| 1. |
- Baran, Jakub D., et al.
(author)
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A Case of Unusually Large Density of States Changes For Physisorption - TetraPhenyl-Porphyrins on Cu(111)
- 2015
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Conference paper (other academic/artistic)abstract
- Conformational changes caused by surface adsorption can dramatically affect a molecule’s properties. The conformational flexibility of the porphyrin family of molecules has been exploited particularly well in a number of contexts, including prototypical molecular switches. Despite this level of study, however, the exact mechanisms underpinning conformational switching are often unclear. We show that the conformation of the tetra(4-bromophenyl) porphyrin (Br4TPP) on Cu(111) depends critically on the precise adsorption site of the molecule, and that, remarkably, large conformational changes are driven entirely by van der Waals (vdW) interactions between the molecule and the substrate surface. A combination of scanning probe microscopy, low temperature single molecule manipulation, dispersion-corrected density functional theory (DFT) and molecular dynamics (MD) simulations shows that van der Waals forces dominate the adsorption of TPP molecules, causing significant distortions of the molecular architecture so that the porphyrin can adopt one of two low energy conformations. In addition, scanning probe manipulation has been used to translate and switch the Br4TPP molecule between conformations via an intermediary, ‘hybrid’ structure. We have used the generalized gradient approximation (GGA) parameterization by Perdew—Burke—Ernzerhof (PBE), and the sparse-matter optBP86b-vdW20 (vdW-DFT) exchange and correlation functional to account for the missing dispersion forces. In order to check for the presence of chemical bonding we have analyzed the molecule-surface complexes using electron localization function (ELF) and Bader charges. We find that vdW-forces alone are capable of causing large shifts in the molecular density of states, despite the complete absence of chemical interactions.
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| 2. |
- Jarvis, Samuel P., et al.
(author)
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Measuring the mechanical properties of molecular conformers
- 2015
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In: Nature Communications. - : Springer Science and Business Media LLC. - 2041-1723. ; 6
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Journal article (peer-reviewed)abstract
- Scanning probe-actuated single molecule manipulation has proven to be an exceptionally powerful tool for the systematic atomic-scale interrogation of molecular adsorbates. To date, however, the extent to which molecular conformation affects the force required to push or pull a single molecule has not been explored. Here we probe the mechanochemical response of two tetra(4-bromophenyl)porphyrin conformers using non-contact atomic force microscopy where we find a large difference between the lateral forces required for manipulation. Remarkably, despite sharing very similar adsorption characteristics, variations in the potential energy surface are capable of prohibiting probe-induced positioning of one conformer, while simultaneously permitting manipulation of the alternative conformational form. Our results are interpreted in the context of dispersion-corrected density functional theory calculations which reveal significant differences in the diffusion barriers for each conformer. These results demonstrate that conformational variation significantly modifies the mechanical response of even simple porpyhrins, potentially affecting many other flexible molecules
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| 3. |
- Jarvis, Samuel P., et al.
(author)
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Physisorption Controls the Conformation and Density of States of an Adsorbed Porphyrin
- 2015
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In: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 119:50, s. 27982-27994
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Journal article (peer-reviewed)abstract
- Conformational changes caused by adsorption can dramatically affect a molecule's properties. Despite extensive study, however, the exact mechanisms underpinning conformational switching are often unclear. Here we show that the conformation of a prototypical flexible molecule, the free-base tetra(4-bromophenyl) porphyrin, adsorbed on Cu(111), depends critically on its precise adsorption site and that, remarkably, large conformational changes are dominated by van der Waals interactions between the molecule and the substrate surface. A combination of scanning probe microscopy, single-molecule manipulation, DFT with dispersion density functional theory, and molecular dynamics simulations show that van der Waals forces drive significant distortions of the molecular architecture so that the porphyrin can adopt one of two low-energy conformations. We find that adsorption driven by van der Waals forces alone is capable of causing large shifts in the molecular density of states, despite the apparent absence of chemical interactions. These findings highlight the essential role that van der Waals forces play in determining key molecular properties.
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| 4. |
- Lexell, Jan, et al.
(author)
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Fibre type composition of rabbit tibialis anterior and extensor digitorum longus muscles
- 1994
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In: Journal of Anatomy. - 0021-8782 .- 1469-7580. ; 185:Pt 1, s. 95-101
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Journal article (peer-reviewed)abstract
- Rabbit tibialis anterior (TA) and extensor digitorum longus (EDL) muscles are used extensively in studies of stimulation-induced fibre type transformation, but the proportions and sizes of the 2 main fibre types, and the way in which they are distributed within the muscles, have never been described in any detail. In this study, transverse sections were processed by enzyme histochemical and immunohistochemical techniques and assessed morphometrically. The data were analysed by multivariate methods. In both TA and EDL muscles, the proportion of type 1 fibres varied significantly, and to a similar extent, within a cross-section, from lateral to medial and from superficial to deep parts. The fibre density, an indirect estimate of the mean muscle fibre area, also varied significantly, but not systematically, within a cross-section. For the EDL muscle, the proportion of type 1 fibres was consistently higher in the distal than in the proximal part of the muscle. The proportion of type 1 fibres was also significantly higher in the EDL than in the TA muscle for each of the 6 rabbits. There was no systematic variation between muscles from left and right limbs. The type proportions and fibre densities for both TA and EDL muscles differed significantly between individual rabbits, but not between sexes. The study provides a database that has hitherto been lacking on normal fibre type composition and its variation within and between these experimentally important muscles.
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