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PDBsum entry 3ef3
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References listed in PDB file
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Key reference
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Title
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Solid-State structural characterization of cutinase-Ece-Pincer-Metal hybrids.
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Authors
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L.Rutten,
B.Wieczorek,
J.P.Mannie,
C.A.Kruithof,
H.P.Dijkstra,
M.R.Egmond,
M.Lutz,
R.J.Klein gebbink,
P.Gros,
G.Van koten.
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Ref.
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Chemistry, 2009,
15,
4270-4280.
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PubMed id
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Abstract
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The first crystal structures of lipases that have been covalently modified
through site-selective inhibition by different organometallic
phosphonate-pincer-metal complexes are described. Two ECE-pincer-type d(8)-metal
complexes, that is, platinum (1) or palladium (2) with phosphonate esters (ECE =
[(EtO)-(O=)P(-O-C(6)H(4)-(NO(2))-4)(-C(3)H(6)-4-(C(6)H(2)-(CH(2)E)(2))](-); E =
NMe(2) or SMe) were introduced prior to crystallization and have been shown to
bind selectively to the Ser(120) residue in the active site of the lipase
cutinase to give cut-1 (platinum) or cut-2 (palladium) hybrids. For all five
presented crystal structures, the ECE-pincer-platinum or -palladium head group
sticks out of the cutinase molecule and is exposed to the solvent. Depending on
the nature of the ECE-pincer-metal head group, the ECE-pincer-platinum and
-palladium guests occupy different pockets in the active site of cutinase, with
concomitant different stereochemistries on the phosphorous atom for the cut-1
(S(P)) and cut-2 (R(P)) structures. When cut-1 was crystallized under
halide-poor conditions, a novel metal-induced dimeric structure was formed
between two cutinase-bound pincer-platinum head groups, which are interconnected
through a single mu-Cl bridge. This halide-bridged metal dimer shows that
coordination chemistry is possible with protein-modified pincer-metal complexes.
Furthermore, we could use NCN-pincer-platinum complex 1 as site-selective tool
for the phasing of raw protein diffraction data, which shows the potential use
of pincer-platinum complex 1 as a heavy-atom derivative in protein
crystallography.
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