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20231223105435.0 |
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231223s2006 xx ||||| 00| ||eng c |
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|a pubmed24n0553.xml
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|a (DE-627)NLM165783427
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|a (NLM)17019721
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|a DE-627
|b ger
|c DE-627
|e rakwb
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| 041 |
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|a eng
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| 100 |
1 |
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|a Gherman, Benjamin F
|e verfasserin
|4 aut
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| 245 |
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|a Characterization of the structure and reactivity of monocopper-oxygen complexes supported by beta-diketiminate and anilido-imine ligands
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| 264 |
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|c 2006
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| 336 |
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|a Text
|b txt
|2 rdacontent
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| 337 |
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|a ohne Hilfsmittel zu benutzen
|b n
|2 rdamedia
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| 338 |
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|a Band
|b nc
|2 rdacarrier
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| 500 |
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|a Date Completed 11.04.2007
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|a Date Revised 21.11.2013
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|a published: Print
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|a Citation Status MEDLINE
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|a Copper-oxygen complexes supported by beta-diketiminate and anilido-imine ligands have recently been reported (Aboelella et al., J Am Chem Soc 2004, 126, 16896; Reynolds et al., Inorg Chem 2005, 44, 6989) as potential biomimetic models for dopamine beta-monooxygenase (DbetaM) and peptidylglycine alpha-hydroxylating monooxygenase (PHM). However, in contrast to the enzymatic systems, these complexes fail to exhibit C--H hydroxylation activity (Reynolds et al., Chem Commun 2005, 2014). Quantum chemical characterization of the 1:1 Cu-O(2) model adducts and related species (Cu(III)-hydroperoxide, Cu(III)-oxo, and Cu(III)-hydroxide) indicates that the 1:1 Cu-O(2) adducts are unreactive toward substrates because of the weakness of the O--H bond that would be formed upon hydrogen-atom abstraction. This in turn is ascribed to the 1:1 adducts having both low reduction potentials and basicities. Cu(III)-oxo species on the other hand, determined to be intermediate between Cu(III)-oxo and Cu(II)-oxyl in character, are shown to be far more reactive toward substrates. Based on these results, design strategies for new DbetaM and PHM biomimetic ligands are proposed: new ligands should be made less electron rich so as to favor end-on dioxygen coordination in the 1:1 Cu-O(2) adducts. Comparison of the relative reactivities of the various copper-oxygen complexes as hydroxylating agents provides support for a Cu(II)-superoxide species as the intermediate responsible for substrate hydroxylation in DbetaM and PHM, and suggests that a Cu(III)-oxo intermediate would be competent in this process as well
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|a Journal Article
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|a Research Support, N.I.H., Extramural
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|a Research Support, U.S. Gov't, Non-P.H.S.
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| 650 |
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7 |
|a Imines
|2 NLM
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| 650 |
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7 |
|a Ligands
|2 NLM
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| 650 |
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|a Multienzyme Complexes
|2 NLM
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| 650 |
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|a Organometallic Compounds
|2 NLM
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| 650 |
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|a Copper
|2 NLM
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| 650 |
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|a 789U1901C5
|2 NLM
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| 650 |
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|a Mixed Function Oxygenases
|2 NLM
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| 650 |
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7 |
|a EC 1.-
|2 NLM
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| 650 |
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|a Dopamine beta-Hydroxylase
|2 NLM
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| 650 |
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7 |
|a EC 1.14.17.1
|2 NLM
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| 650 |
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7 |
|a peptidylglycine monooxygenase
|2 NLM
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| 650 |
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7 |
|a EC 1.14.17.3
|2 NLM
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| 650 |
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|a Oxygen
|2 NLM
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| 650 |
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|a S88TT14065
|2 NLM
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| 700 |
1 |
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|a Tolman, William B
|e verfasserin
|4 aut
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| 700 |
1 |
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|a Cramer, Christopher J
|e verfasserin
|4 aut
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| 773 |
0 |
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|i Enthalten in
|t Journal of computational chemistry
|d 1984
|g 27(2006), 16 vom: 01. Dez., Seite 1950-61
|w (DE-627)NLM098138448
|x 1096-987X
|7 nnns
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| 773 |
1 |
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|g volume:27
|g year:2006
|g number:16
|g day:01
|g month:12
|g pages:1950-61
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|a GBV_USEFLAG_A
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|a SYSFLAG_A
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|a GBV_NLM
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|a GBV_ILN_350
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| 951 |
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|a AR
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|d 27
|j 2006
|e 16
|b 01
|c 12
|h 1950-61
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