Search

Nature uses discrete molecular building blocks to form polymers that assemble into multicomponent, multi-dynamic networks, inside (cytoskeleton) and outside (extracellular matrix) the cell. Both the intra-fibrous molecular dynamics and interactions between fibers dictate (non)linear mechanics, such as stress stiffening and relaxation, and ultimately biological function. Current synthetic systems capture only one dynamic process. Here, we present multi-dynamic hydrogels by uniting a stress-stiffening polymer with supramolecular polymers. Crucial is the molecular dynamics of the supramolecular polymers: They dictate the interaction strength with the stress-stiffening polymer and the subsequent dynamic mechanical properties of the mixed networks. The biological relevance of our multi-dynamic hydrogels is demonstrated by their ability to support fibroblast cell spreading. Future work may address the display of various dynamically presented bioactive cues to cells.

T-cell acute lymphoblastic leukemia causes a disproportional amount of immature white blood cells in the patients' bone marrow. The significant undesired side effects associated with traditional chemotherapy treatment prompted us to study a more effective treatment strategy. We decorated polyisocyanopeptide scaffolds with the selective leukemia cell binding aptamer sgc8c and found that the polymers inhibit proliferation by G0/G1-phase arrest, serving as an opportunity for future therapeutic strategies.

Changing wound dressings inflicts pain and may disrupt wound repair. Novel synthetic thermosensitive hydrogels based on polyisocyanopeptide (PIC) offer a solution. These gels are liquid below 16 °C and form gels beyond room temperature. The architecture and mechanical properties of PIC gels closely resemble collagen and fibrin, and include the characteristic stiffening response at high strains. Considering the reversible thermo-responsive behavior, we postulate that PIC gels are easy to apply and remove, and facilitate healing without eliciting foreign body responses or excessive inflammation. Biocompatibility may be higher in RGD-peptide-functionalized PIC gels due to enhanced cell binding capabilities. Full-thickness dorsal skin wounds in mice were compared to wounds treated with PIC gel and PIC-RGD gel for 3 and 7 days. No foreign body reactions and similar wound closure rates were found in all groups. The level of macrophages, myofibroblasts, epithelial migration, collagen expression, and blood vessels did not significantly differ from controls. Surprisingly, granulocyte populations in the wound decreased significantly in the PIC gel-treated groups, likely because foreign bacteria could not penetrate the gel. RGD-peptides did not further improve any effect observed for PIC. The absence of adverse effects, ease of application, and the possibilities for bio-functionalization make the biomimetic PIC hydrogels suitable for development into wound dressings., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Bundling of single polymer chains is a crucial process in the formation of biopolymer network gels that make up the extracellular matrix and the cytoskeleton. This bundled architecture leads to gels with distinctive properties, including a large-pore-size gel formation at very low concentrations and mechanical responsiveness through nonlinear mechanics, properties that are rarely observed in synthetic hydrogels. Using small-angle X-ray scattering (SAXS), we study the bundle formation and hydrogelation process of polyisocyanide gels, a synthetic material that uniquely mimics the structure and mechanics of biogels. We show how the structure of the material changes at the (thermally induced) gelation point and how factors such as concentration and polymer length determine the architecture, and with that, the mechanical properties. The correlation of the gel mechanics and the structural parameters obtained from SAXS experiments is essential in the design of future (synthetic) mimics of biopolymer networks.

Fibrous networks of biopolymers possess unique properties: mechanical stability at low concentrations, an extremely porous architecture, and strong stiffening at small deformations. An outstanding challenge is to find methods that allow to tailor the mechanical properties of these bionetworks or their synthetic equivalents without changing the polymer concentration, which simultaneously changes all other hydrogel properties. Here, networks of dilute (0.1 wt.%) fibrous hydrogels are prepared and crosslink them with functional rod‐shaped nanoparticles. The crosslinking is observed to induce an architectural change that strongly affects the mechanical properties of the hydrogels with a 40‐fold increase in stiffness. The effect is strongest at the lowest polymer and particle concentrations (99.8% water) and is tailorable through tuning the crosslink density. Moreover, the nanoparticle components in the composite offer the opportunity to introduce additional functions; gels with magnetic and conductive properties are reported. However, through the generic crosslinking approach of a fibrous network with decorated nanoparticle crosslinkers as presented in this work, virtually any functionality may be introduced in highly responsive hydrogels, providing a guide to design next generations of multi‐functional soft materials. [ABSTRACT FROM AUTHOR]

Chemistry quickly moves from a molecular science to a systems science. This requires spatial and temporal control over the organisation of molecules and molecular assemblies. Whilst Nature almost by default (transiently) organises her components at multiple different length scales, scientists struggle to realise even relatively straightforward patterns. In the past decades, supramolecular chemistry has taught us the rules to precisely engineer molecular assembly at the nanometre scale. At higher length scales, however, we are bound to top-down nanotechnology techniques to realise order. For soft, biological matter, many of these top-down techniques come with serious limitations since the molecules generally show low susceptibilities to the applied stimuli. A new method is based on liquid crystal templating. In this hierarchical approach, a liquid crystalline host serves as the scaffold to order polymers or assemblies. Being a liquid crystal, the host material can be ordered at many different length scales and on top of that, is highly susceptible to many external stimuli, which can even be used to manipulate the liquid crystal organisation in time. As a result, we anticipate large control over the organisation of the materials inside the liquid crystalline host. Recently, liquid crystal templating was also realised in water. This suddenly makes this tool highly applicable to start organising more delicate biological materials or even small organisms. We review the scope and limitations of liquid crystal templating and look out to where the technique may lead us. [ABSTRACT FROM AUTHOR]

Control over the organization of assemblies from molecular dimensions up to the macroscopic length scale is an outstanding challenge in science, above all for materials in high dilution. Instead of inducing order by generating very long and stiff structures, an alternative approach is studied: a two-component assembly of a semiflexible polymer with a (self-assembling) chromonic liquid crystal. By following the structure formation in time using different techniques, a mechanistic model is proposed that explains how such unusually well-defined materials can be created from flexible components. It is concluded that at this very low concentration (>99.6% water), these macroscopically organized structures can only be formed when the energies between different assembly states and their interconversion rates are properly balanced. This may, however, be in reach for a wide range of materials, which makes this a generic route toward high definition at low concentration without the need for long and rigid building blocks. [ABSTRACT FROM AUTHOR]

Rigid rod polyisocyanopeptides bearing phthalocyanines as pendant groups have been synthesised through CuAAC of polyisocyanopeptides containing acetylene groups with zinc(II) phthalocyanine azide. As confirmed by UV/Vis, fluorescence, and circular dichroism spectroscopies, the phthalocyanines are arranged in a helical fashion along the polymer backbone, forming the longest reported well-defined phthalocyanine assembly described to date. [ABSTRACT FROM AUTHOR]

We have investigated the effect of structure modification of various discotic liquid crystal side chain polymers on their phase transitions and the resulting dynamics. This has resulted in a better understanding of the structure of the various nematic phases that can be formed, in particular giving rise to the identification of supramolecular thermotropic nematic phases where the fundamental units comprise assemblies of molecules. In addition we have examined the dynamics of field-induced order parameters in the isotropic phase of calamitic side chain polymers using dielectric relaxation spectroscopy and dynamic Kerr effect measurements. [ABSTRACT FROM AUTHOR]

A series of novel mesogens have been prepared by a five-fold Sonogashira reaction of terminal acetylenes with a functionalized pentabromophenol. The corresponding side chain polymers were prepared by a polymer analogous substitution reaction. The mesogens differ in the nature of the substituents, linking five hexyl tails to the aromatic core, i.e. CH2, O, S, SO2 and CONH groups. A wide range of mesophases and corresponding transition temperatures has been detected, ranging from low melting nematic phases to highly stable columnar phases. The widely variable phase behavior is described in terms of specific intermolecular interactions. [ABSTRACT FROM AUTHOR]