One-pot synthesis and self-assembly of supramolecular dendritic polymers

Chen, Senbin; Schulz, Matthias; Lechner, Bob‐Dan; Appiah, Clement; Binder, Wolfgang H.

doi:10.1039/c5py01329a

Cited by 24 publications

(11 citation statements)

References 52 publications

(54 reference statements)

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“…38 Extending to heterotelechelic polymers bearing complementary H-bonding moieties (namely Ba and HW at their αand ω-ends, respectively) a similar head-to-tail fashion assembly is obtained, forming supramolecular polymers with repetitive building blocks at high concentration. 54 When the assembling-unit is designed as a branched structure, such as a X−Y 2 type heterotopic building polymer, supramolecular dendritic architectures can be formed 55 (Figure 3A): as now one barbiturate unit (X) is combined with two Hamilton wedges (Y) in one and the same chain, subsequent assembly leads to the formation of supramolecular hyperbranched polymers, which can either be proven by their significantly enhanced viscosity (by a factor as high as ∼1839 at 20 °C), or directly via AFM after deposition on surfaces (Figure 3B): well-sized nano-objects, shaped into large discs, predominately with diameters of ∼310 and 180 nm have been observed. All of the disclike nano-objects are remarkably uniform in height (∼5−6 nm); the large nanoscopic objects are schematically illustrated in Figure 3B (inset), demonstrating the formation of three-dimensional supramolecular hyperbranched aggregates from the topological X−Y 2 type building blocks.…”

Section: Design and Architecture Of Ordering Inmentioning

confidence: 99%

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Dynamic Ordering and Phase Segregation in Hydrogen-Bonded Polymers

Chen

Binder

2016

Acc. Chem. Res.

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Hydrogen bonds (H-bonds) constitute highly relevant structural units of molecular self-assembly. They bridge biological and synthetic sciences, implementing dynamic properties into materials and molecules, not achieved via purely covalent bonds. Phase segregation on the other hand represents another important assembly principle, responsible for, e.g., cell compartimentation, membrane-formation, and microphase segregation in polymers. Yet, despite the expanding elegant synthetic strategies of supramolecular polymers, the investigation of phase behavior of macromolecules driven by H-bonding forces still remains in its infancy. Compared to phase segregation arising from covalently linked block copolymers, the generation of phase segregated nanostructures via supramolecular polymers facilitates the design of novel functional materials, such as those with stimuli-responsive, self-healing, and erasable-material properties. We here discuss the phase segregation of H-bonding polymers in both the solution and solid state, wherein the molecular recognition elements are based on multiple H-bonding moieties, such as thymine/2,6-diamino-pyridine (THY/DAP), thymine/diamino triazine (THY/DAT), and barbiturate/Hamilton wedge (Ba/HW) elements. The specific aggregation of a series of different H-bonding polymers in solution, both linear and dendritic polymers, bearing heterocomplementary H-bonding moieties are described, in particular focusing on the issue of phase segregation. The exploitation of H-bonded supramolecular dendrons with segregating polymer chains leads to the formation of three-phase segregated hierarchical micelles in solution, purely linking the components via H-bonds, in turn displaying a versatile spectrum of segregated morphologies. We also focus on segregation effects of H-bonded amorphous and crystalline polymers: thus the formation of nanostructures, such as disordered micelles and well-ordered body centered cubic (BCC) packed spheres from telechelic polymers bearing H-bonding moieties at the chain ends is observed. Finally, we discuss the discovery of novel functional microphase separated self-healing supramolecular architectures, illustrating dynamic and self-healing properties with an almost complete recovery of the initial mechanical performances healing within 24h at 30 °C. Collectively, our studies prove that phase segregation in H-bonding polymers is an important principle, capable to generate nanostructures and dynamic properties not achieved in covalently linked polymers. The results discussed illustrate that a rational architectural design within H-bonding polymer systems in interplay with phase segregation in both the amorphous and crystalline state opens perspectives to develop artificial supramolecular systems approaching the level of complexities and properties present in nature's biomaterials.

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Section: Design and Architecture Of Ordering Inmentioning

confidence: 99%

Section: Design and Architecture Of Ordering In Solutionmentioning

confidence: 99%

Dynamic Ordering and Phase Segregation in Hydrogen-Bonded Polymers

Chen

Binder

2016

Acc. Chem. Res.

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“…There are two main approaches to synthesize SDs: untemplated or template‐directed synthesis . Untemplated synthesis is a smart and facile strategy to fabricate well‐defined SDs by using monofunctional dendrons with self‐complementary units, which ensures structural accuracy and simplifies synthesis steps compared to the conventional multistep approach . A series of template‐directed approaches was developed, which are based on mono‐hetero functionalized dendrons to prepare SDs.…”

Section: Structures Properties and Functions Of Nonlinear Supramolementioning

confidence: 99%

Nonlinear Supramolecular Polymers for Therapeutic Applications

Chen

Kretzschmann

Tian

et al. 2018

Advanced Therapeutics

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An elegant combination of supramolecular polymers exhibiting nonlinear topological structures results in a series of brand new, nonlinear supramolecular polymers. Recently, these polymers have attracted increased attention in various fields due to their diverse and advantageous properties. Especially in therapeutic applications, one can take advantage of their unique chemical, physical, and biological properties such as degradability and stimuli‐responsiveness. Due to the large number of possible module modifications, such polymers have great potential as platforms in disease treatments. In this review, the structures, properties, and functions of different nonlinear supramolecular polymers are summarized. Current therapeutic applications are presented and the prospective design trends are discussed for promoting the development of nonlinear supramolecular polymers.

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“…The structural investigation was further made by evaluating mass spectra of polymer 3 and the LVFF–polymer conjugate 4 by matrix‐assisted laser desorption ionization time‐of‐flight (MALDI‐TOF) MS studies . As depicted by Figure A, a clear shift toward larger molecular ions in the spectrum of LVFF–polymer conjugate 4 was observed as compared to polymer 3 .…”

Section: Resultsmentioning

confidence: 99%

One‐Pot Synthesis of Thermoresponsive Amyloidogenic Peptide–Polymer Conjugates via Thio–Bromo “Click” Reaction of RAFT Polymers

Kumar

Deike

Binder

2017

Macromol. Rapid Commun.

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A synthetic strategy to efficiently prepare main-chain peptide-polymer conjugates probing their aggregation in solution is described. An in situ tandem reaction based on aminolysis/thio-bromo "click" reaction is performed to tether an amyloidogenic peptide fragment amyloid-β (Leu-Val-Phe-Phe (LVFF)) to the ω-chain end of poly(diethylene glycol methyl ether acrylate) (PDEGA), prepared via reversible addition fragmentation chain transfer polymerization. Structural confirmation of the constructed conjugates PDEGA-LVFF (M = 5600, Ð = 1.21), (M = 7600, Ð = 1.16), and (M = 8900, Ð = 1.15) is successfully made by combined studies of H NMR, size-exclusion chromatography, matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry, and electrospray ionization time-of-flight (ESI-TOF) mass spectrometry. The effect of the peptidic constituent on the thermoresponsive behavior of the polymer is examined by UV-vis spectroscopy, and the self-assembly behavior of the amphiphilic conjugate is further exploited, exhibiting micellar morphology in aqueous solution.

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One-pot synthesis and self-assembly of supramolecular dendritic polymers

Abstract: A X–Y2 type heterotropic single-chain polymer, Ba-(PnBuA-HW)2, is prepared in a one-pot two-step reaction, subsequently self-assembling into supramolecular dendrimers, which are displaying solvent-dependent disc-like hierarchical nanoscopic structures as evidenced by AFM.

Cited by 24 publications

References 52 publications

Dynamic Ordering and Phase Segregation in Hydrogen-Bonded Polymers

Dynamic Ordering and Phase Segregation in Hydrogen-Bonded Polymers

Nonlinear Supramolecular Polymers for Therapeutic Applications

One‐Pot Synthesis of Thermoresponsive Amyloidogenic Peptide–Polymer Conjugates via Thio–Bromo “Click” Reaction of RAFT Polymers

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