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Interactions between molecules in the synovial fluid and the cartilage surface may play a vital role in the formation of adsorbed films that contribute to the low friction of cartilage boundary lubrication. Osteoarthritis (OA) is the most common degenerative joint disease. Previous studies have shown that in OA-diseased joints, hyaluronan (HA) not only breaks down resulting in a much lower molecular weight (MW), but also its concentration is reduced ten times. Here, we have investigated the structural changes of lipid-HA complexes as a function of HA concentration and MW to simulate the physiologically relevant conditions that exist in healthy and diseased joints. Small angle neutron scattering and dynamic light scattering were used to determine the structure of HA-lipid vesicles in bulk solution, while a combination of atomic force microscopy and quartz crystal microbalance was applied to study their assembly on a gold surface. We infer a significant influence of both MW and HA concentrations on the structure of HA-lipid complexes in bulk and assembled on a gold surface. Our results suggest that low MW HA cannot form an amorphous layer on the gold surface, which is expected to negatively impact the mechanical integrity and longevity of the boundary layer and could contribute to the increased wear of the cartilage that has been reported in joints diseased with OA. 

Recent experimental and theoretical work has shown that sticker clustering can be used to enhance properties such as toughness and creep resistance of polymer networks. While it is clear that the changes in properties are related to a change in network topology, the mechanistic relationship is still not well understood. In this work, the effect of sticker clustering was investigated by comparing the dynamics of random copolymers with those where the stickers are clustered at the ends of the chain in the unentangled regime using both linear mechanics and diffusion measurements. Copolymers of N , N -dimethyl acrylamide (DMA) and pendant histidine groups were synthesized using reversible addition–fragmentation chain transfer (RAFT) polymerization. The clustered polymers were synthesized using a bifunctional RAFT agent, such that the midblock consisted of PDMA and the two end blocks were random copolymers of DMA and the histidine-functionalized monomer. Upon addition of Ni ions, transient metal-coordinate crosslinks are formed as histidine–Ni complexes. Combined studies of rheology, neutron scattering and self-diffusion measurements using forced Rayleigh scattering revealed changes to the network topology and stress relaxation modes. The network topology is proposed to consist of aggregates of the histidine–Ni complexes bridged by the non-associative midblock. Therefore, stress relaxation requires the cooperative dissociation of multiple bonds, resulting in increased relaxation times. The increased relaxation times, however, were accompanied by faster diffusion. This is attributed to the presence of defects such as elastically inactive chain loops. This study demonstrates that the effects of cooperative sticker dissociation can be observed even in the presence of a significant fraction of loop defects which are known to alter the nonlinear properties of conventional telechelic polymers. 

Tuning the optoelectronic properties of donor‐acceptor conjugated polymers (D‐A CPs) is of great importance in designing various organic optoelectronic devices. However, there remains a critical challenge in precise control of bandgap through synthetic approach, since the chain conformation also affects molecular orbital energy levels. Here, D‐A CPs with different acceptor units are explored that show an opposite trend in energy band gaps with the increasing length of oligothiophene donor units. By investigating their chain conformation and molecular orbital energy, it is found that the molecular orbital energy alignment between donor and acceptor units plays a crucial role in dictating the final optical bandgap of D‐A CPs. For polymers with staggered orbital energy alignment, the higher HOMO with increasing oligothiophene length leads to a narrowing of the optical bandgap despite decreased chain rigidity. On the other hand, for polymers with sandwiched orbital energy alignment, the increased band gap with increasing oligothiophene length originates from the reduction of bandwidth due to more localized charge density distribution. Thus, this work provides a molecular understanding of the role of backbone building blocks on the chain conformation and bandgaps of D‐A CPs for organic optoelectronic devices through the conformation design and segment orbital energy alignment.