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@PHDTHESIS{Weirich:836105,
author = {Weirich, Franziska},
title = {{S}tructural characterization of recombinant fibrillar
human {I}slet {A}myloid {P}olypeptide by solid-state
{N}uclear {M}agnetic {R}esonance {S}pectroscopy},
school = {HHU Düsseldorf},
type = {Dissertation},
reportid = {FZJ-2017-05229},
pages = {114 p},
year = {2017},
note = {Dissertation, HHU Düsseldorf, 2017},
abstract = {In this thesis, the method of solid-state Nuclear Magnetic
Resonance spectroscopy was applied to solve a specific
question from the field of protein misfolding diseases.
Representatives of protein misfolding diseases are diabetes
mellitus type II, Alzheimer´s disease, and Parkinson´s
disease. A hallmark of protein misfolding diseases is the
extracellular deposition of misfolded proteins, either
localized in affected tissue, or systemic throughout the
body. The process of protein misfolding leads in many cases
to the formation of insoluble amyloid fibrils. Amyloid
fibrils formed by a range of different proteins show a
highly ordered and repetitive structure, which is rich in
β-sheet content. Elucidation of fibril structures on the
molecular level is one of the central research topics in the
field of protein misfolding diseases.The topic of this
dissertation was the structural characterization of
fibrillar human Islet-Amyloid-Polypeptide (IAPP) by
solid-state NMR. IAPP is a 37 amino acid residue peptide
that is cosecreted with insulin by pancreatic β-cells. IAPP
is soluble and intrinsically disordered in its physiological
form, however it shows a high propensity to aggregation and
fibril formation. Pancreatic amyloid deposits, which consist
mainly of IAPP, correlate with type II diabetes mellitus and
are found in $90\%$ of individuals affected by T2DM. Human
IAPP has an oxidized disulfide bridge in its N-terminus and
an amidated C-terminus. In this thesis, recombinantly
expressed IAPP with an intact disulfide bridge, but without
an amidated C-terminus, was used. It is denoted as
IAPPCOOH.Solid-state NMR is a versatile tool to study the
structure of fibrils built from full length proteins. These
samples are not amenable to X-ray crystallography or
liquid-state NMR, because they are non-crystalline and
insoluble. Solid-state NMR studies on biomolecules are based
on the NMR active isotopes 1H, 13C, and 15N, employing
isotope labelling strategies. Information on secondary and
tertiary structure is contained in chemical shifts and
strengths of dipolar couplings. A full site-specific
resonance assignment was achieved from the ssNMR study on
fibrillar IAPP. An analysis of secondary structure was
performed based on the chemical shifts. One major
conformation was observed, consisting of three β-strands.
The amyloidogenic segment 22NFGAILS28was also found to be
part of a β-strand. Furthermore, the N-terminus showed well
resolved and intense peaks at 0°C, that broadened below
detectability upon freezing to -170°C. These results have
been published in the journal PLoS One in 2016. Following
experiments aimed at the detection of through-space dipolar
couplings, which contain information on the tertiary
structure of the molecules within the fibril. Two more
samples were prepared, applying a labelling approach that
yields a diluted distribution of 13C spins in the samples.
The dilution of NMR-active spins enables the detection of
weak through-space dipolar couplings, which are attenuated
in uniformly labelled samples by the effect of dipolar
truncation. Complementary, long mixing time 13C-13C
correlation experiments were performed on a diluted (1:4)
and an uniformly labelled sample. Four ambiguous long-range
cross-peaks were observed in these spectra. They could
contain information on the tertiary fold of the molecules
within the fibrils. Four ambiguous distance restraints were
created from these cross-peaks and used in a first structure
calculation with the computer program Cyana. Moreover, based
on the analysis of secondary structure and the varying
intensity of Cα-Cβ crosspeaks in short mixing time PDSD
spectra, two more structural models were created.},
cin = {ICS-6},
cid = {I:(DE-Juel1)ICS-6-20110106},
pnm = {553 - Physical Basis of Diseases (POF3-553)},
pid = {G:(DE-HGF)POF3-553},
typ = {PUB:(DE-HGF)11},
url = {https://juser.fz-juelich.de/record/836105},
}