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@ARTICLE{Hochdrffer:16633,
author = {Hochdörffer, K. and März-Berberich, J. and Nagel-Steger,
L. and Epple, M. and Meyer-Zaika, W. and Horn, A.H. and
Sticht, H. and Sinha, S. and Bitan, G. and Schrader, T.},
title = {{R}ational {D}esign of ß-{S}heet {L}igands {A}gainst
{A}ß(42)-{I}nduced {T}oxicity},
journal = {Journal of the American Chemical Society},
volume = {133},
issn = {0002-7863},
address = {Washington, DC},
publisher = {American Chemical Society},
reportid = {PreJuSER-16633},
pages = {4348 - 4358},
year = {2011},
note = {Financial support from the American Health Assistance
Foundation (grant A2008-350) and the UCLA Jim Easton
Consortium for Alzheimer's Drug Discovery and Biomarker
Development is gratefully acknowledged. This work was also
supported by the Deutsche Forschungsgemeinschaft and the
Volkswagen foundation.},
abstract = {A β-sheet-binding scaffold was equipped with long-range
chemical groups for tertiary contacts toward specific
regions of the Alzheimer's Aβ fibril. The new constructs
contain a trimeric aminopyrazole carboxylic acid, elongated
with a C-terminal binding site, whose influence on the
aggregation behavior of the Aβ(42) peptide was studied. MD
simulations after trimer docking to the anchor point
(F19/F20) suggest distinct groups of complex structures each
of which featured additional specific interactions with
characteristic Aβ regions. Members of each group also
displayed a characteristic pattern in their
antiaggregational behavior toward Aβ. Specifically, remote
lipophilic moieties such as a dodecyl, cyclohexyl, or LPFFD
fragment can form dispersive interactions with the nonpolar
cluster of amino acids between I31 and V36. They were shown
to strongly reduce Thioflavine T (ThT) fluorescence and
protect cells from Aβ lesions (MTT viability assays).
Surprisingly, very thick fibrils and a high β-sheet content
were detected in transmission electron microscopy (TEM) and
CD spectroscopic experiments. On the other hand, distant
single or multiple lysines which interact with the ladder of
stacked E22 residues found in Aβ fibrils completely
dissolve existing β-sheets (ThT, CD) and lead to
unstructured, nontoxic material (TEM, MTT). Finally, the
triethyleneglycol spacer between heterocyclic β-sheet
ligand and appendix was found to play an active role in
destabilizing the turn of the U-shaped protofilament.
Fluorescence correlation spectroscopy (FCS) and
sedimentation velocity analysis (SVA) provided experimental
evidence for some smaller benign aggregates of very thin,
delicate structure (TEM, MTT). A detailed investigation by
dynamic light scattering (DLS) and other methods proved that
none of the new ligands acts as a colloid. The evolving
picture for the disaggregation mechanism by these new hybrid
ligands implies transformation of well-ordered fibrils into
less structured aggregates with a high molecular weight. In
the few cases where fibrillar components remain, these
display a significantly altered morphology and have lost
their acute cellular toxicity.},
keywords = {Amyloid beta-Peptides: antagonists $\&$ inhibitors /
Amyloid beta-Peptides: toxicity / Binding Sites: drug
effects / Ligands / Models, Molecular / Molecular Structure
/ Peptide Fragments: antagonists $\&$ inhibitors / Peptide
Fragments: toxicity / Protein Structure, Secondary /
Pyrazoles: chemical synthesis / Pyrazoles: chemistry /
Pyrazoles: pharmacology / Structure-Activity Relationship /
Amyloid beta-Peptides (NLM Chemicals) / Ligands (NLM
Chemicals) / Peptide Fragments (NLM Chemicals) / Pyrazoles
(NLM Chemicals) / amyloid beta-protein (1-42) (NLM
Chemicals) / J (WoSType)},
cin = {ICS-6},
ddc = {540},
cid = {I:(DE-Juel1)ICS-6-20110106},
pnm = {Funktion und Dysfunktion des Nervensystems / BioSoft:
Makromolekulare Systeme und biologische
Informationsverarbeitung},
pid = {G:(DE-Juel1)FUEK409 / G:(DE-Juel1)FUEK505},
shelfmark = {Chemistry, Multidisciplinary},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:21381732},
UT = {WOS:000291715300041},
doi = {10.1021/ja107675n},
url = {https://juser.fz-juelich.de/record/16633},
}