Organic polydisulfides hold immense potential for the design of recyclable materials. Of these, polymers based on lipoic acid are attractive, as they are based on a natural, renewable resource. Herein, we demonstrate that reductive degradation of lipoic acid polydisulfides is a rapid process whereby the quantity of added initiator relative to the polymer content defines the mechanism of polymer degradation, through the main chain scission, self-immolation, or “chain transfer” depolymerization. The latter mechanism is defined as the one during which a thiol group released through the decomposition of one polydisulfide chain initiates depolymerization of the neighbor macromolecule. The chain transfer mechanism afforded the highest yields of recovery of the monomer in its pristine form, and just one molecule of the reducing agent to initiate polymer degradation afforded recovery of over 50% of the monomer. These data are important to facilitate the development of polymer recycling and monomer reuse schemes.

We described an insect-inspired strategy for conferring reversible, high responsivity on polymer microgels to dilute-source CO2 (≤5000 ppm in gas mixtures). This is demonstrated on oligo(ethylene oxide)-based microgels that contain tertiary amines on the polymer chains with proper organic small molecular carbonates in the polymer–solvent system. Similar to the synergistic contribution of the CO2 receptor subunits in mosquitoes for CO2 response, laser light scattering and related studies indicated that the CO2-response of the microgels in terms of the volume changes works through the coordination of different functional moieties in the system, making it different from the conventional CO2-response mechanism. While this pushes the lower response threshold of CO2 concentration down to ca. 1000 ppm, this unique strategy can also satisfy the urge to achieve both effective CO2 capture and facile CO2 release, making it possible to couple the detection with the capture and utilization of indoor excess CO2.

Hexagonally packed (HEX) cylindrical microdomains can be obtained through the self-assembly of block copolymers (BCPs) with a moderately asymmetric volume fraction of one block (f), resulting in the formation of minor cylinders. However, for next-generation lithography and high-density memory devices, it is desirable to obtain densely and tetragonally packed inverted cylindrical microdomains, which are composed of the major block in the minor matrix. The inverted cylinders differ from conventional HEX cylinders, which consist of the minor block in the matrix of the major block. In this study, we achieved this objective by utilizing a binary blend of a polystyrene-b-poly(4-vinylpyridine) copolymer (S4VP) and polystyrene-b-poly(4-hydroxystyrene) copolymer (SHS), where the P4VP block exhibited a strong hydrogen bonding interaction with the PHS block. By carefully controlling the molecular weight ratio of S4VP and SHS as well as the blend composition, we successfully observed tetragonally packed inverted PS cylinders with a square cross-section at a volume fraction of PS of 0.69.

We report the synthesis of block copolymers of monomethoxylated polyethylene glycol and poly(glycerol carbonate) (mPEG-b-PGC) via the ring-opening polymerization of benzyl glycidyl ether, monomethoxylated polyethylene glycol, and carbon dioxide using a cobalt salen catalyst. The resulting block copolymers display high polymer/cyclic carbonate selectivity (>99%) and, if two oxirane monomers are used, random incorporation into the polymer feed. The resulting diblock mPEG-b-PGC polymer shows promise as a nanocarrier for surfactant-free, sustained chemotherapeutic delivery. mPEG-b-PGC, with paclitaxel conjugated to the pendant primary alcohol of the glycerol polymer backbone, readily forms 175 nm diameter particles in solution and contains 4.6 wt % paclitaxel (PTX), which is released over 42 days. The mPEG-b-PGC polymer itself is noncytotoxic, whereas the PTX-loaded nanoparticles are cytotoxic to lung, breast, and ovarian cancer cell lines.

With the trend toward lighter and thinner flexible electronics, developing foldable polymeric substrates that can withstand ultralow folding radiuses has become an urgent issue. Here, a strategy to develop polyimide (PI) films with excellent dynamic and static folding resistance under an ultralarge curvature through copolymerizing one “unidirectional diamine” with classic PMDA-ODA PIs to achieve a kind of folding-chain PI (FPI). It was theoretically and experimentally confirmed that the spring-like folding structure equipped PI films with an enhanced elastic behavior and thus an excellent ability to endure a large curvature. Among them, FPI-20 did not show any crease even after folding over 200000 times under a folding radius of 0.5 mm, while creases were observed on pure PI film only after folding 1000 times. It is noteworthy that the folding radius was almost 5 times smaller than that in current reports (2–3 mm). Meanwhile, the spread angle of FPI-20 films after static folding at 80 °C under a 0.5 mm folding radius get 51% larger than that of films, showing the remarkable static folding resistance.

We report a generalized platform for synthesizing a polymer nanoweb with a high specific surface area via a bicellar template, composed of 1,2-dipalmitoyl phosphocholine (DPPC), 1,2-dihexanoyl phosphocholine (DHPC), and 1,2-dipalmitoyl phosphoglycerol (DPPG). The pristine bicelle (in the absence of monomer or polymer) yields a variety of well-defined structures, including disc, vesicle, and perforated lamella. The addition of styrene monomers in the mixture causes bicelles to transform into lamellae. Monomers are miscible with DPPC and DPPG initially, while polymerization drives polymers to the DHPC-rich domain, resulting in a polymer nanoweb supported by the outcomes of small angle neutron scattering, differential scanning calorimetry, and transmission electron microscopy.

Polyurethane (PU) foams are produced from toxic, petrochemical- and phosgene-derived isocyanates. Although nonisocyanate polyurethane (NIPU) has shown promise as a replacement for traditional PU, the synthesis of NIPU foams has not been widely studied due to the difficulties in replicating the foaming process of PU, in situ CO2 production through the hydrolysis of isocyanates. Hereby, we report the synthesis of amine-CO2 adducts and their CO2 adsorption–desorption characteristics under different conditions. The results show that the amine-CO2 adducts can exhibit up to 87% CO2 desorption at 60 °C after aminolysis with cyclic carbonate. The amine-CO2 adduct is used as both a foaming agent and a comonomer to obtain low-density foams (0.203–0.239 g·cm–3) after heating at 50–60 °C for 24–48 h. This marks the successful synthesis of in situ CO2-blown NIPU foams using an amine-CO2 adduct.

We investigate the molecular origin of mechanical reinforcement in a polymer nanocomposite (PNC) under a glass state via molecular dynamics simulations. The strength of the PNC system is found to be reinforced mainly via reduced plastic deformations of the nanoparticle neighborhood (NN). Such a reinforcement effect is found to decay with an increase in the strain rate. The Arrhenius–Eyring relation is used to analyze its origin. The amplitude of the reinforcement is found to be determined by the difference between the energy barrier (ΔE) for the activation of NN and the work (W) done by the applied stress to conquer that barrier. A larger strain rate is found to result in a larger W and, hence, a weaker reinforcement effect. Such a strain-rate dependence is verified in the experimental tensile tests of a poly(vinyl alcohol)/SiO2 composite system. These results not only provide a new understanding of the molecular origin of the reinforcement effect in the PNC system, but also pave the way for a better design of the PNC material properties.

Efficient routes for the preparation of functional self-healing hydrogels from functional polymers are needed. In this study, we developed a strategy to effectively produce a vanillin-modified poly(vinyl alcohol) (PVA-vanillin) through the Hantzsch reaction. This polymer was cross-linked with a phenylboronic acid-containing polymer (PB) that was also prepared using the Hantzsch reaction to fabricate a hydrogel through borate ester linkages under mild conditions (25 °C, pH ∼ 7.4). This hydrogel had excellent antioxidant abilities due to the 1,4-dihydropyridine (DHP) rings and the vanillin moieties in the hydrogel structures; it was also self-healable and injectable owing to the dynamic borate ester linkages. Furthermore, the antioxidant self-healing hydrogel had low cytotoxicity and exhibited favorable safety in animal experiments, indicating its potential as a safe implantable cell or drug carrier. This study developed a method for preparing functional polymers and related self-healing hydrogels in a facile manner; it demonstrated the value of the Hantzsch reaction in exploiting antioxidant self-healing hydrogels for biomedical applications, which may provide insight into the design of other functional self-healing hydrogels through different multicomponent reactions.

We report the use of l-aspartic acid chiral ionic hydrogen bonds to drive liquid–liquid phase separation (LLPS) and precision two-dimensional electrostatic self-assembly in photo-RAFT aqueous polymerization-induced self-assembly (photo-PISA). Homopolymerization can yield salt-resistant, 3 nm ultrafine fibril-structured 5 nm ultrathin lamellae via LLPS, a left-to-right-handed chirality transition, and a droplets-to-lamellae transition. Like-charge block copolymerization leads to supercharged yet identical fibril-structured ultrathin lamellae, also, via LLPS, the left-to-right chirality transition and the droplets-to-lamellae transition. Ultrafine structures maintain intactness upon the seeded polymerization of the oppositely charged monomer. This work demonstrates that amino acid chiral ionic hydrogen bonds are powerful for the precision synthesis of salt-resistant ultrathin membrane nanomaterials.

The effect of ionic liquids on the reversible addition–fragmentation chain transfer (RAFT) polymerization mediated by a visible-light-induced photoiniferter mechanism was investigated. N,N-Dimethyl acrylamide was polymerized by photoiniferter polymerization in 1-ethyl-3-methylimidazolium ethylsulfate [EMIM][EtSO4] ionic liquid. We observed a considerable increase in the polymerization rate constants in ionic liquids (ILs), as well as in the mixed solvent of water and the IL, compared to those observed with water alone as the solvent. To demonstrate the robustness of the process, block copolymers with varying block ratios were synthesized with precise control over their molecular weight and mass dispersity (Đ). The very high chain-end fidelity provided by the photoiniferter polymerization in IL was described by using MALDI-ToF MS analysis.

Cellulose-based dielectrics with attractive dielectric performance are promising candidates to develop eco-friendly electrostatic energy storage devices. Herein, all-cellulose composite films with superior dielectric constant were fabricated by manipulating the dissolution temperature of native cellulose, where we revealed the relationship among the hierarchical microstructure of the crystalline structure, the hydrogen bonding network, the relaxation behavior at a molecular level, and the dielectric performance of the cellulose film. The coexistence of cellulose I and cellulose II led to a weakened hydrogen bonding network and unstable C6 conformations. The increased mobility of cellulose chains in the cellulose I-amorphous interphase enhanced the dielectric relaxation strength of side groups and localized main chains. As a result, the as-prepared all-cellulose composite films exhibited a fascinating dielectric constant of as high as 13.9 at 1000 Hz. This work proposed here provides a significant step toward fundamentally understanding the dielectric relaxation of cellulose, thus developing high-performance and eco-friendly cellulose-based film capacitors.

Strain-induced crystallization (SIC) is a well-known toughening strategy in elastomers, but is rarely observed in hydrogels due to their high-water content and limited deformability. Here we report a phenomenon of SIC in highly swollen and associative hydrogels by introducing an extremely large deformation by indentation with a needle. Using in situ birefringence imaging, we discovered that SIC occurs close to the needle tip upon large strain, displacing the nucleation of a crack from the needle tip to a position further away from the tip. The morphology of the fracture as well as the force to induce the gel fracture with the needle can be controlled by playing with temperature and cross-linking and hence triggering or not the SIC. Our discovery points to a future direction in creating SIC in highly swollen hydrogels, with potential implications for many biological material designs, and surgical injury prediction or prevention in associative tissues.

T cells play a critical role in the adaptive immune response of the body, especially against intracellular pathogens and cancer. In vitro, T cell activation studies typically employ planar (two-dimensional, 2D) culture systems that do not mimic native cell-to-extracellular matrix (ECM) interactions, which influence activation. The goal of this work was to study T cell responses in a cell line (EL4) and primary mouse T cells in three-dimensional (3D) bioprinted matrices of varied stiffness. Cell-laden hydrogels were 3D bioprinted from gelatin methacryloyl (GelMA) using a digital light processing (DLP)-based 3D bioprinter operated with visible light (405 nm). Mechanical characterization revealed that the hydrogels had pathophysiologically relevant stiffnesses for a lymph node-mimetic tissue construct. EL4, a mouse T cell lymphoma line, or primary mouse T cells were 3D bioprinted and activated using a combination of 10 ng/mL of phorbol myristate acetate (PMA) and 0.1 μM of ionomycin. Cellular responses revealed differences between 2D and 3D cultures and that the biomechanical properties of the 3D bioprinted hydrogel influence T cell activation. Cellular responses of the 2D and 3D cultures in a soft matrix (19.83 ± 2.36 kPa) were comparable; however, they differed in a stiff matrix (52.95 ± 1.36 kPa). The fraction of viable EL4 cells was 1.3-fold higher in the soft matrix than in the stiff matrix. Furthermore, primary mouse T cells activated with PMA and ionomycin showed 1.35-fold higher viable cells in the soft matrix than in the stiff matrix. T cells bioprinted in a soft matrix and a stiff matrix released 7.4-fold and 5.9-fold higher amounts of interleukin-2 (IL-2) than 2D cultured cells, respectively. Overall, the study demonstrates the changes in the response of T cells in 3D bioprinted scaffolds toward engineering an ex vivo lymphoid tissue-mimetic system that can faithfully recapitulate T cell activation and unravel pathophysiological characteristics of T cells in infectious biology, autoimmunity, and cancers.

Ring-opening metathesis polymerization (ROMP) in an aqueous medium provides an important environmentally friendly platform for the preparation of water-soluble polymeric materials. However, it is challenging to keep high synthetic efficacy and good control over molecular weight and distribution due to the inevitable catalyst decomposition in an aqueous medium. To meet this challenge, we propose a facile monomer emulsified aqueous ROMP (ME-ROMP) by injecting a tiny amount of a CH2Cl2 solution of the Grubbs’ third-generation catalyst (G3) into the aqueous solution of norbornene (NB) monomers without deoxygenation. Driven by the minimization of interfacial tension, the water-soluble monomers could serve as surfactants with hydrophobic NB moieties inserted into the CH2Cl2 droplets of G3, leading to the significantly suppressed catalyst decomposition and accelerated polymerization. The ME-ROMP is confirmed to be living with an ultrafast polymerization rate, near quantitative initiation and monomer conversion, for the highly efficient and ultrafast synthesis of well-defined water-soluble polynorbornenes with various compositions and architectures.

The synthesis of a water-soluble polycobaltoceniumylmethylene chloride (PCM-Cl) via ring-opening transmetalation polymerization is presented. Starting from a carba[1]magnesocenophane and cobalt(II) chloride, this route gives access to a polymer with methylene-bridged cobaltocenium moieties within the polymers’ main-chain. The polymer was characterized by NMR spectroscopy, elemental analysis, TGA, DSC, XRD, and CV measurements, as well as UV–vis spectroscopy. Furthermore, GPC measurements in an aqueous eluent versus pullulan standards were conducted to gain insight into the obtained molar masses and distributions. In addition, the ion-dependent solubility was demonstrated by anion exchange, tuning the hydrophobic/hydrophilic properties of this redox-responsive material.

The phase structure with a small domain size in polymers is expected to provide a template for lithography to fabricate electronic devices, while the uniformity and thermal stability of the phase structure are vital in lithography. In this work, we report an accurately microphase-separated system of comb-like poly(ionic liquid) (PIL)-based homopolymers containing imidazolium cation junctions between the main chain parts and the long alkyl side chains, poly(1-((2-acryloyloxy)ethyl)-3-alkylimidazolium bromide) (P(AOEAmI-Br)). The ordered hexagonally packed cylinder (HEX) and lamellar (LAM) structures with small domain sizes (sub-3 nm) were successfully achieved. Since the microphase separation was induced by the incompatibility between the main chain parts and the hydrophobic alkyl chains, the microdomain spacing of the ordered structure was independent of the molecular weight and molecular weight distribution of P(AOEAmI-Br) homopolymers and could be precisely regulated by changing the length of the alkyl side chains. Importantly, the microphase separation was promoted by the charged junction groups; thus, the phase structure and domain size of P(AOEAmI-Br) exhibited excellent thermal stability.

We report the synthesis of a macrocyclic poly(ethylene oxide) (PEO) connected by one [Ru(bpy)3]2+ unit (where bpy = 2,2′-bipyridine), a photoactive metal complex that provides photosensitivity and potential biomedical applications to this polymer structure. The PEO chain provides biocompatibility, water solubility, and topological play. The macrocycles were successfully synthesized by copper-free click cycloaddition between a bifunctional dibenzocyclooctyne (DBCO)-PEO precursor and 4,4′-diazido-2,2′-bipyridine, followed by complexation with [Ru(bpy)2Cl2]. The cyclic product accumulated efficiently in MCF7 cancer cells and exhibited a longer fluorescence lifetime than its linear analogue, likely due to differences in the accessibility of the ligand-centered/intraligand states of Ru polypyridyls in both topologies.

Simultaneous ring-opening copolymerization is a powerful strategy for the synthesis of highly functional copolymers from different types of cyclic monomers. Although copolymers are essential to the plastics industry, environmental concerns associated with current fossil-fuel-based synthetic polymers have led to an increasing interest in the use of renewable feedstock for polymer synthesis. Herein, we report a scalable synthetic platform to afford unique polysaccharides with different pendant functional groups from biomass-derived levoglucosan and ε-caprolactone via cationic ring-opening copolymerization (cROCOP). Biocompatible and recyclable bismuth triflate was identified as the optimal catalyst for cROCOP of levoglucosan. Copolymers from tribenzyl levoglucosan and ε-caprolactone, as well as from tribenzyl and triallyl levoglucosan, were successfully synthesized. The tribenzyl levoglucosan monomer composition ranged from 16% to 64% in the copolymers with ε-caprolactone and 22% to 79% in the copolymers with triallyl levoglucosan. The allylic levoglucosan copolymer can be utilized as a renewably derived scaffold to modify copolymer properties and create other polymer architectures via postpolymerization modification. Monomer reactivity ratios were determined to investigate the copolymer microstructure, indicating that levoglucosan-based copolymers have a gradient architecture. Additionally, we demonstrated that the copolymer glass transition temperature (Tg, ranging from −44.3 to 33.8 °C), thermal stability, and crystallization behavior could be tuned based on the copolymer composition. Overall, this work underscores the utility of levoglucosan as a bioderived feedstock for the development of functional sugar-based copolymers with applications ranging from sustainable materials to biomaterials.

In this study, we developed a double-network hybrid polymer that controls the strength and density of cross-linking points by utilizing the bonds of titania and catechol groups with an o-nitrobenzyl group (ONBg) as the photoreactive cross-linking points. In addition, this hybrid material system, which is composed of thermally dissociable bonds between titania and carboxyl groups, can be molded before light irradiation. The Young’s modulus increased by approximately 1000 times upon irradiation with UV light. Moreover, introducing microstructures using the photolithography technique improved the tensile strength and fracture energy by approximately 32 and 15 times, respectively, compared to the sample without the photoreaction. The improved toughness was achieved by the macrostructures, which enhanced the effective cleavage of sacrificial bonds between the carboxyl groups and titania.