No abstract

Synthetic transformation of d-xylose into a four-membered cyclic ether allows for reactions with CO2 leading to linear polycarbonates by either ring-opening copolymerisation directly or by isolation of a six-membered cyclic carbonate followed by ring-opening polymerisation.

Rigorous investigations of the organobase-catalyzed ring-opening polymerizations (ROPs) of a series of five-membered cyclic carbonate monomers derived from glucose revealed that competing transcarbonylation reactions scrambled the regiochemistries of the polycarbonate backbones. Regioirregular poly(2,3-α- d -glucose carbonate) backbone connectivities were afforded by 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD)-catalyzed ROPs of three monomers having different cyclic acetal protecting groups through the 4- and 6-positions. Small molecule studies conducted upon isolated unimers and dimers indicated a preference for Cx–O2 vs Cx–O3 bond cleavage from tetrahedral intermediates along the pathways of addition–elimination mechanisms when the reactions were performed at room temperature. Furthermore, treatment of isolated 3-unimer or 2-unimer, having the carbonate linkage in the 3- or 2-position as obtained from either Cx–O2 or Cx–O3 bond cleavage, respectively, gave the same 74:26 (3-unimer:2-unimer) ratio, confirming the occurrence of transcarbonylation reactions with a preference for 3-unimer vs. 2-unimer formation in the presence of organobase catalyst at room temperature. In contrast, unimer preparation at −78 °C favored Cx–O3 bond cleavage to afford a majority of 2-unimer, presumably due to a lack of transcarbonylation side reactions. Computational studies supported the experimental findings, enhancing fundamental understanding of the regiochemistry resulting from the ring-opening and subsequent transcarbonylation reactions during ROP of glucose carbonates. These findings are expected to guide the development of advanced carbohydrate-derived polymer materials by an initial monomer design via side chain acetal protecting groups, with the ability to evolve the properties further through later-stage structural metamorphosis.

The maximum capacitive energy stored in polymeric dielectric capacitors, which are ubiquitous in high-power-density devices, is dictated by the dielectric breakdown strength of the dielectric polymer. The fundamental mechanisms of the dielectric breakdown, however, remain unclear. Based on a simple free-volume model of the polymer fluid state, we hypothesized that the free ends of linear polymer chains might act as “defect” sites, at which the dielectric breakdown can initiate. Thus, the dielectric breakdown strength of cyclic polymers should exhibit enhanced stability in comparison to that of their linear counterparts having the same composition and similar molar mass. This hypothesis is supported by the ∼50% enhancement in the dielectric breakdown strength and ∼80% enhancement in capacitive energy density of cyclic polystyrene melt films in comparison to corresponding linear polystyrene control films. Furthermore, we observed that cyclic polymers exhibit a denser packing density than the linear chain melts, an effect that is consistent with and could account for the observed property changes. Our work demonstrates that polymer topology can significantly influence the capacitive properties of polymer films, and correspondingly, we can expect polymer topology to influence the gas permeability, shear modulus, and other properties of thin films dependent on film density.

Interactions between drug molecules, nanocarrier components, and surrounding media influence the properties and therapeutic efficacies of nanomedicines. In this study, we investigate the role that reversible covalent loading of a hydrophobic drug exerts on intra-nanoparticle physical properties and explore the utility of this payload control strategy for tuning the access of active agents and, thereby, the stimuli sensitivity of smart nanomaterials. Glutathione sensitivity was controlled via altering the degree of hydrophobic payload loading of disulfide-linked camptothecin-conjugated sugar-based nanomaterials. Increases in degrees of camptothecin conjugation (f CPT) decreased aqueous accessibility and reduced glutathione-triggered release. Although the lowest f CPT gave the fastest camptothecin release, it resulted in the lowest camptothecin concentration. Remarkably, the highest f CPT resulted in a 5.5-fold improved selectivity against cancer vs noncancerous cells. This work represents an advancement in drug carrier design by demonstrating the importance of controlling the amount of drug loading on the overall payload and its availability.