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Analysis of NMR Spin-lattice Relaxation Dispersion on Complex Systems
Umeå University, Faculty of Science and Technology, Department of Chemistry. (Westlund group)
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis focus on the analysis of spin-lattice NMRD relaxation profilesmeasured in various complex systems such as proteins, zeolites and ionicliquids. Proton, deuterium and fluoride T1-NMRD relaxation profiles wereobtained from a fast-field cycling (FFC) instrument. It is found that alsopossible to obtain NMRD profiles from the molecular dynamics (MD)simulation trajectories. NMRD Profiles were analyzed by using differentrelaxation models, such as the Solomon-Bloembergen-Morgan (SBM) theoryand the Stochastic Liouville (SL) theory.

Paper I described the hydration of protein PrxV obtained from a MDsimulation, and compared with the picture emerges from an analysis byusing a generally accepted relaxation model [appendix C]. The result showsthat the information from NMRD analysis is an averaged picture of watermolecules with similar relaxation times; and the MD simulations containsinformation of all types of interested water molecules with differentresidence times.

In paper II NMRD profiles have been used to characterize the hydration ofthe oxygen-evolving complex in state S1 of photosystem II. NMRDexperiments were performed on both intact protein samples and Mndepletedsamples, and characteristic dispersion difference were foundbetween 0.03 MHz to 1 MHz; approximately. Both the SBM theory and theSL theory have been used to explain this dispersion difference, and it isfound that this is due to a paramagnetic enhancement of 1-2 water moleculesnearby ~10 Å from the spin center of the Mn4CaO5 cluster. The result showsthe reorientation of the molecular cluster is in μs time interval. Whencompare these two theories, the SL theory presented a better interpretationbecause parameters obtained from the SBM theory shows they didn’t fulfilthe presupposed perturbation criterion (the Kubo term).

Paper III deals with the water dynamics in the restricted/confined spaces inthe zeolite samples (H-ZSM-5 and NH4-ZSM-5) and obtained by proton anddeuterium spin-lattice NMRD profiles. The results show that the spin-latticeNMRD can be used to characterize various zeolites. The temperature has aweak effect on the relaxation rate R1, but the change of different counter ionsmay change the hydration and the translational diffusion pores and givedifferent R1.

Proton and fluoride NMRD profiles and MD simulations were both used tostudy the dynamics of BMIM[PF6] in paper IV. Results indicate the reorientation of the molecules are in the ns time regime, and the effectivecorrelation time obtained from 1H and 19F are the same. From the MDsimulation it is found the reorientation of [PF6]- ions is much faster (in ps)compare with BMIM+ ion which moves in the ns time range.

With previous results, the FFC NMRD profiles are indeed very informativetools to study the molecular dynamics of complex systems. The MDsimulation can be used as a complementary method to obtain detailedinformation. By combine these two methods, it provide a more colorfulpicture in the study of protein hydration and liquid molecular dynamics.

Place, publisher, year, edition, pages
Umeå: Umeå university , 2015. , 56 p.
Keyword [en]
NMRD, relaxation theory, hydration, MD, FFC, PrxV, OEC complex, ZSM-5, BMIM [PF6, ]
National Category
Theoretical Chemistry
Research subject
Physical Chemistry
Identifiers
URN: urn:nbn:se:umu:diva-110721ISBN: 978-91-7601-382-3 (print)OAI: oai:DiVA.org:umu-110721DiVA: diva2:865065
Public defence
2015-11-26, KBC-huset, sal KB3B1, Umeå Universitet, Umeå, 10:00 (English)
Opponent
Supervisors
Available from: 2015-11-05 Created: 2015-10-26 Last updated: 2015-10-29Bibliographically approved
List of papers
1. The water R1(ω) NMRD profiles of a hydrated protein from molecular dynamics simulation
Open this publication in new window or tab >>The water R1(ω) NMRD profiles of a hydrated protein from molecular dynamics simulation
2013 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 15, no 33, 14089-14097 p.Article in journal (Refereed) Published
Abstract [en]

 The hydration of a protein, peroxiredoxin 5, is obtained from a molecular dynamics simulation and compared with the picture of hydration which is obtained by analysing the water proton R1 NMRD profiles using a generally accepted relaxation model [K. Venu, V.P. Denisov and B. Halle, J. Am. Chem. Soc. 119,3122(1997)]. The discrepancy between the hydration pictures derived from the water R1 0)-NMRD profiles and MD is relevant in a discussion of the factors behind the stretched NMRD profile, the distribution of orientationalorder parameters and residence times of buried water used in the NMRD model.

Place, publisher, year, edition, pages
RSC Publishing, 2013
National Category
Chemical Sciences
Identifiers
urn:nbn:se:umu:diva-73724 (URN)10.1039/C3CP51147B (DOI)000322517800041 ()
Available from: 2013-06-27 Created: 2013-06-27 Last updated: 2017-12-06Bibliographically approved
2. Hydration of the oxygen-evolving complex of photosystem II probed in the dark-stable S1 state using proton NMR dispersion profiles
Open this publication in new window or tab >>Hydration of the oxygen-evolving complex of photosystem II probed in the dark-stable S1 state using proton NMR dispersion profiles
Show others...
2014 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, no 16, 11924-11935 p.Article in journal (Refereed) Published
Abstract [en]

The hydration of the oxygen-evolving complex (OEC) was characterized in the dark stable S1 state of photosystem II using water R1(ω) NMR dispersion (NMRD) profiles. The R1(ω) NMRD profiles were recorded over a frequency range from 0.01 MHz to 40 MHz for both intact and Mn-depleted photosystem II core complexes from Thermosynechococcus vulcanus (T. vulcanus). The intact-minus-(Mn)-depleted difference NMRD profiles show a characteristic dispersion from approximately 0.03 MHz to 1 MHz, which is interpreted on the basis of the Solomon-Bloembergen-Morgan (SBM) and the slow motion theories as being due to a paramagnetic enhanced relaxation (PRE) of water protons. Both theories are qualitatively consistent with the ST = 1, g = 4.9 paramagnetic state previously described for the S1 state of the OEC; however, an alternative explanation involving the loss of a separate class of long-lived internal waters due to the Mn-depletion procedure can presently not be ruled out. Using a point-dipole approximation the PRE-NMRD effect can be described as being caused by 1-2 water molecules that are located about 10 Å away from the spin center of the Mn4CaO5 cluster in the OEC. The application of the SBM theory to the dispersion observed for PSII in the S1 state is questionable, because the parameters extracted do not fulfil the presupposed perturbation criterion. In contrast, the slow motion theory gives a consistent picture indicating that the water molecules are in fast chemical exchange with the bulk (τw < 1 μs). The modulation of the zero-field splitting (ZFS) interaction suggests a (restricted) reorientation/structural equilibrium of the Mn4CaO5 cluster with a characteristic time constant of τZFS = 0.6-0.9 μs.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2014
National Category
Chemical Sciences
Identifiers
urn:nbn:se:umu:diva-87820 (URN)10.1039/c3cp55232b (DOI)24695863 (PubMedID)
Available from: 2014-04-10 Created: 2014-04-10 Last updated: 2017-12-05Bibliographically approved
3. Water proton and deuterium spin-lattice relaxation in Zeolite ZSM-5 by fast field-cycling NMR relaxometry
Open this publication in new window or tab >>Water proton and deuterium spin-lattice relaxation in Zeolite ZSM-5 by fast field-cycling NMR relaxometry
2015 (English)Manuscript (preprint) (Other academic)
Abstract [en]

The water dynamics in the confined space of the zeolite ZSM-5 has bee ninvestigated by means of the field dependence of 1H- and 2H- spin-lattice relaxation rates using a 1T Stelar FFC2000 fast field-cycling instrument. The NMRD analysis of  the experimental results indicates that the characteristic time dependence ( 50 ns to 1-2.4 μs) is due to water translational diffusion in narrow pores. The temperature dependence of the spin-lattice relaxation rates is weak.Zeolites with different counter ions( H+, NH4+ change the water hydration and the water translational diffusion in the pores drastically. The Zeolite-NH4+ slow down the water motion with a factor of 2.The NMRD profiles show somewhat stretched character and is described by two Lorenzian which indicates that the distribution of pore sizes is broaden.The water 1H and 2H spin lattice relaxation profiles give qualitatively information about water hydration in zeolites with different counter ions and is expected also to indicate structural changes of the zeolites. 

Keyword
proton, deuterium, spin lattice, relaxation, ZSM-5, zeolite
National Category
Theoretical Chemistry
Research subject
Physical Chemistry
Identifiers
urn:nbn:se:umu:diva-110716 (URN)
Note

2015, in manuscript

Available from: 2015-10-26 Created: 2015-10-26 Last updated: 2015-11-11
4. Analysis of proton/fluoride spin-lattice NMR dispersion experiment of an ionic liquid, BMIM[PF6] by using molecular dynamics simulations and relaxation theory
Open this publication in new window or tab >>Analysis of proton/fluoride spin-lattice NMR dispersion experiment of an ionic liquid, BMIM[PF6] by using molecular dynamics simulations and relaxation theory
Show others...
2015 (English)Manuscript (preprint) (Other academic)
Abstract [en]

Proton/Fluoride spin-lattice nuclear magnetic relaxation dispersion(NMRD) measurements of 1-Butyl-3-methylimidazolium-hexa fluorophosphate (BMIM[PF6])have been carried out using a 1T Stelar FFC2000 fast-field-cycling instrument at proton Larmor frequencies ranging from 10 kHz to 40 MHz and at different temperatures. The NMRD profiles are interpreted by means of a simple relaxation modelbased on the inter- and intra-molecular dipole dipole relaxation mechanims. Using an atomic and a coarse-grained (CG)Molecular Dynamics (MD) simulations at temperature 323 K the relevant dipole-dipole correlation functions are calculated. The result indicate that the NMRD profiles can be rationalized using a combination of intra and inter molecular dipole-dipole couplings. However, both are mainly modulated by molecular reorientation whereas translation diffusion plays a minor role. The molecular reorientation dynamics  of BMIM[PF6] ,BMIM+ ion are in the nano secondtime regime whereas the reorientation of  [PF6]- is much faster and loses its correlation in the ps regime. The relaxation mechanism for  [PF6]- is H-F inter-molecular dipole-dipole coupling which is modulated by the reorientation of  the H-containing molecule.

Keyword
proton, fluoride, spin-lattice, relaxation, ionic liquid, MD, BMIM[PF6]
National Category
Theoretical Chemistry
Research subject
Physical Chemistry
Identifiers
urn:nbn:se:umu:diva-110719 (URN)
Note

2015, in manuscript

Available from: 2015-10-26 Created: 2015-10-26 Last updated: 2015-11-11

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