Mechanics from Calorimetry: Probing the Elasticity of Responsive Hydrogels

Temperature-sensitive hydrogels based on polymers such as poly(N-isopropylacrylamide) (PNIPAM) undergo a volume phase transition in response to changes in temperature. During this transition, distinct changes in both thermal and mechanical properties are observed. Here, we illustrate and exploit the inherent thermodynamic link between thermal and mechanical properties by showing that the compressive elastic modulus of PNIPAM hydrogels can be probed using differential scanning calorimetry. We validate our approach by using conventional osmotic compression tests. Our method could be particularly valuable for determining the mechanical response of thermosensitive submicron-sized and/or oddly shaped particles, to which standard methods are not readily applicable

How Historians Play God

This essay recounts the career of Jacques-Pierre Brissot, the leader of the Girondists during the French Revolution, in a manner designed to pose questions about the nature of historical research in general. How, in piecing together information taken from scraps of paper, do historians come to an understanding of other lives? Put in the abstract, the problem belongs to epistemology or ethics. Confronted in practice, it is more like the puzzles uncovered by archaeologists. The historian digs out a shard of evidence from the archives and asks: was Brissot, the ultimate idealist, a spy for the police? By stepping in and out of layers of time, the historian is actually playing a deeper game, one that he or she may be reluctant to admit.Histor

Strain-controlled criticality governs the nonlinear mechanics of fibre networks

Disordered fibrous networks are ubiquitous in nature as major structural components of living cells and tissues. The mechanical stability of networks generally depends on the degree of connectivity: only when the average number of connections between nodes exceeds the isostatic threshold are networks stable (Maxwell, J. C., Philosophical Magazine 27, 294 (1864)). Upon increasing the connectivity through this point, such networks undergo a mechanical phase transition from a floppy to a rigid phase. However, even sub-isostatic networks become rigid when subjected to sufficiently large deformations. To study this strain-controlled transition, we perform a combination of computational modeling of fibre networks and experiments on networks of type I collagen fibers, which are crucial for the integrity of biological tissues. We show theoretically that the development of rigidity is characterized by a strain-controlled continuous phase transition with signatures of criticality. Our experiments demonstrate mechanical properties consistent with our model, including the predicted critical exponents. We show that the nonlinear mechanics of collagen networks can be quantitatively captured by the predictions of scaling theory for the strain-controlled critical behavior over a wide range of network concentrations and strains up to failure of the material

Dual FGF-2 and Intergrin α5β1 Signaling Mediate GRAF-Induced RhoA Inactivation in a Model of Breast Cancer Dormancy

Interactions with the bone marrow stroma regulate dormancy and survival of breast cancer micrometastases. In an in vitro model of dormancy in the bone marrow, we previously demonstrated that estrogen-dependent breast cancer cells are partially re-differentiated by FGF-2, re-express integrin α5β1 lost with malignant transformation and acquire an activated PI3K/Akt pathway. Ligation of integrin α5β1 by fibronectin and activation of the PI3K pathway both contribute to survival of these dormant cells. Here, we investigated mechanisms responsible for the dormant phenotype. Experiments demonstrate that integrin α5β1 controls de novo cytoskeletal rearrangements, cell spreading, focal adhesion kinase rearrangement to the cell perimeter and recruitment of a RhoA GAP known as GRAF. This results in the inactivation of RhoA, an effect which is necessary for the stabilization of cortical actin. Experiments also demonstrate that activation of the PI3K pathway by FGF-2 is independent of integrin α5β1 and is also required for cortical actin reorganization, GRAF membrane relocalization and RhoA inactivation. These data suggest that GRAF-mediated RhoA inactivation and consequent phenotypic changes of dormancy depend on dual signaling by FGF-2-initiated PI3K activation and through ligation of integrin α5β1 by fibronectin

Swap-driven self-adhesion and healing of vitrimers

Vitrimers are covalent network materials, comparable in structure to classical thermosets. Unlike normal thermosets, they possess a chemical bond swap mechanism that makes their structure dynamic and suitable for activated welding and even autonomous self-healing. The central question in designing such materials is the trade-off between autonomy and material stability: the swap mechanism facilitates the healing, but it also facilitates creep, which makes the perfectly stable self-healing solid a hard goal to reach. Here, we address this question for the case of self-healing vitrimers made from star polymers. Using coarse-grained molecular dynamics simulations, we studied the adhesion of two vitrimer samples and found that they bond together on timescales that are much shorter than the stress relaxation time. We showed that the swap mechanism allows the star polymers to diffuse through the material through coordinated swap events, but the healing process is much faster and does not depend on this mobility

Bounds on the shear load of cohesionless granular matter

\u3cp\u3eWe characterize the force state of shear-loaded granular matter by relating the macroscopic stress to statistical properties of the force network. The purely repulsive nature of the interaction between grains naturally provides an upper bound for the sustainable shear stress, which we analyse using an optimization procedure inspired by the so-called force network ensemble. We establish a relation between the maximum possible shear resistance and the friction coefficient between individual grains, and find that anisotropies of the contact network (or the fabric tensor) only have a subdominant effect. These results can be considered the hyperstatic limit of the force network ensemble and we discuss possible implications for real systems. Finally, we argue how force anisotropies can be related quantitatively to experimental measurements of the effective elastic constants.\u3c/p\u3

Dynamics of vitrimers: defects as a highway to stress relaxation:Defects as a Highway to Stress Relaxation

\u3cp\u3eWe propose a coarse-grained model to investigate stress relaxation in star-polymer networks induced by dynamic bond-exchange processes. We show how the swapping mechanism, once activated, allows the network to reconfigure, exploring distinct topological configurations, all of them characterized by complete extent of reaction. Our results reveal the important role played by topological defects in mediating the exchange reaction and speeding up stress relaxation. The model provides a representation of the dynamics in vitrimers, a new class of polymers characterized by bond-swap mechanisms which preserve the total number of bonds, as well as in other bond-exchange materials.\u3c/p\u3

Harnessing entropy to enhance toughness in reversibly crosslinked polymer networks

Reversible crosslinking is a design paradigm for polymeric materials, wherein they are microscopically reinforced with chemical species that form transient crosslinks between the polymer chains. Besides the potential for self-healing, recent experimental work suggests that freely diffusing reversible crosslinks in polymer networks, such as gels, can enhance the toughness of the material without substantial change in elasticity. This presents the opportunity for making highly elastic materials that can be strained to a large extent before rupturing. Here, we employ Gaussian chain theory, molecular simulation, and polymer self-consistent field theory for networks to construct an equilibrium picture for how reversible crosslinks can toughen a polymer network without affecting its elasticity. Maximisation of polymer entropy drives the reversible crosslinks to bind preferentially near the permanent crosslinks in the network, leading to local molecular reinforcement without significant alteration of the network topology. In equilibrium conditions, permanent crosslinks share effectively the load with neighbouring reversible crosslinks, forming multi-functional crosslink points. The network is thereby globally toughened, while the linear elasticity is left largely unaltered. Practical guidelines are proposed to optimise this design in experiment, along with a discussion of key kinetic and timescale considerations

Self-stresses control stiffness and stability in overconstrained disordered networks

\u3cp\u3eWe investigate the interplay between prestress and mechanical properties in random elastic networks. To do this in a controlled fashion, we introduce an algorithm for creating random free-standing frames that support exactly one state of self-stress. By multiplying all the bond tensions in this state of self-stress by the same number-which with the appropriate normalization corresponds to the physical prestress inside the frame-we systematically evaluate the linear mechanical response of the frame as a function of prestress. After proving that the mechanical moduli of affinely deforming frames are rigorously independent of prestress, we turn to nonaffinely deforming frames. In such frames, prestress has a profound effect on linear response: not only can it change the values of the linear modulus-an effect we demonstrate to be related to a suppressive effect of prestress on nonaffinity-but prestresses also generically trigger a bistable mechanical response. Thus, prestress can be leveraged to both augment the mechanical response of network architectures on the fly, and to actuate finite deformations. These control modalities may be of use in the design of both novel responsive materials and soft actuators.\u3c/p\u3