triplet States Interaction Regions in DNA/RNA Nucleobase Hypersurfaces

González‐Luque

Climent

González-Ramírez

et al. 2010

J. Chem. Theory Comput.

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The present study provides new insight into the intrinsic mechanisms for the population of the triplet manifold in DNA nucleobases by determining, at the multiconfigurational CASSCF/CASPT2 level, the singlet-triplet states crossing regions and the main decay paths for their lowest singlet and triplet states after near-UV irradiation. The studied singlet-triplet interacting regions are accessible along the minimum energy path of the initially populated singlet bright (1)ππ* state. In particular, all five natural DNA/RNA nucleobases have, at the end of the main minimum energy path and near a conical intersection of the ground and (1)ππ* states, a low-energy, easily accessible, singlet-triplet crossing region directly connecting the lowest singlet and triplet ππ* excited states. Adenine, thymine, and uracil display additional higher-energy crossing regions related to the presence of low-lying singlet and a triplet nπ* state. These funnels are absent in guanine and cytosine, which have the bright (1)ππ* state lower in energy and less accessible nπ* states. Knowledge of the location and accessibility of these regions, in which the singlet-triplet interaction is related to large spin-orbit coupling elements, may help to understand experimental evidence such as the wavelength dependence measured for the triplet formation quantum yield in nucleobases and the prevalence of adenine and thymine components in the phosphorescence spectra of DNA.

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Section: Discussionsupporting

confidence: 75%

Section: Discussionmentioning

confidence: 99%

Singlet−Triplet States Interaction Regions in DNA/RNA Nucleobase Hypersurfaces

González‐Luque

Climent

González-Ramírez

et al. 2010

J. Chem. Theory Comput.

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“…The absorption spectra of the oligoRNA and the additive sum of the absorption spectra of ribonucleotides are presented in Figure 3 (we take into account that the average quantities of ribonucleotides of the different types are approximately equal for this type of RNA). It is evident that the absorption spectra of RNA is very close to the additive sum of the absorption spectra of model compounds, as it was shown in our previous work [13], including DNA [1,12,14,15]. The similar situation is observed for oligoadenylate 2 0 5 0 A 3 and rAMP ( Fig.…”

Section: Methodssupporting

confidence: 76%

“…It appears that the ribonucleic model compounds are less stable than deoxyribonucleic ones. Unfortunately, this fact was the main cause of the not accurate estimation of the positions of triplet levels in [13], where the lowest triplet level was identified as the rUMP level. So, the lowest electronic triplet level of RNA belongs to adenine.…”

Section: Resultsmentioning

confidence: 99%

Optical Response of the Polynucleotides-Proteins Interaction

Yashchuk

Kudrya

Levchenko

et al. 2011

Molecular Crystals and Liquid Crystals

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The optical absorption, fluorescence, and phosphorescence spectra of RNAs and oligonucleotides of different origin, as well as their mixtures with human albumin are investigated. It is confirmed that the energy structures of DNA, RNA, and complex protein macromolecules are determined mainly by the individual properties of their p-electron systems. The positions of the RNA excited singlet and triplet energy levels obtained by authors' previous work are determined more precisely. It is shown that mainly adenine bases are traps for mobile triplet excitons in RNA (contrary to DNA, in which AT complexes are the triplet traps). The spectral manifestation of the RNA=oligonucleotides-albumin interaction is studied. It turns out that namely the phosphorescence spectra of these compounds due to their sharp structure at 4.2 K are the most suitable for the study of the RNA-albumin interaction. The phosphorescence spectra of albumin-2 0 5 0 A 3 solvents manifest the penetrative binding of 2 0 5 0 A 3 to an albumin macromolecule. The obtained data show that at least a weak non-penetrative binding of RNA to human albumin can exist.

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“…7). It is well known that FL of DNA takes place near 350 nm under the excitation at 260-265 nm [14,15].…”

Section: Emission From Opalmentioning

confidence: 99%

New Optical Properties of Synthetic Opals Infiltrated by DNA

Boyko

Довбешко

Fesenko

et al. 2011

Molecular Crystals and Liquid Crystals

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Optical properties of photonic crystals (synthetic opals) with DNA inserted inside the crystals have been registered and analyzed in the visible and IR ranges. A decrease in the intensity of vibration spectra of DNA infiltrated in opal is observed. Molecules of DNA placed in the cavities of a photonic crystal became invisible for the detection by visible and IR spectroscopies. Spectroscopic features of DNA in a photonic crystal indicate the formation of condensed DNA inside and at the surface of the photonic crystal. The emission of the ''DNA -photonic crystal'' system has been registered at room temperature. By confocal microscopy, we have visualized DNA at the surface of a photonic crystal. The experimental results are explained by assuming the formation of coupled photonic states of DNA and a photonic crystal.

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The Peculiarities of the RNA Luminescence

Cited by 9 publications

References 5 publications

Singlet−Triplet States Interaction Regions in DNA/RNA Nucleobase Hypersurfaces

Singlet−Triplet States Interaction Regions in DNA/RNA Nucleobase Hypersurfaces

Optical Response of the Polynucleotides-Proteins Interaction

New Optical Properties of Synthetic Opals Infiltrated by DNA

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