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@ARTICLE{Rudani:1047243,
author = {Rudani, Binny A. and Docter, Steffen and Schott-Verdugo,
Stephan and Buitenhuis, Johan and Stadler, Andreas M. and
Gohlke, Holger and Wiegand, Simone},
title = {{I}nfluence of α-{H}elical {C}ontent on the
{T}hermodiffusion of {A}pomyoglobin},
journal = {Langmuir},
volume = {41},
number = {42},
issn = {0743-7463},
address = {Washington, DC},
publisher = {ACS Publ.},
reportid = {FZJ-2025-04174},
pages = {28322–28334},
year = {2025},
note = {This is an OA article.},
abstract = {Apo-myoglobin (Apo-Mb) is an extensively studied model
system for investigating protein folding due to its distinct
stable native, partially folded molten globule (MG), and
${\color{black}$ unfolded} states at acidic pH. This study
examines the impact of structural conformational changes on
the thermodiffusive behavior of Apo-Mb using the infrared
thermal diffusion forced Rayleigh scattering (TDFRS)
technique. The conformational states were modulated by
varying pH and buffer conditions, with their structural
changes confirmed via circular dichroism (CD) spectroscopy.
The $\alpha$-helical content decreased with decreasing pH.
The thermodiffusion parameter $\Delta S_{\mathrm{T}}(\Delta
T)$, a measure of the temperature sensitivity of the Soret
coefficient $S_{\mathrm{T}}$, also showed a decrease, which
is typically related to a decreasing hydrophilicity of the
solute. Additionally, the buffer composition significantly
influenced the thermodiffusive behavior: phosphate buffer
promoted Apo-Mb aggregation through electrostatic screening,
whereas acetate buffer favored Apo-Mb solubilization.
Microsecond-long discrete protonation state constant pH
molecular dynamics (CpHMD) simulations support the
experimentally observed, pH- and buffer-dependent changes in
$\alpha$-helical content and highlight the differences in
protein-buffer interactions for phosphate buffer versus
acetate buffer. In conclusion, a strong correlation was
observed between the thermodiffusion parameter $\Delta
S_{\mathrm{T}}(\Delta T)$ and the $\alpha$-helical content,
with $\Delta S_{\mathrm{T}}(\Delta T)$ increasing alongside
hydrophilicity and $\alpha$-helical content. These findings
highlight the role of structural conformation and buffer
environment in modulating the thermodiffusive properties of
proteins.},
cin = {IBG-4 / IBI-4 / JCNS-1},
ddc = {540},
cid = {I:(DE-Juel1)IBG-4-20200403 / I:(DE-Juel1)IBI-4-20200312 /
I:(DE-Juel1)JCNS-1-20110106},
pnm = {2172 - Utilization of renewable carbon and energy sources
and engineering of ecosystem functions (POF4-217) / 323 -
Molecular Targets $\&$ Therapies (POF4-323) / 5241 -
Molecular Information Processing in Cellular Systems
(POF4-524) / IHRS-BioSoft - International Helmholtz Research
School of Biophysics and Soft Matter
(IHRS-BioSoft-20061101)},
pid = {G:(DE-HGF)POF4-2172 / G:(DE-HGF)POF4-323 /
G:(DE-HGF)POF4-5241 / G:(DE-Juel1)IHRS-BioSoft-20061101},
typ = {PUB:(DE-HGF)16},
doi = {10.1021/acs.langmuir.5c02797},
url = {https://juser.fz-juelich.de/record/1047243},
}