Source:http://linkedlifedata.com/resource/pubmed/id/19736940
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rdf:type | |
lifeskim:mentions | |
pubmed:issue |
38
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pubmed:dateCreated |
2009-9-23
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pubmed:abstractText |
A series of butadiyne-linked zinc porphyrin oligomers, with one, two, three, and four porphyrin units and lengths of up to 75 A, have been spin-labeled at both ends with stable nitroxide TEMPO radicals. The pulsed EPR technique of double electron electron resonance (DEER) was used to probe the distribution of intramolecular end-to-end distances, under a range of conditions. DEER measurements were carried out at 50 K in two types of dilute solution glasses: deutero-toluene (with 10% deutero-pyridine) and deutero-o-terphenyl (with 5% 4-benzyl pyridine). The complexes of the porphyrin oligomers with monodentate ligands (pyridine or 4-benzyl pyridine) principally adopt linear conformations. Nonlinear conformations are less populated in the lower glass-transition temperature solvent. When the oligomers bind star-shaped multidentate ligands, they are forced to bend into nonlinear geometries, and the experimental end-to-end distances for these complexes match those from molecular mechanics calculations. Our results show that porphyrin-based molecular wires are shape-persistent, and yet that their shapes can deformed by binding to multivalent ligands. Self-assembled ladder-shaped 2:2 complexes were also investigated to illustrate the scope of DEER measurements for providing structural information on synthetic noncovalent nanostructures.
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pubmed:language |
eng
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pubmed:journal | |
pubmed:citationSubset |
IM
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pubmed:chemical | |
pubmed:status |
MEDLINE
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pubmed:month |
Sep
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pubmed:issn |
1520-5126
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pubmed:author |
pubmed-author:AndersonHarry LHL,
pubmed-author:CnossenArjenA,
pubmed-author:HoffmannMarkusM,
pubmed-author:HogbenHannah JHJ,
pubmed-author:KayChristopher W MCW,
pubmed-author:LovettJanet EJE,
pubmed-author:PascuSofia ISI,
pubmed-author:ShutterAlexander T JAT,
pubmed-author:TimmelChristiane RCR,
pubmed-author:WarrenJohn EJE
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pubmed:issnType |
Electronic
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pubmed:day |
30
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pubmed:volume |
131
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pubmed:owner |
NLM
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pubmed:authorsComplete |
Y
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pubmed:pagination |
13852-9
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pubmed:meshHeading | |
pubmed:year |
2009
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pubmed:articleTitle |
Probing flexibility in porphyrin-based molecular wires using double electron electron resonance.
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pubmed:affiliation |
Centre for Advanced Electron Spin Resonance, Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QR, United Kingdom. janet.lovett@path.ox.ac.uk
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pubmed:publicationType |
Journal Article,
Research Support, Non-U.S. Gov't
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