4 research outputs found
Small Surfactant Concentration Differences Influence Adsorption of Human Serum Albumin on Polystyrene Nanoparticles
Surfactants,
even in miniscule amounts, are often used for the
synthesis and especially the stabilization of nanomaterials, which
is essential for in vivo applications. In this study, we show that
the interaction between nanoparticles and proteins strongly depends
on the type of stabilizing surfactants and their (small) concentration
changes. The reaction between human serum albumin and polystyrene
nanoparticles stabilized by an ionic or nonionic surfactantsodium
dodecyl sulfate or Lutensol AT50, respectivelywas monitored
using isothermal titration calorimetry. It was found that the amount
of surfactant molecules on the surface significantly determines the
protein binding affinity and adsorption stoichiometry, which is important
for all nanomaterials coming into contact with biological components
such as blood plasma proteins. Thus after synthesizing nanomaterials
for in vivo applications as drug delivery agents, it is crucial to
perform a detailed analysis of the obtained surface chemistry that
accounts for the presence of minimal amounts of stabilizing agents
Alternative Pathway for the Stabilization of Reactive Emulsions via Cross-Linkable Surfactants
Highly reactive emulsions were stabilized
by employing a surfmer
analogous concept. An interfacial reaction between an emulsion droplet
and a cross-linkable reactive surfactant was used to provide colloidal
stability and simultaneously maintain the majority of the reactive
groups. Polyaddition-type reaction between epoxy and amine was chosen
as a model system to spontaneously and covalently bond the surfactant
to the emulsion droplets. The interfacial reaction was monitored via
isothermal titration calorimetry analysis. With this method, the increased
colloidal stability could be attributed to a reaction rather than
a pure physical adsorption. The maintained reactivity of the emulsion
droplets enables consecutive conversions with coreactive components,
e.g., for cross-linking reactions, corrosion protection, or functional
coatings
Polyvinylferrocene-Based Amphiphilic Block Copolymers Featuring Functional Junction Points for Cross-Linked Micelles
The
synthesis of high-molecular-weight, well-defined poly(vinylferrocene)-<i>block</i>-poly(ethylene glycol) (PVFc-<i>b</i>-PEG)
diblock copolymers (<i>M</i><sub>n</sub> = 13 000–44 000
g mol<sup>–1</sup>; <i>Đ</i> = 1.29–1.34)
with precisely one allyl group at the junction point is introduced.
Allyl glycidyl ether (AGE) was used to end-functionalize PVFc, resulting
in hydroxyl functional macroinitiators for the oxyanionic polymerization
of ethylene oxide. The self-assembly behavior of the amphiphilic PVFc-<i>b</i>-PEG copolymers in water has been investigated in a detailed
manner, using dynamic light scattering (DLS) and transmission electron
microscopy (TEM). The redox activity of the PVFc block was confirmed
by UV/vis spectroscopy, while cyclovoltammetry (CV) measurements were
carried out to support the stability and full reversibility of the
ferrocene/ferrocenium redox couple. Both formation and dissociation
of the macromolecular self-assemblies in aqueous solution via oxidation
and reduction of the PVFc segments were evidenced by TEM and DLS.
The dye Nile Red was used as model compound to investigate the stabilization
of a water-insoluble molecule in aqueous solution by the block copolymers
via encapsulation inside micellar structures. Oxidation of the PVFc
segments lead to instantaneous and quantitative release of the dye.
Furthermore, incorporation of the allyl moiety at the block junction
point was used to cross-link the shell of the compartments. By this
strategy a stable incorporation of the dye was achieved while triggered
release via oxidation led to quantitative liberation
Redox-Responsive Block Copolymers: Poly(vinylferrocene)‑<i>b</i>‑poly(lactide) Diblock and Miktoarm Star Polymers and Their Behavior in Solution
The synthesis of diblock and miktoarm
star polymers containing
poly(vinylferrocene) (PVFc) and poly(l-lactide) (PLA) blocks
is introduced. End functionalization of PVFc was carried out via end
capping of living carbanionic PVFc chains with benzyl glycidyl ether
(BGE). By hydrogenolysis of the benzyl protecting group a dihydroxyl
end-functionalized PVFc was obtained. Both monohydroxyl- and dihydroxyl-functionalized
PVFcs have been utilized as macroinitiators for the subsequent polymerization
of l-lactide via catalytic ring-opening polymerization. A
series of block copolymers and AB<sub>2</sub> miktoarm star polymers
was synthesized with varied PLA chain lengths. All polymers were characterized
in detail, using <sup>1</sup>H NMR spectroscopy, size exclusion chromatography
(SEC), and matrix-assisted laser desorption/ionization time-of-flight
mass spectrometry (MALDI-ToF). The molecular weight of the block copolymers
and AB<sub>2</sub> miktoarm star polymers are in the range of 8000–15000,
containing a PVFc block of weight 7800. In addition, the self-assembly
behavior of the polymers in dichloromethane (CH<sub>2</sub>Cl<sub>2</sub>) was investigated by using dynamic light scattering (DLS)
and transmission electron microscopy (TEM). In a selective solvent
for PLA the block copolymers and miktoarm star polymers formed vesicle-like
structures with different diameters