Electron-driven proton transfer relieves excited-state antiaromaticity in photoexcited DNA base pairs

Karas, Lucas J.; Wu, Chia‐Hua; Ottosson, Henrik; Wu, Judy I.

doi:10.1039/d0sc02294b

Cited by 37 publications

(39 citation statements)

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“…We can generally conclude that the gas phase calculations show the general features of HBs for the majority of the base pairs presented in this study. It has been confirmed in other studies that the Watson-Crick AT and GC base pairs are electronically complementary through proton transfer [ 147 , 148 ]. These results can be expanded to tautomeric base pairs where photoexcitation studies show a link between UV-excited DNA states and efficient charge production and transmission in DNA [ 147 ].…”

Section: Results and Discussionsupporting

confidence: 53%

“…It has been confirmed in other studies that the Watson-Crick AT and GC base pairs are electronically complementary through proton transfer [ 147 , 148 ]. These results can be expanded to tautomeric base pairs where photoexcitation studies show a link between UV-excited DNA states and efficient charge production and transmission in DNA [ 147 ]. Base pair radical ions behave similarly to those created when ionizing radiation interacts with DNA [ 148 , 149 , 150 , 151 ].…”

Section: Results and Discussionsupporting

confidence: 53%

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Hydrogen Bonding in Natural and Unnatural Base Pairs—A Local Vibrational Mode Study

2021

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In this work hydrogen bonding in a diverse set of 36 unnatural and the three natural Watson Crick base pairs adenine (A)–thymine (T), adenine (A)–uracil (U) and guanine (G)–cytosine (C) was assessed utilizing local vibrational force constants derived from the local mode analysis, originally introduced by Konkoli and Cremer as a unique bond strength measure based on vibrational spectroscopy. The local mode analysis was complemented by the topological analysis of the electronic density and the natural bond orbital analysis. The most interesting findings of our study are that (i) hydrogen bonding in Watson Crick base pairs is not exceptionally strong and (ii) the N–H⋯N is the most favorable hydrogen bond in both unnatural and natural base pairs while O–H⋯N/O bonds are the less favorable in unnatural base pairs and not found at all in natural base pairs. In addition, the important role of non-classical C–H⋯N/O bonds for the stabilization of base pairs was revealed, especially the role of C–H⋯O bonds in Watson Crick base pairs. Hydrogen bonding in Watson Crick base pairs modeled in the DNA via a QM/MM approach showed that the DNA environment increases the strength of the central N–H⋯N bond and the C–H⋯O bonds, and at the same time decreases the strength of the N–H⋯O bond. However, the general trends observed in the gas phase calculations remain unchanged. The new methodology presented and tested in this work provides the bioengineering community with an efficient design tool to assess and predict the type and strength of hydrogen bonding in artificial base pairs.

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Section: Results and Discussionsupporting

confidence: 53%

Section: Results and Discussionsupporting

confidence: 53%

Hydrogen Bonding in Natural and Unnatural Base Pairs—A Local Vibrational Mode Study

2021

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“…Finally, we note that strongly antiaromatic systems with emerging biradical character and low triplet energies would require a multireference treatment [82,83] for a reliable description of the wavefunctions involved, noting that NICS values and current densities may indeed be strongly affected by multireference effects. [80,84,85] Nonetheless, we believe that Figure 4 provides a good, semiquantitative description of the relevant physics.…”

Section: Cyclobuta[l]phenanthrene -Antiaromaticity and Baird Aromaticitymentioning

confidence: 91%

Visualisation of Chemical Shielding Tensors (VIST) to Elucidate Aromaticity and Antiaromaticity**

Plasser

Glöcklhofer

2021

Eur J Org Chem

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Aromaticity is a central concept in chemistry, pervading areas from biochemistry to materials science.Recently, chemists also started to exploit intricate phenomena such as the interplay of local and global (anti)aromaticity or aromaticity in non-planar systems and three dimensions. These phenomena pose new challenges in terms of our fundamental understanding and the practical visualisation of aromaticity. To overcome these challenges, a method for the visualisation of chemical shielding tensors (VIST) is developed here that allows for a 3D visualisation with quantitative information about the local variations and anisotropy of the chemical shielding. After exemplifying the method in different planar hydrocarbons, we study two non-planar macrocycles to show the unique benefits of the VIST method for molecules with competing pi-conjugated systems and conclude with a norcorrole dimer showing clear evidence of through-space aromaticity. We believe that the VIST method will be a highly valuable addition to the computational toolbox. File list (2)download file view on ChemRxiv VIST_submission.pdf (5.13 MiB) download file view on ChemRxiv suppinfo.pdf (3.35 MiB)

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“…Excited‐state aromaticity has been discussed in various contexts. For example, several reports demonstrate that aromatic and antiaromatic character drive reactivity in excited states and therefore can be used to describe and predict photochemical reactions [24–30] . Additionally, new functional materials have been designed by using the concept of excited‐state aromaticity and antiaromaticity as a strategy to modulate the singlet–triplet (S–T) energy gap, [20, 31, 32] which is relevant to organic electronics, [32–34] photoswitching, [35, 36] photoluminescence, [37] and singlet‐fission [33, 38–40] capable materials.…”

Section: Introductionmentioning

confidence: 99%

Prediction of Spin Density, Baird‐Antiaromaticity, and Singlet–Triplet Energy Gap in Triplet‐State Polybenzenoid Systems from Simple Structural Motifs

Markert

Paenurk

Gershoni‐Poranne

2021

Chemistry A European J

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Triplet‐state aromaticity has been recently proposed as a strategy for designing functional organic electronic compounds, many of which are polycyclic aromatic systems. However, in many cases, the aromatic nature of the triplet state cannot be easily predicted. Moreover, it is often unclear how specific structural manipulations affect the electronic properties of the excited‐state compounds. Herein, the relationship between the structure of polybenzenoid hydrocarbons (PBHs) and their spin‐density distribution and aromatic character in the first triplet excited state is studied. Although a direct link is not immediately visible, classifying the PBHs according to their annulation sequence reveals regularities. Based on these, a set of guidelines is defined to qualitatively predict the location of spin and paratropicity and the singlet–triplet energy gap in larger PBHs, using only their smaller tri‐ and tetracyclic components, and subsequently tested on larger systems.

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Electron-driven proton transfer relieves excited-state antiaromaticity in photoexcited DNA base pairs

Abstract: The Watson–Crick A•T and G•C base pairs are not only electronically complementary, but also photochemically complementary. Upon UV irradiation, DNA base pairs undergo efficient excited-state deactivation through electron driven proton...

Cited by 37 publications

References 50 publications

Hydrogen Bonding in Natural and Unnatural Base Pairs—A Local Vibrational Mode Study

Hydrogen Bonding in Natural and Unnatural Base Pairs—A Local Vibrational Mode Study

Visualisation of Chemical Shielding Tensors (VIST) to Elucidate Aromaticity and Antiaromaticity**

Prediction of Spin Density, Baird‐Antiaromaticity, and Singlet–Triplet Energy Gap in Triplet‐State Polybenzenoid Systems from Simple Structural Motifs

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