Multicompartment micelles from a metallo-supramolecular tetrablock quatercopolymer

Ott, Christina; Hoeppener, Stephanie; Schubert, Ulrich S.

doi:10.1039/b912504c

Cited by 31 publications

(28 citation statements)

References 15 publications

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“…Although orthogonal motifs are an emerging field 157 and diblock copolymer morphologies can compete in complexity with triblock terpolymers as shown in the previous section, covalently linked triblock terpolymers cannot evade each other and will microphase-separate to multicompartment nanostructures more readily and reliably. 37,[190][191][192][193][194][195][196] Miktoarm star terpolymers. Besides added directing agents, the miktoarm star terpolymer architecture with block chemistries above the super-strong segregation limit (SSSL) facilitates control over phase separation to form core-MCNs almost independent of the solvent condition.…”

Section: One-step Self-assembly Of Abc Triblock Terpolymersmentioning

confidence: 99%

Self-assembly concepts for multicompartment nanostructures

2015

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Compartmentalization is ubiquitous to many biological and artificial systems, be it for the separate storage of incompatible matter or to isolate transport processes. Advancements in the synthesis of sequential block copolymers offer a variety of tools to replicate natural design principles with tailor-made soft matter for the precise spatial separation of functionalities on multiple length scales. Here, we review recent trends in the self-assembly of amphiphilic block copolymers to multicompartment nanostructures (MCNs) under (semi-)dilute conditions, with special emphasis on ABC triblock terpolymers. The intrinsic immiscibility of connected blocks induces short-range repulsion into discrete nano-domains stabilized by a third, soluble block or molecular additive. Polymer blocks can be synthesized from an arsenal of functional monomers directing self-assembly through packing frustration or response to various fields. The mobility in solution further allows the manipulation of self-assembly processes into specific directions by clever choice of environmental conditions. This review focuses on practical concepts that direct self-assembly into predictable nanostructures, while narrowing particle dispersity with respect to size, shape and internal morphology. The growing understanding of underlying self-assembly mechanisms expands the number of experimental concepts providing the means to target and manipulate progressively complex superstructures.

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Section: One-step Self-assembly Of Abc Triblock Terpolymersmentioning

confidence: 99%

Self-assembly concepts for multicompartment nanostructures

2015

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“…Metallo-supramolecular block copolymers are generated through metal-ligand coordination of ligand end-modified homopolymers with proper metal ions [1]. Various ligands have been utilized in construction of diverse copolymers, such as 2,2 -bipyridine (bpy) [2][3][4], 2,2 :6 ,2"-terpyridine (tpy) [5][6][7][8][9][10][11][12][13], and pincer-type ligands [14][15][16][17][18]. Among them, bis(tpy) complexes are commonly used for preparation of diblock copolymers in a stepwise manner [6][7][8][9][10][11][12].…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Terpyridine End-Modified Polystyrenes through ATRP for Facile Construction of Metallo-Supramolecular P3HT-b-PS Diblock Copolymers

Chan

2020

Polymers

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Complementary complexation between 2,2′:6′,2″-terpyridine (tpy) and 6,6″-dianthracenyl-substituted tpy in the presence of Zn(II) ions provided an efficient strategy for construction of metallo-supramolecular diblock copolymers. To synthesize well-defined tpy-modified polystyrenes (PSs), an Fe(II) bis(tpy) complex bearing α-bromoester as a metallo-initiator was applied to atom transfer radical polymerization (ATRP) to avoid poisoning the Cu(I) catalyst. Subsequently, a series of tpy-functionalized PSs was obtained after the decomplexation of <tpy-Fe(II)-tpy> junction by tetrakis(triethylammonium) ethylenediaminetetraacetate (TEA-EDTA) under mild conditions. The metallo-supramolecular poly(3-hexylthiophene) (P3HT)-block-PS diblock copolymers were prepared by simply mixing the corresponding terminally tpy-modified homopolymers with Zn(II) ions, and further characterized by 1H NMR and diffusion ordered spectroscopy (DOSY) experiments. The approach using metallo-initiators for ATRP offers an opportunity to construct tpy-functionalized polymers with controllable molecular weights and low polydispersities. Through the spontaneous heteroleptic complexation, a variety of metallo-supramolecular diblock copolymers with tunable block ratios can be easily constructed.

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“…There are numerous reports covering several strategies to prepare nanosized polymers; almost all of them are dealing with self-assembled multicompartment micelles of block copolymers for nanobiotechnology, particularly for nanomedicine. [33][34][35][36][37][38][39][40][41][42][43][44][45] Apart from the self-assembly process, ring-closing metathesis reaction has also been used to prepare polymer in the form of nanosized particles for complexation and catalysis application. [46][47][48] All these methods are cumbersome and require critical design and high experimental input.…”

Section: Introductionmentioning

confidence: 99%

“…Preparation of polymers in nanoscale is demand of today's and future nanotechnology. There are numerous reports covering several strategies to prepare nanosized polymers; almost all of them are dealing with self‐assembled multicompartment micelles of block copolymers for nanobiotechnology, particularly for nanomedicine . Apart from the self‐assembly process, ring‐closing metathesis reaction has also been used to prepare polymer in the form of nanosized particles for complexation and catalysis application .…”

Section: Introductionmentioning

confidence: 99%

Dendritic‐Linear Hybrid Multiarm Star Polymers: A Straightforward Synthesis of Polymer as Molecular Nanoparticles

Nasar

Veerapandian

2015

Macro Chemistry & Physics

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Synthesis of multiarm star polymers via “core first” method but possibly through two different chain growth fashions has been described. Two distinct styrenyl‐TEMPO‐based G3 and G4 dendritic unimolecular initiators have been used for this method. Polymerization of styrene using these core‐cum‐initiators at 125 °C varying the monomer to initiator ratio and polymerization time yields multiarm star polymers with molecular weight (Mw) in the range of 1.71 × 105 to 4.75 × 105 g mol−1 and polydispersity in the range of 1.34–1.46. Hydrolysis leading to degradation of inner polyurethane core yields highly narrow dispersed—PDI 1.00 to 1.04—polystyrene chains, and the SEC‐MALLS data of these chains confirm the accurate control on predetermination in the number of arms up to 48 of star polymers. The specific refractive index increment (dn/dc) of the polymers is found to be decreased with decreasing weight fraction of core. The transmission electron microscope (TEM) and atomic force microscopy (AFM) images and hydrodynamic radius of chosen polymers confirm the two different chain growth fashions leading to the formation of star polymers as discrete nanoparticle in the case of initiator in which TEMPO is anchored and formation of peripherally low entangled short chains in the case of initiators in which TEMPO is end‐capped.

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Multicompartment micelles from a metallo-supramolecular tetrablock quatercopolymer

Abstract: Multicompartment micelles with tunable compartment solubility have been prepared in alcohols from a metallo-supramolecular poly(p-tetrafluoromethylstyrene)-block-poly(tert-butylacrylate)-block-poly(styrene)-[Ru]-poly(ethylene glycol) tetrablock quaterpolymer.

Cited by 31 publications

References 15 publications

Self-assembly concepts for multicompartment nanostructures

Self-assembly concepts for multicompartment nanostructures

Synthesis of Terpyridine End-Modified Polystyrenes through ATRP for Facile Construction of Metallo-Supramolecular P3HT-b-PS Diblock Copolymers

Dendritic‐Linear Hybrid Multiarm Star Polymers: A Straightforward Synthesis of Polymer as Molecular Nanoparticles

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