Tuneable pH-regulated supramolecular copolymerisation by mixing mismatched dendritic peptide comonomers

Ahlers, Patrick; Frisch, Hendrik; Besenius, Pol

doi:10.1039/c5py01241d

Cited by 39 publications

(43 citation statements)

References 55 publications

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“…Angewandte Chemie Zuschriften 10.5;Scheme 1) as it is fully protonated at both pH values;the resulting charge repulsion leads to unfolding of the structure. [11] Theo btained hydrogel is mechanically quite stable as confirmed by rheology studies (Table S2 and Figure S6). Upon decreasing the pH value to pH 4, at which the GCP moieties are protonated, the particle size was significantly reduced (only 28 nm at 100 mm).…”

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confidence: 60%

pH‐Controlled Formation of a Stable β‐Sheet and Amyloid‐like Fibers from an Amphiphilic Peptide: The Importance of a Tailor‐Made Binding Motif for Secondary Structure Formation

et al. 2016

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confidence: 60%

pH‐Controlled Formation of a Stable β‐Sheet and Amyloid‐like Fibers from an Amphiphilic Peptide: The Importance of a Tailor‐Made Binding Motif for Secondary Structure Formation

et al. 2016

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“…The C 3 ‐symmetrical dendritic peptide comonomers 1 and 2 were synthesized using a previously reported convergent synthetic approach ( Figure 1 A) . We first employed standard Fmoc solid‐phase peptide synthesis to prepare a Fmoc‐NH‐Phe‐His‐Phe‐His‐Phe‐OH peptide 3 .…”

Section: Resultsmentioning

confidence: 99%

“…To this end we have disclosed an ampholytic supramolecular copolymer design, whereby the multicomponent coassembly of anionic oligo(glutamic acid ‐alt‐ phenylalanine) and cationic oligo(lysine ‐alt‐ phenylalanine) peptide synthons leads to alternating copolymer formation . The pH‐stability window of these copolymers could be tuned by a supramolecular engineering approach, using mismatched comonomer pairs which shifts the pH‐triggered disassembly of the copolymers from pH 4.2 to 5.8 . In this case however the pH‐triggered glutamic acid monomer that is released upon disassembly of the copolymers leads to the formation of homopolymers, in a process that is driven by charge regulation.…”

Section: Introductionmentioning

confidence: 99%

Tuning the pH‐Switch of Supramolecular Polymer Carriers for siRNA to Physiologically Relevant pH

Ahlers

Frisch

Holm

et al. 2017

Macromolecular Bioscience

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Aqueous supramolecular polymers [4] have recently entered the field of biomed ical applications [5] and several systems have been disclosed for regenerative medi cine or drug delivery, using host-guest pairs, [6] peptide amphiphiles, [7] ureido pyrimidineone, [8] and benzenetricarbox amide (BTA) [9] scaffolds. We here focus on the use of 1D supramolecular polymers, with a nanorodlike morphology, based on new dendritic oligo(histidine-alt-phenyla lanine) peptide synthons. These combine high robustness and fidelity in the self assembly with stimuliresponsive proper ties toward pHvalues of the surrounding medium. We have previously reported C 3 symmetrical nonaphenylalanine supra molecular building monomers equipped with dendritic tetraethylene glycol chains, with binding affinities of up to 7 × 10 7 m −1 in water. [10] In order to introduce pHswitchable properties into the supramolecular polymeriza tion, we changed the peripheral dendritic tetraethylene glycol chains for dendritic carboxylic acids in the amphiphilic mono mers that are highly charged and thus molecularly dissolved at neutral pH and selfassemble into anisotropic supramolecular polymers by acidifying the aqueous medium. [11] These sys tems were not applicable when aiming for a pHtriggered dis assembly of supramolecular constructs upon lowering the pH. To this end we have disclosed an ampholytic supramolecular copolymer design, whereby the multicomponent coassembly of anionic oligo(glutamic acid-alt-phenylalanine) and cationic oligo(lysine-alt-phenylalanine) peptide synthons leads to alter nating copolymer formation. [12] The pHstability window of these copolymers could be tuned by a supramolecular engi neering approach, using mismatched comonomer pairs which shifts the pHtriggered disassembly of the copolymers from pH 4.2 to 5.8. [13] In this case however the pHtriggered glutamic acid monomer that is released upon disassembly of the copol ymers leads to the formation of homopolymers, in a process that is driven by charge regulation. [2c,12b,13] Thus, we here aim to develop a facile pHresponsive supramolecular polymeriza tion using an oligo(histidine-alt-phenylalanine) peptide syn thon, that operates in a physiologically relevant pH window, and where the functional and structural dendritic comonomers can be mixed at will, without significantly shifting the pHtriggered disassembly. The hydrophobic-hydrophilic shift upon protona tion of histidine containing amphiphiles under slightly acidic pH-triggered ReleaseThe preparation of histidine enriched dendritic peptide amphiphiles and their self-assembly into multicomponent pH-switchable supramolecular polymers is reported. Alternating histidine and phenylalanine peptide synthons allow the assembly/disassembly to be adjusted in a physiologically relevant range of pH 5.3-6.0. Coassembly of monomers equipped with dendritic tetraethylene glycol chains with monomers bearing peripheral primary amine groups leads to nanorods with a tunable cationic surface charge density. These surface functional supramolecula...

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“…[273][274][275][276][277][278][279][280][281][282][283][284][285][286][287][288] One-dimensional alternating supramolecular copolymers with a nanorod-like morphology are obtained, via a combination of attractive Coulomb interactions, hydrogen bonding, and hydrophobic shielding. [289][290][291] In pHdependent characterization experiments, it was shown that the charges in the ampholytic copolymers are screened by either protonating the carboxylate or deprotonating the ammonium groups in the side chains of the comonomers, which leads to the disassembly of the copolymers at pH 5 3.6 and pH 5 8.9. Experimental characterization of the supramolecular structures included CD spectroscopy, 13 C CP-MAS NMR, TEM, as well as multiscale molecular modeling.…”

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confidence: 99%

“…291 The coassembly of a longer hexapeptidic, stronger b-sheet comonomer, with a second weaker pentapeptidic b-sheet design shifted the pH-triggered disassembly for the copolymers from pH 4.2 for the two strong b-sheet synthons to biologically relevant pH 5.8 for the mismatched pair between a strong cationic and a weak anionic b-sheet monomer. 291 Importantly, the stability towards the addition of NaCl was not compromised. These tuneable pH-triggered polymers will open new avenues for applications in biomedical technologies, for example as drug and gene delivery vehicles, where the release of cargo material in intracellular compartments is generally assumed to be regulated by both a decrease of the pH and by osmotic swelling.…”

mentioning

confidence: 99%

Controlling supramolecular polymerization through multicomponent self‐assembly

Besenius

2016

J. Polym. Sci. Part A: Polym. Chem.

128

102

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The self-assembly into supramolecular polymers is a process driven by reversible non-covalent interactions between monomers, and gives access to materials applications incorporating mechanical, biological, optical or electronic functionalities. Compared to the achievements in precision polymer synthesis via living and controlled covalent polymerization processes, supramolecular chemists have only just learned how to developed strategies that allow similar control over polymer length, (co)monomer sequence and morphology (random, alternating or blocked ordering). This highlight article discusses the unique opportunities that arise when coassembling multicomponent supramolecular polymers, and focusses on four strategies in order to control the polymer architecture, size, stability and its stimuli-responsive properties: (1) endcapping of supramolecular polymers, (2) biomimetic templated polymerization, (3) controlled selectivity and reactivity in supramolecular copolymerization, and (4) living supramolecular polymerization. In contrast to the traditional focus on equilibrium systems, our emphasis is also on the manipulation of selfassembly kinetics of synthetic supramolecular systems. V C 2016

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Tuneable pH-regulated supramolecular copolymerisation by mixing mismatched dendritic peptide comonomers

Abstract: The co-assembly of oppositely charged phenylalanine-rich dendritic comonomers yields supramolecular alternating copolymers, whose stability and pH-triggered disassembly is tuned by mismatching a strong with a weak β-sheet encoded comonomer.

Cited by 39 publications

References 55 publications

pH‐Controlled Formation of a Stable β‐Sheet and Amyloid‐like Fibers from an Amphiphilic Peptide: The Importance of a Tailor‐Made Binding Motif for Secondary Structure Formation

pH‐Controlled Formation of a Stable β‐Sheet and Amyloid‐like Fibers from an Amphiphilic Peptide: The Importance of a Tailor‐Made Binding Motif for Secondary Structure Formation

Tuning the pH‐Switch of Supramolecular Polymer Carriers for siRNA to Physiologically Relevant pH

Controlling supramolecular polymerization through multicomponent self‐assembly

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