| pubmed-article:12817956 | rdf:type | pubmed:Citation | lld:pubmed |
| pubmed-article:12817956 | lifeskim:mentions | umls-concept:C0332307 | lld:lifeskim |
| pubmed-article:12817956 | lifeskim:mentions | umls-concept:C0205131 | lld:lifeskim |
| pubmed-article:12817956 | lifeskim:mentions | umls-concept:C0205145 | lld:lifeskim |
| pubmed-article:12817956 | lifeskim:mentions | umls-concept:C0064566 | lld:lifeskim |
| pubmed-article:12817956 | lifeskim:mentions | umls-concept:C1704675 | lld:lifeskim |
| pubmed-article:12817956 | lifeskim:mentions | umls-concept:C1280500 | lld:lifeskim |
| pubmed-article:12817956 | lifeskim:mentions | umls-concept:C0205419 | lld:lifeskim |
| pubmed-article:12817956 | lifeskim:mentions | umls-concept:C0521033 | lld:lifeskim |
| pubmed-article:12817956 | lifeskim:mentions | umls-concept:C0205217 | lld:lifeskim |
| pubmed-article:12817956 | lifeskim:mentions | umls-concept:C0023688 | lld:lifeskim |
| pubmed-article:12817956 | lifeskim:mentions | umls-concept:C0013850 | lld:lifeskim |
| pubmed-article:12817956 | lifeskim:mentions | umls-concept:C0678594 | lld:lifeskim |
| pubmed-article:12817956 | lifeskim:mentions | umls-concept:C1880022 | lld:lifeskim |
| pubmed-article:12817956 | pubmed:issue | 13 | lld:pubmed |
| pubmed-article:12817956 | pubmed:dateCreated | 2003-6-23 | lld:pubmed |
| pubmed-article:12817956 | pubmed:abstractText | A variety of spectroscopic techniques, combined with density functional calculations, are used to describe the electronic structure of the Leu513His variant of the type 1 Cu site in Myceliophthora thermophila laccase. This mutation changes the type 1 Cu from a blue to a green site. Electron paramagnetic resonance (EPR), optical absorption, circular dichroism, and magnetic circular dichroism (MCD) spectroscopies reveal that, relative to the trigonal planar blue type 1 Cu site in wild-type fungal laccase, the covalency and the ligand field strength at the Leu513His green type 1 Cu center decrease. Additionally, there is a significant reorientation of the d(x)()()2(-)(y)()()2( )singly occupied MO, such that the overlap with the Cys sulfur valence orbital changes from pi to sigma. A density functional study in which internal coordinates are systematically altered reveals that these changes are due to the increased strength of the axial ligand (none to His), leading to a tetragonal distortion and elongation of the equatorial Cu-ligand bonds. These calculations provide insight into the experimental differences in the EPR parameters, charge-transfer absorption spectrum, and ligand-field MCD spectrum between the axial-His variant and blue Cu centers (plastocyanin and the type 1 site in fungal laccase). There are also significant differences between the green site in the Leu513His variant and other naturally occurring, green type 1 Cu sites such as in nitrite reductase, which have short axial Cu-S(Met) bonds. The large difference in EPR parameters between these green type 1 sites derives from a change in ligand field excitation energies observed by MCD, which reflects a decrease in ligand field strength. This is associated with different steric interactions of a His vs an axial Met ligand in a tetragonally distorted type 1 site. Changes in the electronic structure of the Cu site correlate with the difference in reactivity of the green His variant relative to blue wild-type fungal laccase. | lld:pubmed |
| pubmed-article:12817956 | pubmed:grant | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:12817956 | pubmed:language | eng | lld:pubmed |
| pubmed-article:12817956 | pubmed:journal | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:12817956 | pubmed:citationSubset | IM | lld:pubmed |
| pubmed-article:12817956 | pubmed:chemical | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:12817956 | pubmed:chemical | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:12817956 | pubmed:chemical | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:12817956 | pubmed:chemical | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:12817956 | pubmed:chemical | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:12817956 | pubmed:chemical | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:12817956 | pubmed:status | MEDLINE | lld:pubmed |
| pubmed-article:12817956 | pubmed:month | Jun | lld:pubmed |
| pubmed-article:12817956 | pubmed:issn | 0020-1669 | lld:pubmed |
| pubmed-article:12817956 | pubmed:author | pubmed-author:SolomonEdward... | lld:pubmed |
| pubmed-article:12817956 | pubmed:author | pubmed-author:GEARJJ | lld:pubmed |
| pubmed-article:12817956 | pubmed:author | pubmed-author:PalmerAmy EAE | lld:pubmed |
| pubmed-article:12817956 | pubmed:author | pubmed-author:SzilagyiRober... | lld:pubmed |
| pubmed-article:12817956 | pubmed:author | pubmed-author:CherryJoel... | lld:pubmed |
| pubmed-article:12817956 | pubmed:author | pubmed-author:JonesAubreyA | lld:pubmed |
| pubmed-article:12817956 | pubmed:issnType | Print | lld:pubmed |
| pubmed-article:12817956 | pubmed:day | 30 | lld:pubmed |
| pubmed-article:12817956 | pubmed:volume | 42 | lld:pubmed |
| pubmed-article:12817956 | pubmed:owner | NLM | lld:pubmed |
| pubmed-article:12817956 | pubmed:authorsComplete | Y | lld:pubmed |
| pubmed-article:12817956 | pubmed:pagination | 4006-17 | lld:pubmed |
| pubmed-article:12817956 | pubmed:dateRevised | 2008-11-21 | lld:pubmed |
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| pubmed-article:12817956 | pubmed:meshHeading | pubmed-meshheading:12817956... | lld:pubmed |
| pubmed-article:12817956 | pubmed:year | 2003 | lld:pubmed |
| pubmed-article:12817956 | pubmed:articleTitle | Spectroscopic characterization of the Leu513His variant of fungal laccase: effect of increased axial ligand interaction on the geometric and electronic structure of the type 1 Cu site. | lld:pubmed |
| pubmed-article:12817956 | pubmed:affiliation | Department of Chemistry, Stanford University, Stanford, California 94305 and Novozymes Biotech, Davis, California 95616, USA. | lld:pubmed |
| pubmed-article:12817956 | pubmed:publicationType | Journal Article | lld:pubmed |
| pubmed-article:12817956 | pubmed:publicationType | Research Support, U.S. Gov't, P.H.S. | lld:pubmed |
| pubmed-article:12817956 | pubmed:publicationType | Research Support, Non-U.S. Gov't | lld:pubmed |
| http://linkedlifedata.com/r... | pubmed:referesTo | pubmed-article:12817956 | lld:pubmed |
