Macromolecules

Electrostatic interactions are key determinants in the assembly and organization of ionic micelles. Here, we synthesized sequence-defined polypeptoid block copolymers with discrete chain lengths and single or triple charged residues arranged in distinct patterns. Model-free small-angle neutron scattering analysis of semidilute polymer solutions at pH 9.0 revealed that intermicellar interactions f…

A polyisobutylene sample terminated with a succinic anhydride (PIBSA) was modified via succinimide formation with diethylenetriamine (DETA), triethylenetetramine (TETA), and tetraethylenepentamine (TEPA) either alone or as an equimolar mixture of DETA and TETA to form either mono-(m-) or bis-(b-) PIBSI-polyamines (PIBSI-PA). The residual free amines of the PIBSI-PA samples were labeled with 1-pyr…

Designing thermoplastic elastomers (TPEs) that are simultaneously biodegradable, metal-free, and mechanically robust remains a major challenge. Here, we report a one-pot organocatalytic ring-opening polymerization strategy that converts a mixed feed of ε-caprolactone (CL), δ-valerolactone (VL), and l-lactide (LLA) into high-molecular-weight PLLA-b-PCVL-b-PLLA triblock copolyesters without metal c…

Single-chain nanoparticles (SCNPs) are well-defined nanoscale objects formed through the intramolecular cross-linking of individual polymer chains. A longstanding challenge in this field is the inability to synthesize SCNPs at high concentrations, an essential requirement for scalable production and practical applications. Here, we introduce an entropy-driven strategy that enables one-pot prepara…

The mechanical response of intrinsically disordered proteins (IDPs) and polyampholyte (PA) chains is vital for understanding their biological functions and designing functional materials. We investigate the force-extension behavior of a PA chain with distinct charge sequences using molecular dynamics simulations and a theoretical approach based on the generalized random-phase approximation (GRPA)…

The melt oxidation of isotactic polypropylene (iPP) was used to impart functionality relevant for upcycling and repurposing the polymer for new applications. Terminal vinylidene groups (due to chain scission) and oxidized functional groups such as ketones, aldehydes, and hydroxyl groups were present in the melt oxidized samples, forming PP copolymers with functional co-repeat units. Two regimes w…

The performance of semiconducting polymers is strongly influenced by the structural arrangement of the polymer chains. Solvent-induced prestructuring of polymer chains may occur prior to polymer deposition, impacting device performance. We employed fluorescence techniques, including fluorescence correlation spectroscopy (FCS) and single-molecule fluorescence spectroscopy (smFS), to reveal chain c…

We report the synthesis of ultrasmall nanogels (Rg < 6 nm) from branched and hyperbranched cyclic polyglycerols (Mn = 3–200 kg/mol) via intramolecular cross-linking with diboronic acids (benzene-1,4-diboronic acid, Bz-2B, and [(1,2-diphenylethene-1,2-diyl)bis(4,1-phenylene)] diboronic acid, TPE-2B) through dynamic covalent bonding. Structural analysis by small-angle X-ray scattering revealed a cl…

Cardo structures are applied extensively for the preparation of high refractive index polymers (HRIPs) with intrinsically low optical anisotropy. While such design allows for the achievement of low birefringence, the refractive indices of cardo-based polymers have been largely limited to below 1.70. We report herein a modular cardo design based on 9,9-diarylfluorene bearing sulfur-containing arom…

Closed-loop chemical recycling of polymers to their constituent monomers and subsequent repolymerization is a promising strategy for plastic recycling. Within this field, aliphatic polyesters and polycarbonates are often highlighted, and the thermodynamics that describe the ring-opening polymerization (ROP) equilibria have become a common metric to assess their chemical recyclability. The ring-ch…