ACS Macro Letters

The precise use of a widely available and inexpensive metallocene catalyst enabled the synthesis of isotactic polypropylene copolymers characterized by the copresence of randomly distributed cyclic units in the backbone and unsaturated pendant units employing 1,5-hexadiene as comonomer. Optimization of the polymerization conditions avoided the cross-linking phenomena that negatively affects the material processing and final properties, resulting in good yields of samples featuring high molecular masses and a precisely controlled microstructure...

In nature, proteins possess the remarkable ability to sense and respond to mechanical forces, thereby triggering various biological events, such as bone remodeling and muscle regeneration. However, in synthetic systems, harnessing the mechanical force to induce material growth still remains a challenge. In this study, we aimed to utilize low-frequency ultrasound (US) to activate horseradish peroxidase (HRP) and catalyze free radical polymerization. Our findings demonstrate the efficacy of this mechano-enzymatic chemistry in rapidly remodeling the properties of materials through cross-linking polymerization and surface coating...

Cross-linked polyolefins have important advantages over their thermoplastic analogues, particularly improved impact strength and abrasion resistance, as well as increased chemical and thermal stability; however, most strategies for their production involve postpolymerization cross-linking of polyolefin chains. Here, a tandem ring-opening metathesis polymerization (ROMP)/hydrogenation approach is presented. Cyclooctene (COE)- co -dicyclopentadiene (DCPD) networks are first synthesized using ROMP, after which the dispersed Ru metathesis catalyst is activated for hydrogenation through the addition of hydrogen gas...

The reversible formation and cleavage of disulfide bonds under physical/chemical stimuli make it a valuable motif in constructing dynamically cross-linked materials. In the present work, the block copolymer bearing pendent dithiolanes was synthesized and fabricated into isoporous membranes by the combination of self-assembly and nonsolvent-induced phase separation strategy. The cross-linking within the membrane was realized by the thiol-initiated ring-opening cascades of cyclic disulfides. Successful formation of disulfide bond networks within the isoporous membranes was proved by the Raman spectra, UV-vis diffuse reflectance spectroscopy, differential scanning calorimetry, and rheological analysis...

Self-consistent field theory for thin films of AB diblock polymers in the double-gyroid phase reveals that in the absence of preferential wetting of monomer species at the film boundaries, films with the (211) plane oriented parallel to the boundaries are more stable than other orientations, consistent with experimental results. This preferred orientation is explained in the context of boundary frustration. Specifically, the angle of intersection between the A/B interface and the film boundary, the wetting angle, is thermodynamically restricted to a narrow range of values...

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Identifying the origin of scattering from polymer materials is crucial to infer structural features that can relate to functional properties. Here, we use our recently developed virtual-site coarse graining to accelerate atomistic simulations and show how various molecular features govern wide-angle X-ray scattering from a conjugated polymer, poly(3-hexylthiophene) (P3HT). The efficient molecular dynamics simulations can represent the structure and capture the emergence of crystalline order from amorphous melts upon cooling while retaining atomistic details of chain configurations...

Bioadhesives have garnered widespread attention in the biomedical field, for wound healing and tissue sealing. However, challenges exist due to the inferior performance of bioadhesives, including weak adhesion, poor biocompatibility, or lack of biodegradability. In this work, we demonstrate the fabrication of hydrogel adhesive based on polypeptides composed of lysine and glutamic acid. The cation-π interaction between the ammonium cations and phenyl groups endows the hydrogel with strong cohesion, and the hydrophobicity of the phenyl group significantly enhances the interaction between polypeptides and the substrate interface, leading to excellent adhesive performance...

Producing backbone degradable copolymers via free-radical copolymerization is a promising, yet challenging method to develop more sustainable materials for many applications. In this work, we present the copolymerization of 2-methylen-1,3-dioxepane (MDO) with crotonic acid derivative esters. MDO can copolymerize by radical ring-opening polymerization incorporating degradable ester moieties in the polymer backbone, although this can often be difficult due to the very unfavorable reactivity ratios. Crotonic acid derivatives, on the other hand, can be easily produced completely from biomass but are typically very difficult to (co)polymerize due to low propagation rates and very unfavorable reactivity ratios...

Side substitution is an effective way of functionalizing and modifying the properties of polyamides. Meanwhile, side substitution would significantly influence the crystallization kinetics and polymorphic phase transition of polyamides, which, however, has not been well elucidated. Herein, we synthesized the side-substituted long-chain polyamides with various content of methyl pendent groups and investigated their crystallization and phase transition behaviors. We find that the thermal parameters of side-substituted polyamides vary linearly with the side group content, analogous to the isomorphic crystallization of random copolymers...

We introduce an approach in diblock copolymer design, where modifying the junction point with rigid bulky monomer expands the cross-sectional area of the interface and leads to a decrease in the repeat period. Using living anionic polymerization, we synthesized a series of dialkynyl midfunctionalized poly(styrene- b -methyl methacrylate) (PSM-DA) and functionalized them using the thiol-alkyne click reaction with specifically selected rigid bulky monomers: PSS-(3-mercapto)propyl-heptaisobutyl substituted (PSS) and 1-adamantanethiol (ADA)...

Processable polymers of intrinsic microporosity (PIMs) are emerging as promising candidates for next-generation ion exchange membranes (IEMs). However, especially with high ion exchange capacity (IEC), IEMs derived from PIMs suffer from severe swelling, thus, resulting in decreased selectivity. To solve this problem, we report ultramicroporous polymer framework membranes constructed with rigid Tröger's Base network chains, which are fabricated via an organic sol-gel process. These membranes demonstrate excellent antiswelling, with swelling ratios below 4...

The influence of the water content on ion and water transport mechanisms in polymer membranes under low to moderate hydration conditions remains poorly understood. In this study, we combine ion and water diffusivity (PFG-NMR) measurements with atomistic molecular dynamics simulations to better understand transport processes in hydrated salt-doped poly(ethylene glycol). Above the water percolation threshold, the experimental and simulated diffusivities are in good agreement with the free volume transport models...

We present a quantitative comparison of the dynamic structure factors from unentangled and strongly entangled poly(butylene oxide) (PBO) melts. As expected, the low molecular weight PBO displays Rouse dynamics, however, with very significant subdiffusive center-of-mass diffusion. The spectra from high molecular weight entangled PBO can be very well described by the dynamic structure factor based on the concept of local reptation, including the Rouse dynamics within the tube and allowing for non-Gaussian corrections...

We construct a coarse-grained molecular dynamics model based on poly(ethylene oxide) and lithium bis(trifluoromethane)sulfonimide salt to examine the combined effects of temperature and salt concentration on the transport properties. Salt doping notably slows the dynamics of polymer chains and reduces ion diffusivity, resulting in a glass transition temperature increase proportional to the salt concentration. The polymer diffusion is shown to be well represented by a modified Vogel-Fulcher-Tamman (M-VFT) equation that accounts for both the temperature and salt concentration dependence...

Carbon dioxide (CO2 ), as a renewable and nontoxic C1 feedstock, has been recognized as an ideal comonomer to prepare sustainable materials. In this regard, substantial focus has been dedicated to the ring-opening copolymerization of CO2 and epoxides, which results in the creation of aliphatic polycarbonates in most cases. Here, we report an unprecedented strategy to synthesize functional and degradable polyester- co -polyethers from CO2 , butadiene, and epoxides via a CO2 /butadiene-derived δ-valerolactone intermediate (EVP)...

As molecular design and the structure-property relationships of photochemical molecules established in the literature serve as a convenient reference for mechanophore exploration, many typical mechanophores suffer undesired responses to UV light or even sunlight in bulk polymers. We developed a strategy of a poly(methyl acrylate)/polyurethane (PMA/PU) interpenetrating polymer network (IPN) to suppress the photochromic property of the mechanophore and promote its mechanochromic property. A widely used rhodamine mechanophore (Rh-2OH) was first incorporated into polyurethane (P1)...

Branched polymer architectures are used to tune the mechanical properties of impact-resistant thin films through parameters, such as chain length and grafting density. While chain dispersity affects molecular properties, such as interpenetration and entanglements, structure-property relationships accounting for dispersity are challenging to obtain experimentally and are often neglected in computational models. We employ molecular dynamics simulations to model the high-rate tensile elongation and nanoballistic impact of thin films composed of bidisperse star polymers with varying arm lengths...

We report a facile stimuli-responsive strategy to generate reactive oxygen and nitrogen species (ROS and RNS) in the biological milieu from a photocleavable water-soluble block copolymer under visible light irradiation (427 nm, 2.25 mW/cm2 ). An anthraquinone-based water-soluble polymeric nitric oxide (NO) donor ( BCPx-NO ) is synthesized, which exhibits NO release in the range of 40-65 μM within 10 h of photoirradiation with a half-life of 30-103 min. Additionally, BCPx-NO produces peroxynitrite (ONOO- ) and singlet oxygen (1 O2 ) under photoirradiation...

Vinyl ethers are commonly used to deactivate Grubbs catalysts and terminate ring opening metathesis polymerization (ROMP) by forming Fischer carbene species with attenuated metathesis reactivity. However, we recently demonstrated that a cyclic enol ether, 2,3-dihydrofuran (DHF), can in fact be homopolymerized or copolymerized with norbornene derivatives. 1,5-Cyclooctadiene (COD) and cyclooctene (COE) consist of an important class of ROMP monomers, and we describe here a study of their copolymerization with DHF...