Buckling initiation in layered hydrogels during transient swelling

Subjected to compressive stresses, soft polymers with stiffness gradients can display various buckling patterns. These compressive stresses can have different origins, like mechanical forces, temperature changes, or, for hydrogel materials, osmotic swelling. Here, we focus on the influence of the transient nature of osmotic swelling on the initiation of buckling in confined layered hydrogel structures. A constitutive model for transient hydrogel swelling is outlined and implemented as a user-subroutine for the commercial finite element software Abaqus. The finite element procedure is benchmarked against linear perturbation analysis results for equilibrium swelling showing excellent correspondence. Based on the finite element results we conclude that the initiation of buckling in a two-layered hydrogel structure is highly affected by transient swelling effects, with instability emerging at lower swelling ratios and later in time with a lower diffusion coefficient. In addition, for hard-on-soft systems the wavelength of the buckling pattern is found to decrease as the diffusivity of the material is reduced for gels with a relatively low stiffness gradient between the substrate and the upper film. This study highlights the difference between equilibrium and transient swelling when it comes to the onset of instability in hydrogels, which is believed to be of importance as a fundamental aspect of swelling as well as providing input to guiding principles in the design of specific hydrogel systems

Polymer sequencing by molecular machines: A framework for predicting the resolving power of a sliding contact force spectroscopy sequencing method

We evaluate an AFM-based single molecule force spectroscopy method for mapping sequences in otherwise difficult to sequence heteropolymers, including glycosylated proteins and glycans. The sliding contact force spectroscopy (SCFS) method exploits a sliding contact made between a nanopore threaded over a polymer axle and an AFM probe. We find that for sliding α- and β- cyclodextrin nanopores over a wide range of hydrophilic monomers, the free energy of sliding is proportional to the sum of two dimensionless, easily calculable parameters representing the relative partitioning of the monomer inside the nanopore or in the aqueous phase, and the friction arising from sliding the nanopore over the monomer. Using this relationship we calculate sliding energies for nucleic acids, amino acids, glycan and synthetic monomers and predict on the basis of these calculations that SCFS will detect N- and O-glycosylation of proteins and patterns of sidechains in glycans. For these applications, SCFS offers an alternative to sequence mapping by mass spectrometry or newly-emerging nanopore technologies that may be easily implemented using a standard AFM

Tn and STn are members of a family of carbohydrate tumour antigens that possess carbohydrate-carbohydrate interactions

The mucin-type O-glycome in cancer aberrantly expresses the truncated glycans Tn (GalNAcα1-Ser/Thr) and STn (Neu5Acα2,6GalNAcα1-Ser/Thr). However, the role of Tn and STn in cancer and other diseases is not well understood. Our recent discovery of the self-binding properties (carbohydrate–carbohydrate interactions, CCIs) of Tn (Tn–Tn) and STn (STn–STn) provides a model for their possible roles in cellular transformation. We also review evidence that Tn and STn are members of a larger family of glycan tumor antigens that possess CCIs, which may participate in oncogenesis

Competitive ligand exchange of crosslinking ions for ionotropic hydrogel formation

Currently there are limitations to gelation strategies to form ionically crosslinked hydrogels, derived in particular from a lack of control over the release kinetics of crosslinking ions, which severely restrict applications. To address this challenge, we describe a new approach to form hydrogels of ionotropic polymers using competitive displacement of chelated ions, thus making specific ions available to induce interactions between polymer chains and form a hydrogel. This strategy enables control of ion release kinetics within an aqueous polymer solution and thus control over gelation kinetics across a wide range of pH. The described technique simplifies or facilitates the use of ionotropic hydrogels in a range of applications, such as 3D printing, microfluidic-based cell encapsulation, injectable preparations and large scale bubble and solid free mouldable gels. We investigate a range of chelator-ion combinations and demonstrate this powerful method to form hydrogels across a wide range of pH and µm–cm length scales. We highlight our findings by applying this gelation strategy to some of the more challenging hydrogel application areas using alginate and polygalacturonate as model polymer systems

Versatile, cell and chip friendly method to gel alginate in microfluidic devices

Alginate is used extensively in microfluidic devices to produce discrete beads or fibres at the microscale. Such structures may be used to encapsulate sensitive cargoes such as cells and biomolecules. On chip gelation of alginate represents a significant challenge since gelling kinetics or physicochemical conditions are not biocompatible. Here we present a new method that offers a hitherto unprecedented level of control over the gelling kinetics and pH applied to the encapsulation of a variety of cells in both bead and fibre geometries. This versatile approach proved straightforward to adjust to achieve appropriate solution conditions required for implementation in microfluidic devices and resulted in highly reliable device operation and very high viability of several different encapsulated cell types for prolonged periods. We believe this method offers a paradigm shift in alginate gelling technology for application in microfluidics