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- Owenius, Rikard, et al.
(author)
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Influence of solvent polarity and hydrogen bonding on the EPR parameters of a nitroxide spin label studied by 9-GHz and 95-GHz EPR spectroscopy and DFT calculations
- 2001
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In: Journal of Physical Chemistry A. - : American Chemical Society (ACS). - 1089-5639 .- 1520-5215. ; 105:49, s. 10967-10977
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Journal article (peer-reviewed)abstract
- The isotropic and anisotropic hyperfine coupling constants and g-values of the nitroxide spin label (1-oxyl-2,2,5,5-tetramethylpyrroline-3-methyl)methanethiosulfonate (MTSSL) were determined from 9-GHz and 95-GHz electron paramagnetic resonance (EPR) measurements in various solvents with a large distribution in polarity and proticity. The parameters Aiso, giso, Azz, and gxx of MTSSL were found to be sensitive to changes in solvent properties, where A-values increased and g-values decreased due to increased solvent polarity or proticity. A linear correlation was found for the isotropic (giso, Aiso) and anisotropic (gxx, Azz) parameters, respectively. Furthermore, density functional theory (DFT) calculations of the same parameters were performed for a model spin label with the possibility to vary the dielectric constant (e) of the medium and the number of hydrogen bonds formed with the nitroxide oxygen. From a qualitative analysis of experimental and calculated results, it was possible to specify the causes of the parameter shifts in more detail. In the "apolar region" (e < 25), the sensitivity of Aiso and Azz to e is large. However, in the "polar region" (e > 25), the sensitivity to epsi, is small, and the shifts in Aiso and Azz are mainly determined by the proticity of the solvent. Methanol was found to form ~1 and water ~2 hydrogen bonds to the nitroxide on average. The DFT method determined the shifts in giso and gxx due to hydrogen bonding more accurately compared with the restricted open-shell Hartree-Fock method. The anisotropic spin label-solvent data can be used in the interpretation of rigid-limit data from spin-labeled proteins to gain further insight in local environmental properties.
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- Aberg, J, et al.
(author)
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Electrical properties of the TiSi2-Si transition region in contacts : The influence of an interposed layer of Nb
- 2001
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In: Journal of Applied Physics. - : AIP Publishing. - 0021-8979 .- 1089-7550. ; 90:5, s. 2380-2388
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Journal article (peer-reviewed)abstract
- The influence of an interposed ultrathin Nb layer between Ti and Si on the silicide formation and the electrical contact between the silicide formed and the Si substrate is investigated. The presence of the Nb interlayer results in the formation of ternary alloy (Nb,Ti)Si-2 in the C40 crystallographic structure adjacent to the Si substrate. Depending on the nature of the Si substrates and/or the amount of the initial Nb, the interfacial C40 (Nb,Ti)Si-2 leads, in turn, to either epitaxial growth of a highly faulted metastable C40 TiSi2 or formation of the desired C54 TiSi2 at a lower temperature than needed for it to form in reference samples with Ti deposited directly on Si. On p-type substrates doped to various concentrations, the Nb also leads to a considerably lower specific contact resistivity than that obtained in the reference samples: a twofold to fourfold reduction in the contact resistivity is found using cross-bridge Kelvin structures in combination with two-dimensional numerical simulation. As C40 (Nb,Ti)Si-2 forms at the interface when an interfacial Nb is present, the interface characterized is likely to represent the one between (Nb,Ti)Si-2 and Si. For the reference samples, the interface studied is between TiSi2 and Si.
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