Interface-enforced complexation between copolymer blocks

Steinschulte, Alexander A.; Xu, Weinan; Draber, Fabian M.; Hebbeker, Pascal; Jung, A; Bogdanovski, Dimitri; Schneider, Stefanie; Tsukruk, Vladimir V.; Plamper, Felix A.

doi:10.1039/c5sm00242g

Cited by 23 publications

(41 citation statements)

References 49 publications

(69 reference statements)

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“…The linear homopolymers (Fig. 3 red curve) have a single-stepped course, in agreement with literature 39 . The reason for this is that flexible polymers can fully spread and cover the interface uniformly 40 .…”

Section: Resultssupporting

confidence: 91%

“…The confinement of ULC microgels at oil–water interfaces makes their polymeric nature dominant over their colloidal behavior. The compression isotherms of ULC microgels show a single-step increase as expected for flexible homopolymers 39 . Their weakly crosslinked network spreads more than regular crosslinked microgels creating a homogeneous coverage similar to linear pNIPAM.…”

Section: Discussionmentioning

confidence: 57%

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Exploring the colloid-to-polymer transition for ultra-low crosslinked microgels from three to two dimensions

et al. 2019

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Microgels are solvent-swollen nano- and microparticles that show prevalent colloidal-like behavior despite their polymeric nature. Here we study ultra-low crosslinked poly( N -isopropylacrylamide) microgels (ULC), which can behave like colloids or flexible polymers depending on dimensionality, compression or other external stimuli. Small-angle neutron scattering shows that the structure of the ULC microgels in bulk aqueous solution is characterized by a density profile that decays smoothly from the center to a fuzzy surface. Their phase behavior and rheological properties are those of soft colloids. However, when these microgels are confined at an oil-water interface, their behavior resembles that of flexible macromolecules. Once monolayers of ultra-low crosslinked microgels are compressed, deposited on solid substrate and studied with atomic-force microscopy, a concentration-dependent topography is observed. Depending on the compression, these microgels can behave as flexible polymers, covering the substrate with a uniform film, or as colloidal microgels leading to a monolayer of particles.

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Section: Resultssupporting

confidence: 91%

Section: Discussionmentioning

confidence: 57%

Exploring the colloid-to-polymer transition for ultra-low crosslinked microgels from three to two dimensions

et al. 2019

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“…Either the dehydration of PPO has little or no influence on the copolymer association or PPO blocks directly associate with t BA units and no longer exist in hydrated form. Interactions of PPO with other moiety like poly(dimethylaminoethyl methacrylate) have already been reported in the literature …”

Section: Resultsmentioning

confidence: 99%

“…Interactions of PPO with other moiety like poly(dimethylaminoethyl methacrylate) have already been reported in the literature. 20,21 Hydrophobically Controlled Association Although incorporation of tBA units conceals the thermoresponsive behavior in the monophasic domain, it does not mean that the tBA/AA ratio has no influence on the selfassociation. Thus, following experiments were conducted at 25 8C.…”

Section: Temperature-controlled Associationmentioning

confidence: 99%

Hydrophobically controlled self‐association of pH‐ and thermo‐sensitive triblock copolymers based on poly(acrylic acid‐co‐tert‐butyl acrylate) and poly(propylene oxide)

Pottier

Morandi

Rihouey

et al. 2016

J Polym Sci B Polym Phys

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Aqueous solution properties of amphiphilic P(AAco-tBA)-b-PPO-b-P(AA-co-tBA) copolymers having various tBA contents are presented in this article. These copolymers show pH-sensitive behavior depending on tBA/AA ratio. Hydrophobic interactions between tBA units leading to pH-dependent macroscopic aggregates were evidenced by turbidimetry. The aggregation behavior of the PPO middle block was concealed in presence of tBA units. The formation of water-soluble aggregated objects was characterized by Asymmetrical Flow Field Flow Fractionation (AsF4). By increasing tBA/AA ratio, we observed an increase of aggregates size as well as a reduction of the critical concentration aggregation.

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“…To study the properties of such systems, we employed a generic model and performed simulations. So far, we have focused on star polymers and on the effect of architecture, interfaces, composition, and spacer polymers on the intramolecular complex formation. These insights will help to understand the experimental results from complex‐forming star‐shaped polymer systems .…”

Section: Introductionmentioning

confidence: 99%

Aggregation of Star Polymers: Complexation versus Segregation

Hebbeker

Plamper

Schneider

2018

Macro Theory & Simulations

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ionic complexes [23] due to the absence of long-ranged interactions. It is assumed that such complex-forming polymers form new structures, which would broaden the classical micellization scheme. [22] To study the properties of such systems, we employed a generic model and performed simulations. So far, we have focused on star polymers and on the effect of architecture, [24] interfaces, [25] composition, [26] and spacer polymers [27] on the intramolecular complex formation. These insights will help to understand the experimental results from complex-forming star-shaped polymer systems. [28,29] In this work, we investigate the effect of the intermolecular complexation on the aggregation behavior of star-shaped polymers.Star polymers are a well-studied class of polymer architectures. A subclass is the so-called miktoarm star polymers, which possess arms of different types emanating from the same core unit. Regular star polymers with only entropic interactions form the bridge between linear polymers and colloids and their phase diagram is well described. [30,31] When segregation is occurring, amphiphilic star polymers form diverse structures [32][33][34][35] and are able to form various micellar structures. [12,[36][37][38][39] As mentioned, we always looked at a single star polymer in the regime of infinite dilution and studied the intramolecular complexation up to now. To expand on this work, we now investigated how the complex-forming miktoarm star polymers behave when the concentration is high enough for intermolecular aggregation to occur. For segregating polymers, it is well known that they easily form micelles. [2,10,[40][41][42] For complexforming polyelectrolytes with substantial interaction strength, the structures of polyampholytes [43][44][45][46][47] and interpolyelectrolyte complexes [23,[48][49][50] are well investigated, often leading to micellar structures.In contrast, non-aggregating, but complex-forming starshaped polymers were observed experimentally as well (probably due to intermediate interaction strengths). [28] This is counter-intuitive, as one would expect that the attractive intermolecular interactions would lead to aggregation as was observed for segregating star polymers. [51,52] Our goal is to show whether star polymers which form complexes due to non-ionic interactions, aggregate. We investigate the aggregation behavior by calculating the effective interaction between the star polymers (and comparing it with theoretical results), by resolving the radial distribution function of star polymers in solution, quantifying the contact number and measuring the Star PolymersComplex-forming copolymers (polymers whose monomeric units of different type attract each other) are often discussed to be a pathway to achieve selfassembled structures, which differ from the classical micellization scheme. Here, coarse-grained Monte Carlo simulations are performed to investigate the aggregation behavior of miktoarm star polymers/diblock copolymers, which are able to form complexes between the constitutional ...

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Interface-enforced complexation between copolymer blocks

Cited by 23 publications

References 49 publications

Exploring the colloid-to-polymer transition for ultra-low crosslinked microgels from three to two dimensions

Exploring the colloid-to-polymer transition for ultra-low crosslinked microgels from three to two dimensions

Hydrophobically controlled self‐association of pH‐ and thermo‐sensitive triblock copolymers based on poly(acrylic acid‐co‐tert‐butyl acrylate) and poly(propylene oxide)

Aggregation of Star Polymers: Complexation versus Segregation

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