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1.
Macromol Rapid Commun ; 44(3): e2200682, 2023 Feb.
Article in English | MEDLINE | ID: mdl-36285394

ABSTRACT

The unique corona structure of surface-compartmentalized micelles (Janus micelles, patchy micelles) opens highly relevant applications, e.g. as efficient particulate surfactants for emulsion stabilization or compatibilization of polymer blends. Here, stereocomplex-driven self-assembly (SCDSA) as a facile route to micelles with a semicrystalline stereocomplex (SC) core and a patch-like microphase separated corona, employing diblock copolymers with enantiomeric poly(L-lactide)/poly(D-lactide) blocks and highly incompatible corona-forming blocks (polystyrene (PS), poly(tert-butyl methacrylate)) is introduced. The spherical patchy SC micelles feature a narrow size distribution and show a compartmentalized, shamrock-like corona structure. Compared to SC micelles with a homogeneous PS corona the patchy micelles have a significantly higher interfacial activity attributable to the synergistic combination of an amphiphilic corona with the Pickering effect of nanoparticles. The patchy micelles are successfully employed in the stabilization of emulsions, underlining their application potential.


Subject(s)
Micelles , Nanoparticles , Polymers/chemistry , Nanoparticles/chemistry , Surface-Active Agents
2.
Macromol Rapid Commun ; 43(12): e2200052, 2022 Jun.
Article in English | MEDLINE | ID: mdl-35320608

ABSTRACT

Functional, hierarchically mesostructured nonwovens are of fundamental importance because complex fiber morphologies increase the active surface area and functionality allowing for the effective immobilization of metal nanoparticles. Such complex functional fiber morphologies clearly widen the property profile and enable the preparation of more efficient and selective filter media. Here, the realization of hierarchically mesostructured nonwovens with barbed wire-like morphology is demonstrated by combining electrospun polystyrene fibers, decorated with patchy worm-like micelles, with solution-processed supramolecular short fibers composed of 1,3,5-benzenetricarboxamides with peripheral N,N-diisopropylaminoethyl substituents. The worm-like micelles with a patchy microphase-separated corona are prepared by crystallization-driven self-assembly of a polyethylene based triblock terpolymer and deposited on top of the polystyrene fibers by coaxial electrospinning. The micelles are designed in a way that their patches promote the directed self-assembly of the 1,3,5-benzenetricarboxamide and the fixation of the supramolecular nanofibers on the supporting polystyrene fibers. Functionality of the mesostructured nonwoven is provided by the peripheral N,N-diisopropylaminoethyl substituents of the 1,3,5-benzenetricarboxamide and proven by the effective immobilization of individual palladium nanoparticles on the supramolecular nanofibers. The preparation of hierarchically mesostructured nonwovens and their shown functionality demonstrate that such systems are attractive candidates to be used for example in filtration, selective separation and heterogenous catalysis.


Subject(s)
Metal Nanoparticles , Nanofibers , Micelles , Palladium , Polymers , Polystyrenes
3.
Angew Chem Int Ed Engl ; 61(15): e202117570, 2022 04 04.
Article in English | MEDLINE | ID: mdl-35129881

ABSTRACT

Responsive fluorescent materials offer a high potential for sensing and (bio-)imaging applications. To investigate new concepts for such materials and to broaden their applicability, the previously reported non-fluorescent zinc(II) complex [Zn(L)] that shows coordination-induced turn-on emission was encapsulated into a family of non-fluorescent polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) diblock copolymer micelles leading to brightly emissive materials. Coordination-induced turn-on emission upon incorporation and ligation of the [Zn(L)] in the P4VP core outperform parent [Zn(L)] in pyridine solution with respect to lifetimes, quantum yields, and temperature resistance. The quantum yield can be easily tuned by tailoring the selectivity of the employed solvent or solvent mixture and, thus, the tendency of the PS-b-P4VP diblock copolymers to self-assemble into micelles. A medium-dependent off-on sensor upon micelle formation could be established by suppression of non-micelle-borne emission background pertinent to chloroform through controlled acidification indicating an additional pH-dependent process.


Subject(s)
Micelles , Polymers , Solvents
4.
Polymers (Basel) ; 13(24)2021 Dec 13.
Article in English | MEDLINE | ID: mdl-34960909

ABSTRACT

The confinement assembly of block copolymers shows great potential regarding the formation of functional microparticles with compartmentalized structure. Although a large variety of block chemistries have already been used, less is known about microdomain degradation, which could lead to mesoporous microparticles with particularly complex morphologies for ABC triblock terpolymers. Here, we report on the formation of triblock terpolymer-based, multicompartment microparticles (MMs) and the selective degradation of domains into mesoporous microparticles. A series of polystyrene-block-polybutadiene-block-poly(L-lactide) (PS-b-PB-b-PLLA, SBL) triblock terpolymers was synthesized by a combination of anionic vinyl and ring-opening polymerization, which were transformed into microparticles through evaporation-induced confinement assembly. Despite different block compositions and the presence of a crystallizable PLLA block, we mainly identified hexagonally packed cylinders with a PLLA core and PB shell embedded in a PS matrix. Emulsions were prepared with Shirasu Porous Glass (SPG) membranes leading to a narrow size distribution of the microparticles and control of the average particle diameter, d ≈ 0.4 µm-1.8 µm. The core-shell cylinders lie parallel to the surface for particle diameters d < 0.5 µm and progressively more perpendicular for larger particles d > 0.8 µm as verified with scanning and transmission electron microscopy and particle cross-sections. Finally, the selective degradation of the PLLA cylinders under basic conditions resulted in mesoporous microparticles with a pronounced surface roughness.

5.
J Am Chem Soc ; 143(38): 15582-15586, 2021 Sep 29.
Article in English | MEDLINE | ID: mdl-34529422

ABSTRACT

Surface-compartmentalized micellar nanostructures (Janus and patchy micelles) have gained increasing interest due to their unique properties opening highly relevant applications, e.g., as efficient particulate surfactants, compatibilizers in polymer blends, or templates for catalytically active nanoparticles. We present a facile method for the production of worm-like Janus micelles based on crystallization-driven self-assembly of a double-crystalline triblock terpolymer with a crystallizable polyethylene middle block and two highly incompatible corona blocks, polystyrene and poly(ethylene oxide). This approach enables the production of amphiphilic Janus micelles with excellent interfacial activity by a comparably simple heating and cooling protocol directly in solution.

6.
Polymers (Basel) ; 13(9)2021 May 04.
Article in English | MEDLINE | ID: mdl-34064413

ABSTRACT

Crystallization-driven self-assembly (CDSA) of block copolymers bearing one crystallizable block has emerged to be a powerful and highly relevant method for the production of one- and two-dimensional micellar assemblies with controlled length, shape, and corona chemistries. This gives access to a multitude of potential applications, from hierarchical self-assembly to complex superstructures, catalysis, sensing, nanomedicine, nanoelectronics, and surface functionalization. Related to these applications, patchy crystalline-core micelles, with their unique, nanometer-sized, alternating corona segmentation, are highly interesting, as this feature provides striking advantages concerning interfacial activity, functionalization, and confinement effects. Hence, this review aims to provide an overview of the current state of the art with respect to self-assembly concepts, properties, and applications of patchy micelles with crystalline cores formed by CDSA. We have also included a more general discussion on the CDSA process and highlight block-type co-micelles as a special type of patchy micelle, due to similarities of the corona structure if the size of the blocks is well below 100 nm.

7.
Angew Chem Int Ed Engl ; 60(40): 21767-21771, 2021 Sep 27.
Article in English | MEDLINE | ID: mdl-34038613

ABSTRACT

Combining the unique corona structure of worm-like patchy micelles immobilized on a polymer fiber with the molecular self-assembly of 1,3,5-benzenetricarboxamides (BTAs) leads to hierarchical superstructures with a fir-tree-like morphology. For this purpose, worm-like patchy micelles bearing pendant, functional tertiary amino groups in one of the corona patches were prepared by crystallization-driven self-assembly and immobilized on a supporting polystyrene fiber by coaxial electrospinning. The obtained patchy fibers were then immersed in an aqueous solution of a tertiary amino-functionalized BTA to induce patch-mediated molecular self-assembly to well-defined fir-tree-like superstructures upon solvent evaporation. Interestingly, defined superstructures are obtained only if the pendant functional groups in the surface patches match with the peripheral substituents of the BTA, which is attributed to a local increase in BTA concentration at the polymer fibers' surface.

8.
ACS Nano ; 15(1): 1111-1120, 2021 Jan 26.
Article in English | MEDLINE | ID: mdl-33332958

ABSTRACT

Self-assembly of block copolymers (BCPs) in three-dimensional (3D) confinement of emulsion droplets has emerged as a versatile route for the formation of functional micro- and nanoparticles. While the self-assembly of amorphous coil-coil BCPs is fairly well documented, less is known about the behavior of crystalline-coil BCPs. Here, we demonstrate that confining a linear ABC triblock terpolymer with a crystallizable middle block in oil-in-water (O/W) emulsions results in a range of microparticles with frustrated inner structure originating from the conflict between crystallization and curved interfaces. Polystyrene-block-polyethylene-block-poly(methyl methacrylate) (PS-b-PE-b-PMMA, S32E36M3293) in toluene droplets was subjected to different preparation protocols. If evaporation was performed well above the bulk crystallization temperature of the PE block (Tevap > Tc), S32E36M3293 first microphase-separated into microparticles with lamella morphology followed by crystallization into a variety of frustrated morphologies (e.g., bud-like, double staircase, spherocone). By evaporating at significantly lower temperatures that allow the PE block to crystallize from solution (Tevap < Tc), S32E36M3293 underwent crystallization-driven self-assembly into patchy crystalline-core micelles, followed by confinement assembly into lenticular microparticles with compartmentalized hexagonal cylinder lattices. The frequency of these frustrated morphologies depends on polymer concentration and the evaporation protocol. These results provide a preliminary understanding of the morphological behavior of semicrystalline block copolymers in 3D soft confinement and may provide alternative routes to structure multicompartment microparticles from a broader range of polymer properties.

9.
Biomacromolecules ; 21(8): 3152-3162, 2020 08 10.
Article in English | MEDLINE | ID: mdl-32603096

ABSTRACT

The formation and rheological properties of hydrogels based on amphiphilic ABA triblock polyether copolymers are described, relying solely on the hydrophobic interaction of long-chain alkyl glycidyl ether (AlkGE)- based A-blocks that are combined with a hydrophilic poly(ethylene glycol) (PEG) midblock. Via anionic ring-opening copolymerization (AROP), ethylene oxide (EO) and long-chain alkyl glycidyl ethers (AlkGEs) were copolymerized, using deprotonated poly(ethylene glycol) (PEG) macroinitiators (Mn of 10, 20 kg mol-1). The polymerization afforded amphiphilic ABA triblock copolymers with molar masses in the range of 21-32 kg mol-1 and dispersities (D) of D = 1.07-1.17. Kinetic studies revealed random copolymerization of EO and AlkGE, indicating random spacing of the hydrophobic AlkGE units by polar EO units. Following this approach, the hydrophobicity of the apolar blocks of amphiphilic ABA triblock polyethers can be tailored. Detailed rheological measurements confirmed the successful formation of hydrogels at different pH values as a consequence of nonpolar interactions and alkyl chain crystallization. Hydrogel formation was also observed at different ionic strengths (i.e., varied salt concentration), based on the hydrophobic aggregates. This behavior is in contrast to other often-used supramolecular cross-linking strategies, such as Coulomb interactions, complexation, or hydrogen bonding. Micro-differential scanning calorimetry (µ-DSC) measurements of the hydrogels revealed crystalline hydrophobic domains with melting temperatures in the physiological temperature range. In 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazoliumbromide (MTT) assays, diblock copolymers possessing structural analogy to the triblock copolymers were studied to assess the general cytotoxicity of amphiphilic polyethers bearing long alkyl chains at the polyether backbone, using splenic immune cells. At intermediate polymer concentrations, no cytotoxic effects were observed. This indicates that long-chain alkyl glycidyl ethers are promising for the introduction of highly hydrophobic as well as crystalline motifs at the polyether backbone in hydrogels for biomedical purposes.


Subject(s)
Ethylene Oxide , Hydrogels , Epoxy Compounds , Hydrogen-Ion Concentration , Kinetics , Polyethylene Glycols , Polymers
10.
Chemistry ; 26(25): 5611-5614, 2020 May 04.
Article in English | MEDLINE | ID: mdl-32065458

ABSTRACT

Multiresponsive polymers that can respond to several external stimuli are promising materials for a manifold of applications. Herein, a facile method for the synthesis of triple-responsive (pH, temperature, CO2 ) poly(N,N-diethylaminoethyl methacrylamide) by a post-polymerization amidation of poly(methyl methacrylate) (PMMA) is presented. Combined with trivalent counterions ([Fe(CN)6 ]3- ) both an upper and lower critical solution temperature (UCST/LCST)-type phase behavior can be realized at pH 8 and 9. PMMA and PMMA-based block copolymers are readily accessible by living anionic and controlled radical polymerization techniques, which opens access to various responsive polymer architectures based on the developed functionalization method. This method can also be applied on melt-processed bulk PMMA samples to introduce functional, responsive moieties at the PMMA surface.

11.
Angew Chem Int Ed Engl ; 59(14): 5765-5770, 2020 Mar 27.
Article in English | MEDLINE | ID: mdl-31891660

ABSTRACT

Nanoparticles of the spin-crossover coordination polymer [FeL(bipy)]n were synthesized by confined crystallization within the core of polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) diblock copolymer micelles. The 4VP units in the micellar core act as coordination sites for the Fe complex. In the bulk material, the spin-crossover nanoparticles in the core are well isolated from each other allowing thermal treatment without disintegration of their structure. During annealing above the glass transition temperature of the PS block, the transition temperature is shifted gradually to higher temperatures from the as-synthesized product (T1/2 ↓=163 K and T1/2 ↑=170 K) to the annealed product (T1/2 ↓=203 K and T1/2 ↑=217 K) along with an increase in hysteresis width from 6 K to 14 K. Thus, the spin-crossover properties can be shifted towards the properties of the related bulk material. The stability of the nanocomposite allows further processing, such as electrospinning from solution.

12.
Nanoscale Adv ; 2(1): 438-452, 2020 Jan 22.
Article in English | MEDLINE | ID: mdl-36133996

ABSTRACT

In this work, we provide a detailed study on the influence of patch size and chemistry on the catalytic activity of patchy hybrid nonwovens in the gold nanoparticle (Au NP) catalysed alcoholysis of dimethylphenylsilane in n-butanol. The nonwovens were produced by coaxial electrospinning, employing a polystyrene solution as the core and a dispersion of spherical or worm-like patchy micelles with functional, amino group-bearing patches (dimethyl and diisopropyl amino groups as anchor groups for Au NP) as the shell. Subsequent loading by dipping into a dispersion of preformed Au NPs yields the patchy hybrid nonwovens. In terms of NP stabilization, i.e., preventing agglomeration, worm-like micelles with poly(N,N-dimethylaminoethyl methacrylamide) (PDMA) patches are most efficient. Kinetic studies employing an extended 1st order kinetics model, which includes the observed induction periods, revealed a strong dependence on the accessibility of the Au NPs' surface to the reactants. The accessibility is controlled by the swellability of the functional patches in n-butanol, which depends on both patch chemistry and size. As a result, significantly longer induction (t ind) and reaction (t R) times were observed for the 1st catalysis cycles in comparison to the 10th cycles and nonwovens with more polar PDMA patches show a significantly lower t R in the 1st catalysis cycle. Thus, the unique patchy surface structure allows tailoring the properties of this "tea-bag"-like catalyst system in terms of NP stabilization and catalytic performance, which resulted in a significant reduction of t R to about 4 h for an optimized system.

13.
Nanoscale ; 10(38): 18257-18268, 2018 Oct 04.
Article in English | MEDLINE | ID: mdl-30238948

ABSTRACT

Block copolymer self-assembly in solution paves the way for the construction of well-defined compartmentalized nanostructures. These are excellent templates for the incorporation and stabilisation of nanoparticles (NPs), giving rise to highly relevant applications in the field of catalysis or sensing. However, the regio-selective incorporation of NPs in specific compartments is still an issue, especially concerning the loading with different NP types. Using crystallisation-driven self-assembly (CDSA), functional worm-like crystalline-core micelles (wCCMs) with a tailor-made, nanometre-sized patchy corona were prepared as versatile templates for the incorporation and stabilisation of metal and metal oxide NPs. Different strategies, like ligand exchange or co-precipitation of polymer stabilised NPs with one surface patch, were developed that allow the incorporation of NPs in specific regions of the patchy wCCM corona. Independent of the NP type and the incorporation method, the NPs showed no tendency for agglomeration and were fixed within the corona patches of the wCCMs. The binary loading of patchy micelles with metal and metal oxide NPs was realised by combining different loading strategies, yielding hybrids with homogeneously dispersed NPs guided by the patchy structure of the template.

14.
Angew Chem Int Ed Engl ; 56(1): 405-408, 2017 01 02.
Article in English | MEDLINE | ID: mdl-27921346

ABSTRACT

Heterogeneous catalysis with supported nanoparticles (NPs) is a highly active field of research. However, the efficient stabilization of NPs without deteriorating their catalytic activity is challenging. By combining top-down (coaxial electrospinning) and bottom-up (crystallization-driven self-assembly) approaches, we prepared patchy nonwovens with functional, nanometer-sized patches on the surface. These patches can selectively bind and efficiently stabilize gold nanoparticles (AuNPs). The use of these AuNP-loaded patchy nonwovens in the alcoholysis of dimethylphenylsilane led to full conversion under comparably mild conditions and in short reaction times. The absence of gold leaching or a slowing down of the reaction even after ten subsequent cycles manifests the excellent reusability of this catalyst system. The flexibility of the presented approach allows for easy transfer to other nonwoven supports and catalytically active NPs, which promises broad applicability.

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