Reversible polypeptide hydrogels from asymmetric telechelics with temperature-dependent and Ni2+-dependent connectors

Thao T.H. Pham, Jasper van der Gucht, Mieke Kleijn, Martien A. Cohen Stuart*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

2 Citations (Scopus)

Abstract

An asymmetric ('hybrid') triblock polypeptide TR4H with two different, orthogonally self-assembling end blocks has been constructed by conjugating a long (37 kDa) random coil block (R4) with a triple helix former T = (Pro-Gly-Pro)9 at the N terminus, and a histidine hexamer ('Histag', H) at the C terminus. This molecule can form trimers at room temperature by assembly of the T blocks, which can in turn assemble upon addition of Ni2+, by association of Ni complexes involving the H block. This results in reversible hydrogels with dual responsiveness. We have studied mechanical properties of these gels, and compared them to gels formed by the symmetric triblock TR8T which is equivalent to a dimer of TR4H, but can only form triple helix-based networks. We find that there is an optimum mole ratio for Ni2+ with respect to the polypeptide of about 1; gels are weaker at both lower and higher Ni2+ dose. At the optimum dose, the high-frequency storage modulus is in between the value expected for nickel-induced dimerization and trimerization of the H blocks. We also find that the gels relax on time scales of about 50 s, which is two orders of magnitude faster than for TR8T gels, implying that relaxation is dominated by the dynamics of the Ni2+ complex.

Original languageEnglish
Pages (from-to)4979-4984
JournalSoft Matter
Volume12
Issue number22
DOIs
Publication statusPublished - 2016

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Hydrogels
connectors
polypeptides
Gels
gels
Peptides
helices
Temperature
temperature
dosage
Dimerization
histidine
dimerization
trimers
assembling
Nickel
Histidine
Dimers
coils
assembly

Cite this

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title = "Reversible polypeptide hydrogels from asymmetric telechelics with temperature-dependent and Ni2+-dependent connectors",
abstract = "An asymmetric ('hybrid') triblock polypeptide TR4H with two different, orthogonally self-assembling end blocks has been constructed by conjugating a long (37 kDa) random coil block (R4) with a triple helix former T = (Pro-Gly-Pro)9 at the N terminus, and a histidine hexamer ('Histag', H) at the C terminus. This molecule can form trimers at room temperature by assembly of the T blocks, which can in turn assemble upon addition of Ni2+, by association of Ni complexes involving the H block. This results in reversible hydrogels with dual responsiveness. We have studied mechanical properties of these gels, and compared them to gels formed by the symmetric triblock TR8T which is equivalent to a dimer of TR4H, but can only form triple helix-based networks. We find that there is an optimum mole ratio for Ni2+ with respect to the polypeptide of about 1; gels are weaker at both lower and higher Ni2+ dose. At the optimum dose, the high-frequency storage modulus is in between the value expected for nickel-induced dimerization and trimerization of the H blocks. We also find that the gels relax on time scales of about 50 s, which is two orders of magnitude faster than for TR8T gels, implying that relaxation is dominated by the dynamics of the Ni2+ complex.",
author = "Pham, {Thao T.H.} and {van der Gucht}, Jasper and Mieke Kleijn and {Cohen Stuart}, {Martien A.}",
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journal = "Soft Matter",
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Reversible polypeptide hydrogels from asymmetric telechelics with temperature-dependent and Ni2+-dependent connectors. / Pham, Thao T.H.; van der Gucht, Jasper; Kleijn, Mieke; Cohen Stuart, Martien A.

In: Soft Matter, Vol. 12, No. 22, 2016, p. 4979-4984.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Reversible polypeptide hydrogels from asymmetric telechelics with temperature-dependent and Ni2+-dependent connectors

AU - Pham, Thao T.H.

AU - van der Gucht, Jasper

AU - Kleijn, Mieke

AU - Cohen Stuart, Martien A.

PY - 2016

Y1 - 2016

N2 - An asymmetric ('hybrid') triblock polypeptide TR4H with two different, orthogonally self-assembling end blocks has been constructed by conjugating a long (37 kDa) random coil block (R4) with a triple helix former T = (Pro-Gly-Pro)9 at the N terminus, and a histidine hexamer ('Histag', H) at the C terminus. This molecule can form trimers at room temperature by assembly of the T blocks, which can in turn assemble upon addition of Ni2+, by association of Ni complexes involving the H block. This results in reversible hydrogels with dual responsiveness. We have studied mechanical properties of these gels, and compared them to gels formed by the symmetric triblock TR8T which is equivalent to a dimer of TR4H, but can only form triple helix-based networks. We find that there is an optimum mole ratio for Ni2+ with respect to the polypeptide of about 1; gels are weaker at both lower and higher Ni2+ dose. At the optimum dose, the high-frequency storage modulus is in between the value expected for nickel-induced dimerization and trimerization of the H blocks. We also find that the gels relax on time scales of about 50 s, which is two orders of magnitude faster than for TR8T gels, implying that relaxation is dominated by the dynamics of the Ni2+ complex.

AB - An asymmetric ('hybrid') triblock polypeptide TR4H with two different, orthogonally self-assembling end blocks has been constructed by conjugating a long (37 kDa) random coil block (R4) with a triple helix former T = (Pro-Gly-Pro)9 at the N terminus, and a histidine hexamer ('Histag', H) at the C terminus. This molecule can form trimers at room temperature by assembly of the T blocks, which can in turn assemble upon addition of Ni2+, by association of Ni complexes involving the H block. This results in reversible hydrogels with dual responsiveness. We have studied mechanical properties of these gels, and compared them to gels formed by the symmetric triblock TR8T which is equivalent to a dimer of TR4H, but can only form triple helix-based networks. We find that there is an optimum mole ratio for Ni2+ with respect to the polypeptide of about 1; gels are weaker at both lower and higher Ni2+ dose. At the optimum dose, the high-frequency storage modulus is in between the value expected for nickel-induced dimerization and trimerization of the H blocks. We also find that the gels relax on time scales of about 50 s, which is two orders of magnitude faster than for TR8T gels, implying that relaxation is dominated by the dynamics of the Ni2+ complex.

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