3D bioprinting is usually implemented on flat surfaces, posing serious limitations in the fabrication of multilayered curved constructs. 4D bioprinting, combining 3D bioprinting with time-dependent stimuli-induced transformation, enables the fabrication of shape-changing constructs. Here, a 4D biofabrication method is reported for cartilage engineering based on the differential swelling of a smart multi-material system made from two hydrogel-based materials: hyaluronan and alginate. Two ink formulations are used: tyramine-functionalized hyaluronan (HAT, high-swelling) and alginate with HAT (AHAT, low-swelling). Both inks have similar elastic, shear-thinning, and printability behavior. The inks are 3D printed into a bilayered scaffold before triggering the shape-change by using liquid immersion as stimulus. In time (4D), the differential swelling between the two zones leads to the scaffold's self-bending. Different designs are made to tune the radius of curvature and shape. A bioprinted formulation of AHAT and human bone marrow cells demonstrates high cell viability. After 28 days in chondrogenic medium, the curvature is clearly present while cartilage-like matrix production is visible on histology. A proof-of-concept of the recently emerged technology of 4D bioprinting with a specific application for the design of curved structures potentially mimicking the curvature and multilayer cellular nature of native cartilage is demonstrated.

We show that the interaction potential between sterically stabilized, nearly hard-sphere [poly(methyl methacrylate)-poly(lauryl methacrylate) (PMMA-PLMA)] colloids at a water-oil interface has a negligible unscreened-dipole contribution, suggesting that models previously developed for charged particles at liquid interfaces are not necessarily applicable to sterically stabilized particles. Interparticle potentials, U (r), are extracted from radial distribution functions [g(r), measured by fluorescence microscopy] via Ornstein-Zernike inversion and via a reverse Monte Carlo scheme. The results are then validated by particle tracking in a blinking optical trap. Using a Bayesian model comparison, we find that our PMMA-PLMA data is better described by a screened monopole only rather than a functional form having a screened monopole plus an unscreened dipole term. We postulate that the long range repulsion we observe arises mainly through interactions between neutral holes on a charged interface, i.e., the charge of the liquid interface cannot, in general, be ignored. In agreement with this interpretation, we find that the interaction can be tuned by varying salt concentration in the aqueous phase. Inspired by recent theoretical work on point charges at dielectric interfaces, which we explain is relevant here, we show that a screened 1 r 2 term can also be used to fit our data. Finally, we present measurements for poly(methyl methacrylate)-poly(12-hydroxystearic acid) (PMMA-PHSA) particles at a water-oil interface. These suggest that, for PMMA-PHSA particles, there is an additional contribution to the interaction potential. This is in line with our optical-tweezer measurements for PMMA-PHSA colloids in bulk oil, which indicate that they are slightly charged.

We consider the surface pressure of a colloid-laden liquid interface. As micron-sized particles of suitable wettability can be irreversibly bound to the liquid interface on experimental timescales, we use the...

No abstract

Electrostatic interactions between point charges embedded into interfaces separating dielectric media are omnipresent in soft matter systems and often control their stability. Such interactions are typically complicated and do not resemble their bulk counterparts. For instance, the electrostatic potential of a point charge at an air-water interface falls off as r −3 , where r is the distance from the charge, exhibiting a dipolar behaviour. This behaviour is often assumed to be generic, and is widely referred to when interpreting experimental results. Here we explicitly calculate the in-plane potential of a point charge at an interface between two electrolyte solutions with different, finite dielectric permittivities and Debye screening lengths, such as oil and water. We show that the asymptotic behaviour of this potential is neither a dipole, which characterises the potential at airwater interfaces, nor a screened monopole, which describes the bulk behaviour in a single electrolyte solution. By considering the same problem in arbitrary dimensions, we find that the physics behind this difference can be traced to the asymmetric propagation of the interaction in the two media. Our results should be relevant to understand the effective potential acting between interfacial proteins in biofilms, and the self-assembly of charged colloids at droplet surfaces in oil-water emulsions.