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Swelling of micro-hydrogels with a crosslinker gradient.

ABSTRACT: A heterogeneous distribution of crosslinker in micro-hydrogels (microgels) results in a non-uniform polymer density inside the particles. Identifying the morphology of the hydrogel backbone enables a bottom-up approach towards the structural and rheological properties of microgel systems. On a local level we use a Flory-Rehner inspired model that focuses on highly swollen networks, characterized by a Poisson's ratio of 1/4. Our ab initio calculations take account for the nonuniform distribution of crosslinker species during the synthesis of poly(N-isopropylacylamide) (PNIPAM) microgels, yet the method is also applicable to other microgel architectures. We recover a single-particle density profile that is in close agreement with SAXS data. Comparison with experimental data confirms that the surface of the cross-linked particle is decorated with dangling polymers ends of considerable size.

SUBMITTER: Boon N

PROVIDER: S-EPMC5778843 | biostudies-literature | 2017 Sep

REPOSITORIES: biostudies-literature

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Swelling of micro-hydrogels with a crosslinker gradient.

Boon Niels N Schurtenberger Peter P

Physical chemistry chemical physics : PCCP 20170901 35

A heterogeneous distribution of crosslinker in micro-hydrogels (microgels) results in a non-uniform polymer density inside the particles. Identifying the morphology of the hydrogel backbone enables a bottom-up approach towards the structural and rheological properties of microgel systems. On a local level we use a Flory-Rehner inspired model that focuses on highly swollen networks, characterized by a Poisson's ratio of 1/4. Our ab initio calculations take account for the nonuniform distribution ...[more]

PMID: 28607971

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Project description:Dynamic covalent crosslinked (DCC) hydrogels represent a significant advance in biomaterials for regenerative medicine and mechanobiology. These gels typically offer viscoelasticity and self-healing properties that more closely mimic in vivo tissue mechanics than traditional, predominantly elastic, covalent crosslinked hydrogels. Despite their promise, the effects of varying crosslinker architecture - side chain versus telechelic crosslinks - on the viscoelastic properties of DCC hydrogels have not been thoroughly investigated. This study introduces hydrazone-based alginate hydrogels and examines how side-chain and telechelic crosslinker architectures impact hydrogel viscoelasticity and stiffness. In hydrogels with side-chain crosslinking (SCX), higher polymer concentrations enhance stiffness and decelerates stress relaxation, while an off-stoichiometric hydrazine-to-aldehyde ratio leads to reduced stiffness and shorter relaxation time. In hydrogels with telechelic crosslinking, maximal stiffness and slowest stress relaxation occurs at intermediate crosslinker concentrations for both linear and star crosslinkers, with higher crosslinker valency further increasing stiffness and relaxation time. Our result suggested different ranges of stiffness and stress relaxation are accessible with the different crosslinker architectures, with SCX hydrogels leading to slower stress relaxation relative to the other architectures, and hydrogels with star crosslinking (SX) providing increased stiffness and slower stress relaxation relative to hydrogels with linear crosslinking (LX). The mechanical properties of SX hydrogels are more robust to changes induced by competing chemical reactions compared to LX hydrogels. Our research underscores the pivotal role of crosslinker architecture in defining hydrogel stiffness and viscoelasticity, providing crucial insights for the design of DCC hydrogels with tailored mechanical properties for specific biomedical applications.

Project description:Synthetic hydrogels are attractive platforms due in part to their highly tunable mechanics, which impact cell behavior and secretory profile. These mechanics are often controlled by altering the number of crosslinks or the total polymer concentration in the gel, leading to structure-property relationships that inherently couple network connectivity to the overall modulus. In contrast, the native extracellular matrix (ECM) contains structured biopolymers that enable stiff gels even at low polymer content, facilitating 3D cell culture and permeability of soluble factors. To mimic the hierarchical order of natural ECM, this work describes a synthetic hydrogel system in which mechanics are tuned using the structure of sequence-defined peptoid crosslinkers, while fixing network connectivity. Peptoid crosslinkers with different secondary structures are investigated: 1) a helical, molecularly stiff peptoid, 2) a non-helical, less stiff peptoid, and 3) an unstructured, relatively flexible peptoid. Bulk hydrogel storage modulus increases when crosslinkers of higher chain stiffness are used. In-vitro studies assess the viability, proliferation, cell morphology, and immunomodulatory activity of human mesenchymal stem cells (hMSCs) on each hydrogel substrate. Matrix mechanics regulate the morphology of hMSCs on the developed substrates, and all of the hydrogels studied upregulate IDO production over culture on TCP. Softer substrates further this upregulation to a plateau. Overall, this system offers a biomimetic strategy for decoupling hydrogel storage modulus from network connectivity, enabling systematic study of biomaterial properties on hMSC behavior and enhancement of cellular functionality for therapeutic applications. STATEMENT OF SIGNIFICANCE: Various strategies to tune hydrogel mechanics have been developed to control human mesenchymal stem cell (hMSC) behavior and regulate their immunomodulatory potential. However, these strategies typically couple mechanics to network connectivity, which in turn changes other hydrogel properties such as permeability that may have unintended effects on hMSC behavior. This work presents a strategy to tune hydrogel mechanics using crosslinkers with different secondary structure and molecular rigidity. This strategy successfully decouples hydrogel moduli from crosslinker stoichiometry and mimics the hierarchical nature of the native extracellular matrix. The moduli of the developed hydrogels led to significant impacts on hMSC morphology and proliferation, and increased immunomodulatory potential, indicating that molecular rigidity is a promising avenue to control engineered ECM mechanics for therapeutic applications.

Dataset Information

Swelling of micro-hydrogels with a crosslinker gradient.

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Swelling of micro-hydrogels with a crosslinker gradient.

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