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EPR spin Hamiltonian parameters of encapsulated spin-labels: impact of the hydrogen bonding topology
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology. (Swedish E-Science Research Center (SeRC))
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.ORCID iD: 0000-0003-0185-5724
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.ORCID iD: 0000-0002-9123-8174
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2013 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 15, no 7, 2427-2434 p.Article in journal (Refereed) Published
Abstract [en]

Encapsulation of spin-labels into "host'' compounds, like cucurbit[n]urils or cyclodextrins, in solutions has profound effects on the EPR spin Hamiltonian parameters of the spin-labels. In this work we study the microscopic origin of the EPR spin Hamiltonian parameters of spin-labels enclosed in hydrophobic cavities. We focus on the dependence of the EPR properties of encapsulated spin-labels on the hydrogen bonding topologies that occur upon encapsulation, and quantize various contributions to these parameters according to specific hydrogen bonding patterns. The obtained results provide refined insight into the role of the hydrogen bonding induced encapsulation shifts of EPR spin Hamiltonian parameters in solvated "spin-label@host compound'' complexes.

Place, publisher, year, edition, pages
2013. Vol. 15, no 7, 2427-2434 p.
Keyword [en]
Accurate Prediction, Condensed Phases, Exact Exchange, G-Tensors, Density, Nitroxides, Radicals, Inclusion, Probes, Approximation
National Category
Physical Sciences Chemical Sciences
URN: urn:nbn:se:kth:diva-118627DOI: 10.1039/c2cp43951dISI: 000313891400022ScopusID: 2-s2.0-84873020192OAI: diva2:607024
EU, FP7, Seventh Framework Programme, RI-283493Swedish e‐Science Research Center

QC 20130221

Available from: 2013-02-21 Created: 2013-02-21 Last updated: 2013-03-18Bibliographically approved
In thesis
1. Theoretical studies of EPR parameters of spin-labels incomplex environments
Open this publication in new window or tab >>Theoretical studies of EPR parameters of spin-labels incomplex environments
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis encloses quantum chemical calculations performed in the framework of density functional response theory for evaluating electron paramagnetic resonance (EPR) spin Hamiltonian parameters of various spin-labels in different environments. These parameters are the well known electronic g-tensor and the nitrogen hyperfine coupling constants, which are extensively explored in this work for various systems. A special attention was devoted to the relationships that form between the structural and spectroscopic properties that can be accounted for as an environmental inuence. Such environmental effects were addressed either within a fully quantum mechanical formalism, involving simplified model structures that still capture the physical properties of the extended system, or by employing a quantum mechanics/molecular mechanics (QM/MM) approach. The latter implies that the nitroxide spin label is treated quantum mechanically, while the environment is treated in a classical discrete manner, with appropriate force fields employed for its description. The state-of- the art techniques employed in this work allow for an optimum accounting of the environmental effects that play an important role for the behaviour of EPR properties of nitroxides spin labels. One achievement presented in this thesis includes the first theoretical con_rmation of an empirical assumption that is usually made for inter-molecular distance measurement experiments in deoxyribonucleic acid (DNA), involving pulsed electron-electron double resonance (PELDOR) and site-directed spin labeling (SDSL) techniques. This refers to the fact that the EPR parameters of the spin-labels are not affected by their interaction with the nucleobases from which DNA is constituted. Another important result presented deals with the inuence of a supramolecular complex on the EPR properties of an encapsulated nitroxide spin-label. The enclusion complex affects the hydrogen bonding topology that forms around the R2NO moiety of the nitroxide. This, on the other hand has a major impact on its structure which further on governs the magnitude of the spectroscopic properties. The projects and results presented in this thesis offer an example of successful usage of modern quantum chemistry techniques for the investigation of EPR parameters of spin-labels in complex systems.


Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2013. iv, 57 p.
Trita-BIO-Report, ISSN 1654-2312 ; 2013:6
EPR, DFT, spin-labels, QM/MM, Breit-Pauli Hamiltonian
National Category
Theoretical Chemistry
urn:nbn:se:kth:diva-119515 (URN)978-91-7501-681-8 (ISBN)
Public defence
2013-04-05, FB 54, AlbaNova University Center, Stockholm, 10:00 (English)

QC 20130318

Available from: 2013-03-18 Created: 2013-03-15 Last updated: 2013-03-18Bibliographically approved

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