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@PHDTHESIS{Vakili:422891,
author = {Vakili, Mohammad},
othercontributors = {Trebbin, Martin and Pearson, Arwen},
title = {{M}icrofluidic {S}ample {E}nvironments for {T}ime-resolved
{M}acromolecular {S}tructure {F}ormation {S}tudies},
school = {University of Hamburg},
type = {Dissertation},
address = {Hamburg},
reportid = {PUBDB-2019-02383},
pages = {186},
year = {2019},
note = {Dissertation, University of Hamburg, 2019},
abstract = {This thesis deals with the polymerization-induced
self-assembly (PISA) of amphiphilic blockcopolymer
nano-objects, which were synthesized using a controlled
radical polymerization(CRP) method, in particular, the
reversible addition-fragmentation chain-transfer
(RAFT)aqueous polymerization in the presence of a
poly(N,N-dimethylacrylamide) stabilizer agent(macro RAFT
agent). Besides the use of N-isopropylacrylamide (NIPAm) as
core-formingblock for thermo-responsive nanoparticle, the
aqueous dispersion polymerization of 2-methoxyethyl acrylate
(MEA) was pursued as a model to study
hydrophilic-hydrophobic phasetransitions: as a monomer, MEA
is water-soluble. However, upon chain growth, the
poly(MEA)block becomes hydrophobic which eventually drives
micellar self-assembly. The underlyingprocesses and the time
scales of the self-assembly are still not completely
understood.Finding the answers to such questions can be
answered by the investigation of a system’s
timeresolvedreaction kinetics and structural dynamics in
situ. However, it can be challenging tocontrol the
experimental conditions accurately, such as the precise
initiation of a reaction byrapid mixing. This challenge can
be overcome by using microfluidic reaction systems
whichenable precise control over fluids within micron-sized
channels. These very well defined flowand reaction
conditions make microfluidics predestined for the
time-resolved studies ofpolymers using X-ray sources. In
microfluidic laminar flows, the temporal structural
evolutionduring a polymerization process can be mapped onto
different positions in the downstreammicrochannel. Besides
the ability to access time scales down to the
microseconds-scale, thisapproach has many advantages
compared to more traditional set-ups in terms of a low
sampleconsumption (experiments on the nanoliter scale),
highly efficient and homogeneous mixing bydiffusion, as well
as the possibility to adjust the temporal resolution by
manipulation of the flowrates.Microfluidic channels can be
fabricated using a number of different materials, each
havingdifferent optical and mechanical properties as well as
manufacturing challenges: glass, metaland most importantly
polymers, such as polydimethylsiloxane (PDMS), thermoplastic
cyclicolefin copolymers (TOPAS® COC) or highly inert
polyimide films (Kapton®) are currentlyused. With the
advent of more powerful and brighter X-ray sources, COCs and
Kapton inparticular have received tremendous interest as
sample environment due to their X-raycompatibility and low
background signal. Another approach for low-background
sampleenvironments are microfluidic liquid jet devices based
on the gas dynamic virtual nozzle(GDVN) design. These
devices contain a network of very narrow channels and
nozzles andprovide a very defined free-flowing sample stream
in vacuum, making them especiallydesirable for experiments
at X-ray free electron laser (XFEL) facilities.In this work,
the tailored design, fabrication and experimental
implementation of novelmicrofluidic sample environments that
address specific experimental conditions for
controlledradical polymerization are described. In
particular, these devices were applied to in situ
timeresolveddiffusive mixing experiments to access very
early stages of the PISA reaction. In situhere means
monitoring the structural changes during chain growth/phase
transition by probingthe sample with X-rays while the
polymerization/self-assembly occurs.Supported by
complimentary dynamic light scattering (DLS) experiments,
fluorescentmicroscopy and 3D finite-element computational
fluid dynamics (CFD) simulations, theinsights of these
experiments aim to provide a better understanding of
amphiphilic blockcopolymer self-assembly and, in general,
may help to tailor polymers for their specificapplications,
such as micellar drug delivery vehicles in medical
applications.},
cin = {UNI/CUI / UNI/PHY / UNI/INF},
cid = {$I:(DE-H253)UNI_CUI-20121230$ /
$I:(DE-H253)UNI_PHY-20170505$ /
$I:(DE-H253)UNI_INF-20151211$},
pnm = {6G3 - PETRA III (POF3-622) / DFG project 194651731 - EXC
1074: Hamburger Zentrum für ultraschnelle Beobachtung
(CUI): Struktur, Dynamik und Kontrolle von Materie auf
atomarer Skala (194651731) / PHGS, VH-GS-500 - PIER
Helmholtz Graduate School $(2015_IFV-VH-GS-500)$},
pid = {G:(DE-HGF)POF3-6G3 / G:(GEPRIS)194651731 /
$G:(DE-HGF)2015_IFV-VH-GS-500$},
experiment = {EXP:(DE-H253)P-P03-20150101 /
EXP:(DE-H253)CFEL-Exp-20150101 /
EXP:(DE-MLZ)External-20140101},
typ = {PUB:(DE-HGF)11},
doi = {10.3204/PUBDB-2019-02383},
url = {https://bib-pubdb1.desy.de/record/422891},
}