Modulating Excited Charge-Transfer States of G‑Quartet Self- Assemblies by Earth Alkaline Cations and Hydration
Article (Accepted Version)
Metadata
Show full item recordAbstract
Guanine self-assemblies are promising supramolecularplatforms for optoelectronic applications. The study (Hua et al., J. Phys. Chem. C 2012, 116, 14,682−14,689) reported that alkaline cations cannot modulate the electronic absorption spectrum of G-quadruplexes, although a cation effect is observableduring electronic relaxation due to different mobility of Na+ and K+ cations. In this work, we theoretically examined whether divalent Mg2+ and Ca2+ cations and hydration might shift excited charge-transfer states of a cation-templated stacked G-quartet to the absorption red tail. Our results showed that earth alkaline cationsblue-shifted nπ* states and stabilized charge-transfer ππ* states relative to those of complexes with alkaline cations, although the number of charge-separation states was not significantly modified. Earth alkaline cations were not able to considerably increase theamount of charge-transfer states below the Lb excitonic states. Hydration shifted charge-transfer states of... the Na+-coordinated Goctet to the absorption red tail, although this part of the spectrum was still dominated by monomer-like excitations. We found Goctet electron detachment states at low excitation energies in aqueous solution. These states were distributed over a broad range of excitation energies and could be responsible for oxidative damage observed upon UV irradiation of biological G-quadruplexes.
Keywords:
Charge-Transfer States / G-Quartet / Band structure / G-Quadruplex / Guanine / DFT / Electronic absorption spectrum / Hydration Effects / Excited statesSource:
The Journal of Physical Chemistry A, 2020, 124, 40, 8101-8111Publisher:
- American Chemical Society (ACS)
Funding / projects:
- VRE for regional Interdisciplinary communities in Southeast Europe and the Eastern Mediterranean (EU-H2020-675121)
- Ministry of Science, Technological Development and Innovation of the Republic of Serbia, institutional funding - 200146 (University of Belgrade, Faculty of Physical Chemistry) (RS-MESTD-inst-2020-200146)
Note:
- This is the peer-reviewed version of the article: Branislav Milovanović, Ivana M. Stanković, Milena Petković, and Mihajlo Etinski, Modulating Excited Charge-Transfer States of G‑Quartet Self- Assemblies by Earth Alkaline Cations and Hydration, The Journal of Physical Chemistry A, 2020, 124, 40, 8101-8111, DOI: https://doi.org/10.1021/acs.jpca.0c05022
- The published version: https://cer.ihtm.bg.ac.rs/handle/123456789/3733
DOI: 10.1021/acs.jpca.0c05022
ISSN: 1089-5639; 1520-5215
PubMed: 32936636
WoS: 000580563800001
Scopus: 2-s2.0-85092749673
Collections
Institution/Community
IHTMTY - JOUR AU - Milovanović, Branislav AU - Stanković, Ivana AU - Petković, Milena AU - Etinski, Mihajlo PY - 2020 UR - https://cer.ihtm.bg.ac.rs/handle/123456789/3734 AB - Guanine self-assemblies are promising supramolecularplatforms for optoelectronic applications. The study (Hua et al., J. Phys. Chem. C 2012, 116, 14,682−14,689) reported that alkaline cations cannot modulate the electronic absorption spectrum of G-quadruplexes, although a cation effect is observableduring electronic relaxation due to different mobility of Na+ and K+ cations. In this work, we theoretically examined whether divalent Mg2+ and Ca2+ cations and hydration might shift excited charge-transfer states of a cation-templated stacked G-quartet to the absorption red tail. Our results showed that earth alkaline cationsblue-shifted nπ* states and stabilized charge-transfer ππ* states relative to those of complexes with alkaline cations, although the number of charge-separation states was not significantly modified. Earth alkaline cations were not able to considerably increase theamount of charge-transfer states below the Lb excitonic states. Hydration shifted charge-transfer states of the Na+-coordinated Goctet to the absorption red tail, although this part of the spectrum was still dominated by monomer-like excitations. We found Goctet electron detachment states at low excitation energies in aqueous solution. These states were distributed over a broad range of excitation energies and could be responsible for oxidative damage observed upon UV irradiation of biological G-quadruplexes. PB - American Chemical Society (ACS) T2 - The Journal of Physical Chemistry A T1 - Modulating Excited Charge-Transfer States of G‑Quartet Self- Assemblies by Earth Alkaline Cations and Hydration VL - 124 IS - 40 SP - 8101 EP - 8111 DO - 10.1021/acs.jpca.0c05022 ER -
@article{ author = "Milovanović, Branislav and Stanković, Ivana and Petković, Milena and Etinski, Mihajlo", year = "2020", abstract = "Guanine self-assemblies are promising supramolecularplatforms for optoelectronic applications. The study (Hua et al., J. Phys. Chem. C 2012, 116, 14,682−14,689) reported that alkaline cations cannot modulate the electronic absorption spectrum of G-quadruplexes, although a cation effect is observableduring electronic relaxation due to different mobility of Na+ and K+ cations. In this work, we theoretically examined whether divalent Mg2+ and Ca2+ cations and hydration might shift excited charge-transfer states of a cation-templated stacked G-quartet to the absorption red tail. Our results showed that earth alkaline cationsblue-shifted nπ* states and stabilized charge-transfer ππ* states relative to those of complexes with alkaline cations, although the number of charge-separation states was not significantly modified. Earth alkaline cations were not able to considerably increase theamount of charge-transfer states below the Lb excitonic states. Hydration shifted charge-transfer states of the Na+-coordinated Goctet to the absorption red tail, although this part of the spectrum was still dominated by monomer-like excitations. We found Goctet electron detachment states at low excitation energies in aqueous solution. These states were distributed over a broad range of excitation energies and could be responsible for oxidative damage observed upon UV irradiation of biological G-quadruplexes.", publisher = "American Chemical Society (ACS)", journal = "The Journal of Physical Chemistry A", title = "Modulating Excited Charge-Transfer States of G‑Quartet Self- Assemblies by Earth Alkaline Cations and Hydration", volume = "124", number = "40", pages = "8101-8111", doi = "10.1021/acs.jpca.0c05022" }
Milovanović, B., Stanković, I., Petković, M.,& Etinski, M.. (2020). Modulating Excited Charge-Transfer States of G‑Quartet Self- Assemblies by Earth Alkaline Cations and Hydration. in The Journal of Physical Chemistry A American Chemical Society (ACS)., 124(40), 8101-8111. https://doi.org/10.1021/acs.jpca.0c05022
Milovanović B, Stanković I, Petković M, Etinski M. Modulating Excited Charge-Transfer States of G‑Quartet Self- Assemblies by Earth Alkaline Cations and Hydration. in The Journal of Physical Chemistry A. 2020;124(40):8101-8111. doi:10.1021/acs.jpca.0c05022 .
Milovanović, Branislav, Stanković, Ivana, Petković, Milena, Etinski, Mihajlo, "Modulating Excited Charge-Transfer States of G‑Quartet Self- Assemblies by Earth Alkaline Cations and Hydration" in The Journal of Physical Chemistry A, 124, no. 40 (2020):8101-8111, https://doi.org/10.1021/acs.jpca.0c05022 . .