There exists a need for an innovative reconstructive approach for breast reconstruction, tackling current drawbacks and limitations present in the clinic. In this respect, adipose tissue engineering could offer a promising alternative. We have previously shown that methacrylamide-functionalized gelatin scaffolds are suitable to support the adhesion of adipose tissue-derived stem cells as well as their subsequent differentiation into the adipogenic lineage. The current paper aims to compare different techniques to produce such scaffolds including direct versus indirect 3D printing. Extrusion-based (direct) 3D printing was compared to indirect 3D printing exploiting a polylactic acid (PLA) sacrificial mould, thereby focussing on the physico-chemical characteristics of the obtained scaffolds. The results indicate that similar properties can be achieved irrespective of the technique applied. It can therefore be concluded that indirect 3D printing could offer some benefits over direct additive manufacturing (AM) as a more complex design can be created while materials that were previously unsuited for direct printing because of limitations associated with their characteristics (e.g. low viscosity), could potentially be applied as starting materials for indirect 3D printing to generate porous constructs with full control over their design.

In techniques such as Dynamic Light Scattering (DLS), Fluorescence Correlation Spectroscopy, and image mining, motion is tracked by the autocorrelation of a signal over logarithmic time scales. For instance the tracking signal in DLS is the scattered light intensity; it remains correlated at time scales where scant changes in the arrangement of the scattering particles occur, but decays exponentially at the time scales of their diffusion. When there are multiple time scales of motion (for instance due to scatterers of different sizes), the correlation curve has more than one exponential fall. Extracting the decay constants or hydrodynamic sizes due to each exponential fall in a multi-species field correlation curve becomes an ill-conditioned mathematical problem. We describe a new algorithm to invert a multi-modal correlation curve by Sequential Extraction of the Late Exponentials (SELE). The idea is that while the inversion of a multi-exponential equation may be ill posed, that of a single exponential is not. So we fit data windows towards to base of the correlation curve to extract the largest contribution species, remove the species contribution from the correlation curve, and repeat the process with the remnant curve. The single exponent can be robustly fitted by least-square minimization with initial guesses generated by an adapted cumutant technique (power-series) that includes stretch coefficients (measure of sample dispersity). The proposed algorithm resolves particle sizes separated by 3X, and is reliable against fluctuations in the correlation curve and to localized regions of suboptimal data. The algorithm can be used to track particle dynamics in solution in multi-species problems such as self-assembly.

Edible devices are an emergent technology and in this paper the simplicity and efficacy that poly(acrylic acid)/calcium hydroxide possess in creating a pH sensitive ingestible actuator which responds to acidic environments such as gastric fluid is demonstrated. It was found that poly(acrylic acid)/calcium hydroxide hydrogels exhibit reversible actuation upon submerging in 0.1 M sodium citrate for 2 hours. Our results show that these hydrogels can restore their compressive stress to 0.19 ± 0.06 MPa, swelling ratio to 26 ± 2 and volume to 56% ± 3% of its original volume. This work offers new possibilities for developments in a variety of fields such as drug delivery, 4D printed materials, soft robotics and edible devices.

Small angle neutron scattering (SANS) and dynamic light scattering (DLS) measurements were made on near physiological solutions of a bottlebrush shape polyelectrolyte, aggrecan. Aggrecan is a biologically important molecule whose complexes with hyaluronic acid (HA) provide the osmotic resistance of cartilage. We have investigated the effect of complexation of aggrecan with HA on the structure and dynamic properties of aggrecan solutions. SANS reveals that the supramolecular structure of aggrecan assemblies is only marginally affected by the HA. DLS indicates that the dynamic response of the aggrecan-HA complex is slower than that of the corresponding aggrecan solution. However, addition of calcium ions slightly increases the relaxation rate of the autocorrelation function of the aggrecan solution.

We investigate the structure of neutral and charged bottlebrush polymers in salt-free solutions at different polymer concentrations. In particular, we use molecular dynamics simulations by utilizing a coarse-grained bead-spring model that includes an explicit solvent and complementary experiments made by small angle neutron scattering (SANS). We find that the charged groups along the side chains exert significant repulsive forces, resulting in polymer swelling and backbone stretching. In addition to the primary polyelectrolyte peak, we find that bottlebrush polymers exhibit an additional peak in the form and static structure factors, a feature that is absent in neutral polymers. We show that this additional peak describes the intra-molecular correlations between the charged side chains.

Ionic hydrogels are an abundant class of materials with applications ranging from drug delivery devices to high performance concrete to baby diapers. A more thorough understanding of interactions between polyelectrolyte networks and ionic solutes is critical as these materials are further tailored for performance applications in highly targeted ionic environments. In this work, we seek to develop structure-property relationships between polyelectrolyte gels and environments containing high concentrations of multivalent ions. Specifically, this work seeks to elucidate the causes behind differences in hydrogel response to divalent ions of main group metals versus transition metals. PANa-co-PAM hydrogels containing low and high fractions of ionic groups are investigated in solutions of DI water, NaCl, CaCl2, and CuSO4 at concentrations ranging from 5 to 100 mM in order to understand 1) the transient or permanent nature of crosslinks produced in these networks by divalent counter-ions, 2) the role of polymer ionic content in these interactions, and 3) how these interactions scale with salt concentration. Gravimetric swelling and mechanical compression testing are employed to characterize water and salt-swollen hydrogels in order to develop guiding principles to control and manipulate material properties through polymer-counter-ion interactions. The work presented here confirms the formation of permanent crosslinks by transition metal ions, offers explanation for the behavioral discrepancy observed between ionic hydrogels and main group versus transition metal ions, and illustrates how such hydrogel properties scale with counter-ion concentration.

A simple model system towards an impedance-probing strain sensor based on conducting tough hydrogels is demonstrated. A poly(acrylamide) hydrogel, cross-linked with N,N’-methylene-bis(acrylamide) was contacted with carbon fibres for electrical impedance analysis. The conductivity of the salt-containing hydrogel was determined to be 114 ± 10 mS/cm. Upon stretching the hydrogel samples to their fourfold initial length, the impedance response increased according to a power law. This was used to establish a sensing equation for the relation between the resistive component of the impedance signal and the applied mechanical strain under tension. This work contributes to the development of highly stretchable and soft strain sensors for applications in soft robotics.

Controlled degradation of hydrogels enables several applications of these materials, including controlled drug and cell release applications and directed growth of neural networks. These applications motivate the need of a simulation framework for modeling controlled degradation in hydrogels. We develop a Dissipative Particle Dynamics (DPD) framework for hydrogel degradation. As a model hydrogel, we prepare a network formed by end-linking tetra-arm polyethylene glycol precursors. We model bond breaking during degradation of this hydrogel as a stochastic process. The fraction of degradable bonds follows first order degradation kinetics. We characterize the rate of mass loss during degradation process.