Elucidation of Substantial Differences in Ring-Opening Polymerization Outcomes from Subtle Variation of Glucose Carbonate-Based Monomer Substitution Patterns and Substituent Types.

The substituents present upon five-membered bicyclic glucose carbonate monomers were found to greatly affect the reactivities and regioselectivities during ring-opening polymerization (ROP), which contrast in significant and interesting ways from previous studies on similar systems, while also leading to predictable effects on the thermal properties of the resulting polycarbonates. Polymerization behaviors were probed for a series of five five-membered bicyclic 2,3-glucose-carbonate monomers having 4,6-ether, -carbonate, or -sulfonyl urethane protecting groups, under catalysis with three different organobase catalysts. Irrespective of the organobase catalyst employed, regioregular polycarbonates were obtained via ROP of monomers with ether substituents, while the backbone connectivities of polymers derived from monomers with carbonate protecting groups suffered transcarbonylation reactions, resulting in irregular backbone connectivities and broad molar mass distributions. The sulfonyl urethane-protected monomers were unable to undergo organobase-catalyzed ROP, possibly due to the acidity of the proton in urethane functionality. The thermal behaviors of polycarbonates with ether and carbonate pendant groups were investigated in terms of thermal stability and glass transition temperature (Tg). A two-stage thermal decomposition was observed when tert-butyloxycarbonyl (BOC) groups were employed as protecting side chains, while all other polycarbonates presented high thermal stabilities with a single-stage thermal degradation. Tg was greatly affected by side-chain bulkiness, with values ranging from 39 to 139 °C. These fundamental findings of glucose-based polycarbonates may facilitate the development of next-generation sustainable highly functional materials.

Fused Filament Fabrication 4D Printing of a Highly Extensible, Self-Healing, Shape Memory Elastomer Based on Thermoplastic Polymer Blends.

A polymer blend with high extensibility, exhibiting both shape memory and self-healing, was 4D printed using a low-cost fused filament fabrication (FFF, or fused deposition modeling, FDM) 3D printer. The material is composed of two commercially available commodity polymers, polycaprolactone (PCL), a semi-crystalline thermoplastic, and polystyrene-block-poly(ethylene-co-butylene)-block-polystyrene (SEBS), a thermoplastic elastomer. The shape memory and self-healing properties of the blends were studied systematically through thermo-mechanical and morphological characterization, providing insight into the shape memory mechanism useful for tuning the material properties. In 3D-printed articles, the orientation of the semi-crystalline and micro-phase-separated domains leads to improvement of the shape memory property and extensibility of this material compared to compression-molded samples. By controlling the orientation of the printed fibers, we achieved a high strain at break over 1200%, outperforming previously reported flexible 4D-printed materials. The self-healing agent, PCL, enables the material to heal scratches and cracks and adhere two surfaces after annealing at 80 °C for 30 min. The high performance, multi-functionality, and potential scalability make it a promising candidate for a broad spectrum of applications, including flexible electronics, soft actuators, and deployable devices.

Structural characterization of steroidal saponins by electrospray ionization and fast-atom bombardment tandem mass spectrometry.

The structural characterization of four steroidal saponin compounds involving two and three sugar groups, namely spirostanol saponins and furostanol saponins, were investigated by positive ion fast-atom bombardment (FAB), electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (MS/MS) techniques. Important structural information was obtained from collision-induced dissociation (CID) and FAB-MS spectra with different liquid matrices. It was found that a characteristic fragmentation involving the loss of 144 Da arising from the cleavage of the E-ring was observed when there was no sugar chain at the C-26 position. When a glucoside group was substituted at the C-26 position, this C-26 sugar moiety was preferentially eliminated. All of these compounds produced a major product ion with a stable skeleton structure at m/z 255. The results of this paper can assist structural analysis of mixtures of steroidal saponins.