There are distinct advantages to designing polymer systems that afford two distinct sets of material properties– an intermediate polymer that would enable optimum handling and processing of the material, while maintaining the ability to tune in different, final polymer properties that enable the optimal functioning of the material. In this study, by designing a series of non‐stoichiometric thiol‐acrylate systems, a polymer network is initially formed via a base catalyzed Michael addition reaction that proceeds stoichiometrically via the thiol‐acrylate “click” reaction. This self‐limiting reaction results in a polymer with excess acrylic functional groups within the network. At a later point in time, the photoinitiated, free radical polymerization of the excess acrylic functional groups results in a highly crosslinked, robust material system. These two stage reactive thiol‐acrylate networks that have intermediate stage rubbery moduli and glass transition temperatures that range from 0.5 MPa and ‐10 °C to 22 MPa and 22 °C, respectively, are formulated and characterized. The same polymer networks can then attain glass transition temperatures that range from 5 °C to 195 °C and rubbery moduli of up to 200 MPa after the subsequent photocuring stage. The two stage reactive networks formed by varying the stoichiometric ratios of the thiol and acrylate monomers were shown to perform as substrates for three specific applications: shape memory polymers, impression materials, and as optical materials for writing refractive index patterns.

Summary Polycomb Group RING finger homologs (PCGF1, 2, 3, 4, 5 and 6) are critical components in the assembly of distinct Polycomb Repression Complex 1 (PRC1) related complexes. Here we identify a protein interaction domain in BCL6 co-repressor, BCOR, which binds the ubiquitin-like RAWUL domain of PCGF1 (NSPC1) and PCGF3 but not of PCGF2 (MEL18) or PCGF4 (BMI1). Because of the selective binding, we have named this domain PCGF Ub-like fold Discriminator (PUFD). The structure of BCOR PUFD bound to PCGF1 reveals 1. that PUFD binds to the same surfaces as observed for a different Polycomb Group RAWUL domain and 2. the ability of PUFD to discriminate among RAWULs stems from the identity of specific residues within these interaction surfaces. These data are the first to show the molecular basis for determining the binding preference for a PCGF homolog, which ultimately helps determine the identity of the larger PRC1-like assembly.

In this study, we develop thiol/acrylate two-stage reactive network forming polymer systems that exhibit two distinct and orthogonal stages of curing. Using a thiol-acrylate system with excess acrylate functional groups, a first stage polymer network is formed via a 1 to 1 stoichiometric thiol-acrylate Michael addition reaction (stage 1). At a later point in time, the excess acrylate functional groups are homopolymerized via a photoinitiated free radical polymerization to form a second stage polymer network (stage 2). By varying the monomers within the system as well as the stoichiometery of the thiol to acrylate functional groups, we demonstrate the ability of the two-stage polymer network forming systems to encompass a wide range of properties at the end of both the stage 1 and stage 2 polymerizations. Using urethane di- and hexa-acrylates within the formulations led to two-stage reactive polymeric systems with stage 1 Tgs that ranged from −12 to 30 °C. The systems were then photocured, upon which the Tg of the systems increases by up to 90 °C while also achieving a nearly 20 fold modulus increase.

Summary: High modulus two-stage reactive polymer systems are fabricated and characterized in regards to their thermomechanical properties and behavior. The polymer networks comprise thiol-acrylate formulations in which a polymer matrix is initially formed via an amine catalyzed thiol-Michael addition 'click' reaction, eventually followed by photoinitiated, free radical polymerization of the excess acrylic functional groups to result in formation of a highly crosslinked, high modulus polymer material. Composites were formed and evaluated using two distinct polymerizable thiol-acrylate formulations, each with three different filler types. Here, the fillers were used primarily to improve the mechanical performance of the polymer material following the initial Michael addition reaction though improvements were also observed in some materials following the photopolymerization as well. The fillers used were 0.7 mm methacrylated silica particles, translucent Kevlar veil and PET mesh. Thermomechanical analysis showed that the fillers resulted in a significant increase in the modulus in both the polymer networks formed at the end of each of the orthogonal reactions without a significant change in the glass transition temperatures (T g ). The two-stage matrix formed with a hexa-acrylate matrix and 20 volume % silica particles showed a 125% increase in the modulus at the end of the Michael-addition reaction and a 100% increase in the modulus after photopolymerization of the acrylates, when compared with the modulus of the unfilled polymer.