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An H-polymer has an architecture that consists of four branches symmetrically attached to the ends of a polymer backbone, similar in shape to the letter "H". Here, a renewable H-polymer efficiently synthesized using only ring-opening transesterification is demonstrated. The strategy relies on a tetrafunctional poly(±-lactide) macroinitiator, from which four poly(±-lactide) branches are grown simultaneously. 1 H NMR spectroscopy, size exclusion chromatography (SEC), and matrix-assisted laser desorption/ionization (MALDI) spectrometry were used to verify the macroinitiator purity. Branch growth was probed using 1 H NMR spectroscopy and SEC to reveal unique transesterification phenomena that can be controlled to yield architecturally pure or more complex materials. H-shaped PLA was prepared at the multigram scale with a weight-average molar mass M w > 100 kg/mol and low dispersity Đ < 1.15. Purification involved routine precipitations steps, which yielded products that were architecturally relatively pure (∼93%). Small-amplitude oscillatory shear and extensional rheology measurements demonstrate the unique viscoelastic behavior associated with the H-shaped architecture.

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 reaction temperature for hydrogenation must be sufficiently high to allow mobility within the system, as dictated by thermal transitions (i.e., glass and melting transitions) of the polymeric matrix. COE-rich materials exhibit branched-polyethylene-like crystallinity (25% crystallinity) and melting points ( T m = 107 °C), as well as excellent ductility (>750% extension), while majority DCPD materials are glassy ( T g = 84 °C) and much stiffer ( E = 710 MPa); all materials exhibit high tensile toughness. Importantly, hydrogenation of olefins in these cross-linked materials leads to notable improvements in oxidative stability, as saturated networks do not experience the same substantial degradation of mechanical performance as their unsaturated counterparts upon prolonged exposure to air.

This work aimed to decrease the water permeability ( P H2O ) in ethylene vinyl alcohol (EVOH)-based copolymers by introducing high levels of backbone regioregularity and stereoregularity. Both regioregular atactic and isotactic EVOH samples with 75 mol % ethylene were prepared by a ring-opening metathesis polymerization (ROMP)-hydrogenation-deprotection approach and then compared to commercial EVOH(44) (containing 44 mol % ethylene) as a low P O2 ) in ethylene vinyl alcohol (EVOH)-based copolymers by introducing high levels of backbone regioregularity and stereoregularity. Both regioregular atactic and isotactic EVOH samples with 75 mol % ethylene were prepared by a ring-opening metathesis polymerization (ROMP)-hydrogenation-deprotection approach and then compared to commercial EVOH(44) (containing 44 mol % ethylene) as a low P O2 standard with poor water barrier characteristics (i.e., high P H2O ). The high levels of regioregularity and stereoregularity in these copolymers increased the melting temperature ( T m values as compared to that of the isotactic polymer. Wide-angle X-ray scattering showed that semicrystalline EVOH(44) exhibited a monoclinic structure characteristic of commercial materials, while ROMP-derived polymers displayed an intermediate structure between monoclinic and orthorhombic. Tensile testing showed that isotacticity resulted in brittle mechanical behavior, while the atactic and commercial EVOH(44) samples had higher tensile toughness values. Although EVOH(44) had the lowest c ), and glass-transition temperature ( T while having a g ) compared to less regular structures. EVOH(44) demonstrated the highest T m but lower χ c and T g values as compared to that of the isotactic polymer. Wide-angle X-ray scattering showed that semicrystalline EVOH(44) exhibited a monoclinic structure characteristic of commercial materials, while ROMP-derived polymers displayed an intermediate structure between monoclinic and orthorhombic. Tensile testing showed that isotacticity resulted in brittle mechanical behavior, while the atactic and commercial EVOH(44) samples had higher tensile toughness values. Although EVOH(44) had the lowest P O2 of the samples explored, the atactic and tough ROMP-derived polymer approached this value of P O2 while having a P H2O over 3 times lower than that of commercial EVOH(44)., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

High-density polyethylene (HDPE) is a widely used commercial plastic due to its excellent mechanical properties, chemical resistance, and water vapor barrier properties. However, less than 10% of HDPE is mechanically recycled, and the chemical recycling of HDPE is challenging due to the inherent strength of the carbon-carbon backbone bonds. Here, we report chemically recyclable linear and branched HDPE with sparse backbone ester groups synthesized from the transesterification of telechelic polyethylene macromonomers. Stoichiometrically self-balanced telechelic polyethylenes underwent transesterification polymerization to produce the PE-ester samples with high number-average molar masses of up to 111 kg/mol. Moreover, the transesterification polymerization of the telechelic polyethylenes and the multifunctional diethyl 5-(hydroxymethyl)isophthalate generated branched PE-esters. Thermal and mechanical properties of the PE-esters were comparable to those of commercial HDPE and tunable through control of the ester content in the backbone. In addition, branched PE-esters showed higher levels of melt strain hardening compared with linear versions. The PE-ester was depolymerized into telechelic macromonomers through straightforward methanolysis, and the resulting macromonomers could be effectively repolymerized to generate a high molar mass recycled PE-ester sample. This is a new and promising method for synthesizing and recycling high-molar-mass linear and branched PE-esters, which are competitive with HDPE and have easily tailorable properties.

Porous materials with pore dimensions of the nanometer length scale are useful as nanoporous membranes. ABA triblock copolymers are convenient precursors to such nanoporous materials if the end blocks are easily degradable ( e.g. , polylactide or PLA), leaving nanoporous polymeric membranes (NPMs) if in thin film form. The membrane properties are dependent on midblock monomer structure, triblock copolymer composition, overall molar mass, and polymer processing conditions. Polycyclooctene (PCOE) NPMs were prepared using this method, with tunable pore sizes on the order of tens of nanometers. Solvent casting was shown to eliminate film defects and allowed achievement of superior mechanical properties over melt processing techniques, and PCOE NPMs were found to be very tough, a major advance over previously reported NPMs. Oxygen plasma etching was used to remove the surface skin layer to obtain membranes with higher surface porosity, membrane hydrophilicity, and flux of both air and water. This is a straightforward method to reliably produce highly tough NPMs with high levels of porosity and hydrophilic surface properties.

Star block (ABC) 4 terpolymers consisting of a rubbery poly(γ-methyl-ε-caprolactone) (PγMCL) (C) core and hard poly(l-lactide) (PLLA) (B) and poly(d-lactide) (PDLA) (A) end-blocks with varying PDLA to PLLA block ratios were explored as high-performance, sustainable, aliphatic polyester thermoplastic elastomers (APTPEs). The stereocomplexation of the PDLA/PLLA blocks within the hard domains provided the APTPEs with enhanced thermal stability and an increased resistance to permanent deformation compared to nonstereocomplex analogs. Variations in the PDLA:PLLA block ratio yielded tunable mechanical properties likely due to differences in the extent and location of stereocomplex crystallite formation as a result of architectural constraints. This work highlights the improvements in mechanical performance due to stereocomplexation within the hard domains of these APTPEs and the tunable nature of the hard domains to significantly impact material properties, furthering the development of sustainable materials that are competitive with current industry standard materials.

The performance of sustainable polymers can be modified and enhanced by incorporating functional groups in the backbone of the polymer chain that increases intermolecular interactions, thus impacting the thermal properties of the material. However, in-depth studies on the role of intermolecular interactions on the crystallization of these polymers are still needed. This work aims to ascertain whether incorporating functional groups able to induce intermolecular interactions can be used as a suitable systematic strategy to modify the polymer thermal properties and crystallization kinetics. Thus, amide and additional ester groups have been incorporated into aliphatic polyesters (PEs). The impact of intermolecular interactions on the melting and crystallization behavior, crystallization kinetics, and crystalline structure has been determined. Functional groups that form strong intermolecular interactions increase both melting and crystallization temperatures but retard the crystallization kinetics. Selecting appropriate functional groups allows tuning the crystallinity degree, which can potentially improve the mechanical properties and degradability in semicrystalline materials. The results demonstrate that it is possible to tune the thermal transitions and the crystallization kinetics of PEs independently by varying their chemical structure., (© 2023 Author(s). Published under an exclusive license by AIP Publishing.)

Poloxamers, also known by their trade name, Pluronics, are known to mitigate damage to cellular membranes. However, the mechanism underlying this protection is still unclear. We investigated the effect of poloxamer molar mass, hydrophobicity, and concentration on the mechanical properties of giant unilamellar vesicles, composed of 1-palmitoyl-2-oleoyl-glycero-3-phosphocholine, using micropipette aspiration (MPA). Properties including the membrane bending modulus (κ), stretching modulus ( K ), and toughness are reported. We found that poloxamers tend to decrease K , with an impact largely dictated by their membrane affinity, i.e., both a high molar mass and less hydrophilic poloxamers depress K at lower concentrations. However, a statistically significant effect on κ was not observed. Several poloxamers studied here showed evidence of membrane toughening. Additional pulsed-field gradient NMR measurements provided insight into how polymer binding affinity connects to the trends observed by MPA. This model study provides important insights into how poloxamers interact with lipid membranes to further understanding of how they protect cells from various types of stress. Furthermore, this information may prove useful for the modification of lipid vesicles for other applications, including use in drug delivery or as nanoreactors.

Chemically crosslinked elastomers are a class of polymeric materials with properties that render them useful as adhesives, sealants, and in other engineering applications. Poly(γ-methyl-ε-caprolactone) (PγMCL) is a hydrolytically degradable and compostable aliphatic polyester that can be biosourced and exhibits competitive mechanical properties to traditional elastomers when chemically crosslinked. A typical limitation of chemically crosslinked elastomers is that they cannot be reprocessed; however, the incorporation of dynamic covalent bonds can allow for bonds to reversibly break and reform under an external stimulus, usually heat. In this work, we study the dynamic behavior and mechanical properties of PγMCL elastomers synthesized from aliphatic dianhydride crosslinkers. The crosslinked elastomers in this work were synthesized using the commercially available crosslinkers, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, and 1,2,3,4-cyclobutanetetracarboxylic dianhydride and three-arm hydroxy-telechelic PγMCL star polymers. Stress relaxation experiments on the crosslinked networks showed an Arrhenius dependence of viscosity with temperature with an activation energy of 118 ± 8 kJ/mol, which agrees well with the activation energy of transesterification exchange chemistry obtained from small molecule model studies. Dynamic mechanical thermal analysis and rheological experiments confirmed the dynamic nature of the networks and provided insight into the mechanism of exchange (i.e., associative or dissociative). Tensile testing showed that these materials can exhibit high strains at break and low Young's moduli, characteristic of soft and strong elastomers. By controlling the exchange chemistry and understanding the effect of macromolecular structure on mechanical properties, we prepared the high-performance elastomers that can be potentially reprocessed at moderately elevated temperatures., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Polymer blend compatibilization is an attractive solution for mechanical recycling of mixed plastic waste because it can result in tough blends. In this work, hydroxy-telechelic polyethylene (HOPEOH) reactive additives were used to compatibilize blends of polyethylene terephthalate (PET) and linear low-density polyethylene (LLDPE). HOPEOH additives were synthesized with molar masses of 1-20 kg/mol by ring-opening metathesis polymerization of cyclooctene followed by catalytic hydrogenation. Melt-compounded blends containing 0.5 wt % HOPEOH displayed reduced dispersed phase LLDPE particle sizes with ductilities comparable to virgin PET and almost seven times greater than neat blends, regardless of additive molar mass. In contrast, analogous blends containing monohydroxy PE additives of comparable molar masses did not result in compatibilization even at 2 wt % loading. The results strongly suggest that both hydroxy ends of HOPEOH undergo transesterification reactions during melt mixing with PET to form predominantly PET-PE-PET triblock copolymers at the interface of the dispersed and matrix phases. We hypothesize that the triblock copolymer compatibilizers localized at the interface form trapped entanglements of the PE midblocks with nearby LLDPE homopolymer chains by a hook-and-clasp mechanism. Finally, HOPEOH compounds were able to efficiently compatibilize blends derived solely from postconsumer PET and PE bottles and film, suggesting their industrial applicability.

First-in-class membrane stabilizer Poloxamer 188 (P188) has been shown to confer membrane protection in an extensive range of clinical conditions; however, elements of the systemic distribution and localization of P188 at the organ, tissue, and muscle fiber levels in vivo have not yet been elucidated. Here we used non-invasive fluorescence imaging to directly visualize and track the distribution and localization of P188 in vivo . The results demonstrated that the Alx647 probe did not alter the fundamental properties of P188 to protect biological membranes. Distribution kinetics in mdx mice demonstrated that Alx647 did not interface with muscle membranes and had fast clearance kinetics. In contrast, the distribution kinetics for P188-Alx647 was significantly slower, indicating a dramatic depot and retention effect of P188. Results further demonstrated the significant retention of P188-Alx647 in the skeletal muscle of mdx mice, showing a significant genotype effect with a higher fluorescence signal in the mdx muscles over BL10 mice. High-resolution optical imaging provided direct evidence of P188 surrounding the sarcolemma of skeletal and cardiac muscle cells. Taken together, these findings provide direct evidence of muscle-disease-dependent molecular homing and retention of synthetic copolymers in striated muscles thereby facilitating advanced studies of copolymer-membrane association in health and disease., Competing Interests: J.M.M. is on the scientific advisory board and holds shares in Phrixus Pharmaceuticals Inc., a company developing novel therapeutics for heart failure. The terms of this arrangement have been reviewed and approved by the University of Minnesota in accordance with its conflict of interest policies., (© 2022 The Author(s).)

Selective ion separations are increasingly needed to combat water scarcity, recover resources from wastewater, and enable the efficient recycling of electronics waste. Emulsion liquid membranes (ELMs) have received interest due to rapid kinetics, high selectivities, and low solvent requirements but are too unstable for industrial usage. We demonstrate that polymeric microcapsules can serve as robust, solvent-free mimics of ELMs. As a proof of concept, we incorporated the copper-selective ligand Lix 84-I in the walls of microcapsules formed from a commercial polystyrene- b -polybutadiene- b -polystyrene triblock polymer. The microcapsules were formed from a double-emulsion template, resulting in particles typically 20-120 μm in diameter that encapsulated even smaller droplets of a dilute (≤0.5 M) H 2 SO 4 solution. Batch experiments demonstrated facilitated-transport behavior, with equilibrium reached in as little as 10 min for microcapsules with 1% ligand, and with ∼15-fold selectivity for Cu 2+ over Ni 2+ . Furthermore, the microcapsules could be packed readily in columns for flow-through operation, thus enabling near-complete Cu 2+ removal in ∼2 min under certain conditions, recovery of Cu 2+ by flowing through fresh dilute H 2 SO 4 , and reuse for at least 10 cycles. The approach in this work can serve as a template for using selective ligands to enable robust and simple flow-through processes for a variety of selective ion separations.

Hydroxy-telechelic polyalkenamers have long been synthesized using ring-opening metathesis polymerization (ROMP) in the presence of an acyclic olefin chain-transfer agent (CTA); however, this route typically requires protected diols in the CTA due to the challenge of alcohol-mediated degradation of ruthenium metathesis catalysts that can not only deactivate the catalysts, but also compromise the CTA. We demonstrate the synthesis and implementation of a new hydroxyl-containing CTA in which extended methylene spacers isolate the olefin and alcohol moieties to mitigate decomposition pathways. This CTA enabled the direct ROMP synthesis of hydroxy-telechelic polycyclooctene with controlled chain lengths dictated by the initial ratio of monomer to CTA. The elimination of protection/deprotection steps resulted in improved atom economy. Subsequent hydrogenation of the backbone olefins was performed by a one-pot, catalytic approach employing the ruthenium complex used for the initial ROMP. The resultant approach is a streamlined, atom-economic, and low-waste route to hydroxy-telechelic linear polyethylene that uses a green solvent, succeeds with miniscule quantities of catalyst (0.005 mol %), and requires no additional purification steps.

The origin of melt memory effects associated with semicrystalline polymers and the physical parameters involved in this process have been widely studied in the literature. However, a comprehensive understanding of the role of intermolecular interactions on melt memory is still being developed. For this purpose, we have considered aliphatic polyesters and we have incorporated amide and additional ester groups. Inserting these additional functional groups, the strength of the intermolecular interactions increases widening the melt memory effect. Not only the presence of the functional groups but also the position of these groups in the repeating unit plays a role in the melt memory effect as it impacts the strength of the intermolecular interactions in the crystals. The study of the effect of intermolecular interactions has been extended to successive self-nucleation and annealing thermal fractionation experiments to explore for the first time the role of intermolecular forces on the fractionation capacity of linear polymers. We demonstrated that intermolecular interactions act as intrinsic defects interrupting the crystallizable chain length, thus facilitating thermal fractionation. Overall, this work sheds light on the role of intermolecular interactions on the crystallization behavior of a series of aliphatic polyesters.

Transforming how plastics are made, unmade, and remade through innovative research and diverse partnerships that together foster environmental stewardship is critically important to a sustainable future. Designing, preparing, and implementing polymers derived from renewable resources for a wide range of advanced applications that promote future economic development, energy efficiency, and environmental sustainability are all central to these efforts. In this Chemical Reviews contribution, we take a comprehensive, integrated approach to summarize important and impactful contributions to this broad research arena. The Review highlights signature accomplishments across a broad research portfolio and is organized into four wide-ranging research themes that address the topic in a comprehensive manner: Feedstocks, Polymerization Processes and Techniques, Intended Use, and End of Use. We emphasize those successes that benefitted from collaborative engagements across disciplinary lines.

Poloxamers consisting of poly(ethylene oxide) (PEO) and poly(propylene oxide) segments can protect cell membranes against various forms of stress. We investigated the role of the hydrophobic block chemistry on polymer/membrane binding and cell membrane protection by comparing a series of poly(butylene oxide)- b -PEO (PBO- b -PEO) copolymers to poloxamer analogues, using a combination of pulsed-field-gradient (PFG) NMR experiments and a lactate dehydrogenase (LDH) cell assay. We found that the more hydrophobic PBO- b -PEO copolymers bound more significantly to model liposomes composed of 1-palmitol-2-oleoyl-glycero-3-phosphocholine (POPC) compared to poly(propylene oxide) (PPO)/PEO copolymers. However, both classes of polymers performed similarly when compared by an LDH assay. These results present an important comparison between polymers with similar structures but with different binding affinities. They also provide mechanistic insight as enhanced polymer/lipid membrane binding did not directly translate to increased cell protection in the LDH assay, and therefore, additional factors need to be considered when trying to achieve greater membrane protection efficacy.

Graft polymers are useful in a versatile range of material applications. Understanding how changes to the grafted architecture, such as the grafting density ( z ), the side-chain degree of polymerization ( N sc ), and the backbone degree of polymerization ( N bb ), affect polymer properties is critical for accurately tuning material performance. For graft-through copolymerizations, changes to N sc ), respectively. We show that changes to these parameters can influence the copolymerization reactivity ratios and, in turn, impact the side-chain distribution along a graft polymer backbone. Poly((±)-lactide) macromonomers with z values as low as ca. 1 and as high as 72 were copolymerized with a small-molecule dimethyl ester norbornene comonomer over a range of N MM ) and the initial fraction of the macromonomer in the feed ( f MM 0 ), respectively. We show that changes to these parameters can influence the copolymerization reactivity ratios and, in turn, impact the side-chain distribution along a graft polymer backbone. Poly((±)-lactide) macromonomers with N MM values as low as ca. 1 and as high as 72 were copolymerized with a small-molecule dimethyl ester norbornene comonomer over a range of f MM 0 values (0.1 ≤ f MM 0 ≤ 0.8) using ring-opening metathesis polymerization (ROMP). Monomer conversion was determined using 1 H nuclear magnetic resonance spectroscopy, and the data were fit with terminal and nonterminal copolymerization models. The results from this work provide essential information for manipulating N sc and z while maintaining synthetic control over the side-chain distribution for graft-through copolymerizations.

Polyesters constitute nearly 10% of the global plastic market, but most are essentially non-degradable under ambient conditions or in engineered environments. A range of degradable polyesters have been developed as more sustainable alternatives; however, limitations of practical degradability and scalability have hindered their viability. Here, we utilized transesterification approaches, including in situ polymerization-transesterification, between a salicylate and a polyester to incorporate salicylate units into commercial polyester backbones. The strategy is scalable and practically relevant given that high molar mass polymers can be obtained from melt-processing of commercial polyesters using common compounders or extruders. Polylactide containing sparse salicylate moieties shows enhanced hydrolytic degradability in aqueous buffer, seawater, and alkaline solutions without sacrificing the thermal, mechanical, and O 2 barrier properties of the parent material. Additionally, salicylate sequences were incorporated into polycaprolactone and a derivative of poly(ethylene terephthalate), and those modified polymers also exhibited facile degradation behavior in alkaline solution, further expanding the scope of this approach. This work provides insights and direction for the development of high-performance yet more sustainable and degradable alternatives to conventional polyesters.

An efficient, fast, and reliable method for the synthesis of high-molar-mass polyglycolide (PGA) in bulk using bismuth (III) subsalicylate through ring-opening transesterification polymerization is described. The difference between the crystallization ( T c ≈ 180 °C)/degradation ( T d ≈ 245 °C) temperatures and the melting temperature ( T m ≈ 222 °C) significantly affects the ability to melt-process PGA homopolymer. To expand these windows, the effect of copolymer microstructure differences through incorporation of methyl groups in pairs using lactide or isolated using methyl glycolide (≤10% methyl) as comonomers on the thermal, mechanical, and barrier properties were studied. Structures of copolymers were characterized by nuclear magnetic resonance ( 1 H and 13 C NMR) spectroscopies. Films of copolymers were obtained, and the microstructural and physical properties were analyzed. PGA homopolymers exhibited an approximately 30 °C difference between T m and T c , which increased to 68 °C by incorporating up to 10% methyl groups in the chain while maintaining overall thermal stability. Oxygen and water vapor permeation values of solvent-cast nonoriented films of PGA homopolymers were found to be 4.6 cc·mil·m -2 , respectively. Different methyl distributions in the copolymer sequence, provided through either lactide or methyl glycolide, affected the resulting gas barrier properties. At 10% methyl insertion, using lactide as a comonomer significantly increased both O -1 ·atm -1 and 2.6 g·mil·m -2 ·d -1 ·atm -1 , respectively. Different methyl distributions in the copolymer sequence, provided through either lactide or methyl glycolide, affected the resulting gas barrier properties. At 10% methyl insertion, using lactide as a comonomer significantly increased both O 2 (32 cc·mil·m -2 ·d -1 ·atm -1 ) and water vapor (12 g·mil·m -2 ·d -1 ·atm -1 ) permeation. However, when methyl glycolide was utilized for methyl insertion at 10% Me content, excellent barrier properties for both O 2 (2.9 cc·mil·m -2 ·d -1 ·atm -1 ) and water vapor (1.0 g·mil·m -2 ·d -1 ·atm -1 ) were achieved.

Polymerization-induced microphase separation has been used to prepare solid cross-linked monoliths containing bicontinuous and nanostructured polymer domains. We use this process to fabricate a monolith containing either a negatively or positively charged polyelectrolyte domain inside of the neutral styrene/divinylbenzene-derived matrix. First, the materials are made with a neutral pre-ionic polymer containing masked charged groups. The monoliths are then functionalized to a charged state by treatment with trimethylamine; small-angle X-ray scattering shows no significant morphological change in the microphase-separated structure upon postpolymerization modification. By exchanging dyes with the counterions in the material, we corroborated the continuity of the charged domains. Using ion-exchange capacity measurements, we estimate the number of accessible charges within the material based on macro-chain transfer agent molar mass and loading.

Poly(ethylene terephthalate) (PET) is one of the most prevalent polymers in the world due to its combined thermal, mechanical, and gas barrier attributes. Blending PET with other polymers is an appealing strategy to further tailor properties to meet the needs of an even more diverse range of applications. Most blends with PET are macrophase-separated; only a few miscible systems have been reported. Here, the miscibility of the aromatic polyesters poly(salicylic glycolide) (PSG) and poly(salicylic methyl glycolide) (PSMG) with PET is described. Both PSG and PSMG have similar chemical structures to PET but are derived from sustainable resources and readily degradable. This study suggests that they are fully miscible with PET over the entire composition range, which is attributed to favorable interactions with PET. Negative polymer-polymer interaction parameters (χ) were determined using Flory-Huggins theory to describe melting temperature variations in the blends. In addition, the PET blends showed mechanical properties that are intermediate between the two homopolymers.

Self-assembled polymer nanoparticles have tremendous potential in biomedical and environmental applications. For all applications, tailored polymer chemistries are critical. In this study, we demonstrate a precursor approach in which an activated, organic solvent-soluble block polymer precursor is modified through mild postpolymerization modifications to access new polymer structures. We synthesized and characterized poly(isoprene)- block -poly(di-Boc acrylamide) diblock polymers. This activated-acrylamide-based polymer was then reacted with amines or reductants in the absence of catalysts to yield the hydrophilic blocks polyacrylamide, poly(hydroxypropylene), and poly( N -ethyl acrylamide). The resulting amphiphilic block polymers self-assembled in water to form polymersomes, as confirmed by cryo-electron microscopy and confocal microscopy. The approach also enables simple functionalization with specialized ligands, which we demonstrated by tagging polymers with an amino-fluorophore and imaging by confocal microscopy. We expect that the methodologies established in this study will open doors to new and useful solution nanostructures with surface chemistries that can be optimized for various applications.

Reliable and equitable access to safe drinking water is a major and growing challenge worldwide. Membrane separations represent one of the most promising strategies for the energy-efficient purification of potential water sources. In particular, porous membranes are used for the ultrafiltration (UF) of water to remove contaminants with nanometric sizes. However, despite exhibiting excellent water permeability and solution processability, existing UF membranes contain a broad distribution of pore sizes that limit their size selectivity. To maximize the potential utility of UF membranes and allow for precise separations, improvements in the size selectivity of these systems must be achieved. Block polymers represent a potentially transformative solution, as these materials self-assemble into well-defined domains of uniform size. Several different strategies have been reported for integrating block polymers into UF membranes, and each strategy has its own set of materials and processing considerations to ensure that uniform and continuous pores are generated. This Review aims to summarize and critically analyze the chemistries, processing techniques, and properties required for the most common methods for producing porous membranes from block polymers, with a particular focus on the fundamental mechanisms underlying block polymer self-assembly and pore formation. Critical structure-property-performance metrics will be analyzed for block polymer UF membranes to understand how these membranes compare to commercial UF membranes and to identify key research areas for continued improvements. This Review is intended to inform readers of the capabilities and current challenges of block polymer UF membranes, while stimulating critical thought on strategies to advance these technologies.

Self-assembly of poly(styrene)- block -poly(isoprene)- block -poly(lactide)- block -poly(styrene) (PS-PI-PLA-PS' or SILS') tetrablock terpolymers, where the volume fractions of the first three blocks are nearly equivalent, was studied both experimentally and using the self-consistent field theory (SCFT). SCFT indicates that addition of the terminal PS' chain to a low-molecular-mass, hexagonally packed cylinders forming, SIL precursor can produce a disordered state due to preferential mixing of the polystyrene end-blocks with the PI and PLA midblocks in the SILS' tetrablock, alleviating the unfavorable contact between the highly incompatible PI and PLA segments. In contrast, SCFT predicts that higher-molar-mass triblock precursors will maintain an ordered morphology upon addition of the terminal PS' block due to stronger overall segregation strengths. These predictions were tested using three sets of SILS' polymers that were synthesized based on three precursor SIL triblock polymers differing in total molar mass (14, 30, and 47 kg mol -1 ) and varying the length of the terminal PS' chain. In the lowest-molar-mass set of tetrablock polymers, the shift from order to disorder was observed in the materials at ambient temperature as the molar mass of the terminal PS' block was increased, consistent with SCFT calculations. Disorder with longer S' chain lengths was not found in the two higher-molar-mass polymer sets; the medium-molar-mass set showed both microphase separation and long-range order based on transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS), while the largest of these block polymers microphase separated but showed limited long-range order. The combination of the experimental and theoretical results presented in this work provides insights into the self-assembly of ABCA'-type polymers and highlights potential complications that arise from frustration in accessing well-ordered materials.

Amorphous solid dispersions (ASDs) of crystallizable drugs and polymer excipients are attractive for enhancing the solubility and bioavailability of hydrophobic drug molecules. In this study, the solution behavior of poly( N -isopropylacrylamide- co - N , N -dimethylacrylamide) (PND) and poly(vinylpyrrolidone- co -vinylacetate) (PVPVA), as polymer excipients, and nilutamide (NLT), phenytoin (PHY), and itraconazole (ITN) as model drugs, were monitored by an in vitro dissolution assay, small-angle X-ray scattering (SAXS), dynamic light scattering (DLS), cryogenic transmission electron microscopy (cryo-TEM), and polarized optical microscopy (POM). High degrees of drug supersaturation were coincident with the formation of amorphous nanoparticles in each system. The difference in particle size and kinetic stability between PND and PVPVA systems suggest a difference in how the polymers interact with the drug-rich phase. A series of scenarios are proposed based on whether the polymer interacts more strongly with the drug-rich nanoparticles or with water. Understanding the contribution of drug-rich nanoparticles to achievable supersaturation and the effect of polymer excipients on these particles will inform the design of future solid dispersion systems through a better understanding of the polymer/drug solution relationship.

Highly selective and water permeable dual-layer ultrafiltration (UF) membranes comprising a disordered poly(methyl methacrylate- stat -styrene)- block -poly(lactide) selective layer and a polysulfone (PSF) support layer were fabricated using a co-casting technique. A dilute solution of diblock polymer was spin coated onto a solvent-swollen PSF layer, rapidly heated to dry and disorder the block polymer layer, and subsequently immersed into an ice water coagulation bath to kinetically trap the disordered state in the block polymer selective layer and precipitate the support layer by nonsolvent-induced phase separation. Subsequent removal of the polylactide block generated porous membranes suitable for UF. The permeability of these dual-layer membranes was modulated by tuning the concentration of the PSF casting solution, while the size-selectivity was maintained because of the narrow pore size distribution of the self-assembled block polymer selective layer. Elimination of the thermal annealing step resulted in a dramatic increase in the water permeability without adversely impacting the size-selectivity, as the disordered nanostructure present in the concentrated casting solution was kinetically trapped upon rapid drying. The co-casting strategy outlined in this work may enable the scalable fabrication of block polymer membranes with both high permeability and high selectivity.

Numerous ion-selective and reference electrodes have been developed over the years. Following the need for point-of-care and wearable sensors, designs have transitioned recently from bulky devices with an aqueous inner filling solution to planarizable solid-contact electrodes. However, unless the polymeric sensing and reference membranes are held in place mechanically, delamination of these membranes from the underlying solid to which they adhere physically limits sensor lifetime. Even minor external mechanical stress or thermal expansion can result in membrane delamination and, thereby, device failure. To address this problem, we designed a sensing platform based on poly(ethylene terephthalate) substrates to which polyacrylate-based sensing and polymethacrylate-based reference membranes are attached covalently. Ion-selective membranes with covalently attached or freely dissolved ionophore- and ionic-liquid-doped reference membranes can be directly photopolymerized onto surface-functionalized poly(ethylene terephthalate), resulting in the formation of covalent bonds between the underlying substrate and the attached membranes. H + - and K + -selective electrodes thus prepared exhibit highly selective responses with the theoretically expected (Nernstian) response slope, and reference electrodes provide sample-independent reference potentials over a wide range of electrolyte concentrations. Even repeated mechanical stress does not result in the delamination of the sensing and reference membranes, leading to electrodes with much improved long-term performance. As demonstrated for poly(ethylene- co -cyclohexane-1,4-dimethanol terephthalate) (PETG), this approach may be expanded to a wide range of other polyester, polyamide, and polyurethane platform materials. Covalent attachment of sensing and reference membranes to an inert plastic platform material is a very promising approach to a problem that has plagued the field of ion-selective electrodes and field effect transistors for over 30 years.

Using molecular dynamics simulations and transferable force fields, we designed a series of symmetric triblock amphiphiles (or high-χ block oligomers) comprising incompatible sugar-based (A) and hydrocarbon (B) blocks that can self-assemble into ordered nanostructures with sub-1 nm domains and full domain pitches as small as 1.2 nm. Depending on the chain length and block sequence, the ordered morphologies include lamellae, perforated lamellae, and hexagonally perforated lamellae. The self-assembly of these amphiphiles bears some similarities, but also some differences, to those formed by symmetric triblock polymers. In lamellae formed by ABA amphiphiles, the fraction of B blocks "bridging" adjacent polar domains is nearly unity, much higher than that found for symmetric triblock polymers, and the bridging molecules adopt elongated conformations. In contrast, "looping" conformations are prevalent for A blocks of BAB amphiphiles. Above the order-disorder transition temperature, the disordered states are locally well-segregated yet the B blocks of ABA amphiphiles are significantly less stretched than in the lamellar phases. Analysis of both hydrogen-bonded and nonpolar clusters reveals the bicontinuous nature of these network phases. This simulation study furnishes detailed insights into structure-property relationships for mesophase formation on the 1 nm length scale that will aid further miniaturization for numerous applications.

Drug delivery systems are designed to control the release rate and location of therapeutic agents in the body to achieve enhanced drug efficacy and to mitigate adverse side effects. In particular, drug-releasing implants provide sustained and localized release. We report nanostructured polymer monoliths synthesized by polymerization-induced microphase separation (PIMS) as potential implantable delivery devices. As a model system, free poly(ethylene oxide) homopolymers were incorporated into the nanoscopic poly(ethylene oxide) domains contained within a cross-linked polystyrene matrix. The in vitro release of these poly(ethylene oxide) molecules from monoliths was investigated as a function of poly(ethylene oxide) loading and molar mass as well as the molar mass and weight fraction of poly(ethylene oxide) macro-chain transfer agent used in the PIMS process for forming the monoliths. We also developed nanostructured microneedles targeting efficient and long-term transdermal drug delivery by combining PIMS and microfabrication techniques. Finally, given the prominence of poly(lactide) in drug delivery devices, the degradation rate of microphase-separated poly(lactide) in PIMS monoliths was evaluated and compared with bulk poly(lactide).

Eight 4-carboalkoxyvalerolactones ( CRVL s), varying in the composition of their alkyl ( R ) side chains, were synthesized from malic acid and subjected to ring-opening transesterification polymerization (ROTEP) using diphenyl phosphate [DPP, (PhO) 2 PO 2 H] as a catalyst. Each CRVL produced a semicrystalline poly(4-carboalkoxyvalerolactone) ( PCRVL ), and the nature of the R group impacted the thermal transitions of these polyesters. Bulk polymerizations at 70 °C allowed for preparation of high molar mass samples that contained small amounts of branching, as evidenced by 1 H NMR spectroscopy, MALDI spectrometry, size-exclusion chromatography, and eliminative degradation. Tensile testing of these lightly branched, high molar mass samples revealed that these polyesters are tough (tensile toughness values up to 88 ± 33 MJ•m -3 ) and have Young's moduli ( E ) up to 186 ± 13 MPa. The acid- and base-catalyzed hydrolytic degradation of the PCRVL s was quantitatively monitored using total organic carbon analysis, and effect of the alkyl chain length on PCRVL hydrolysis rate was determined. Finally, the methyl ester variant of these malic acid-derived thermoplastics is known to be chemically recyclable., Competing Interests: The authors have no competing financial interests to declare.

To date, scalability limitations have hindered the exploration and application of sequence-defined polymers in areas such as synthetic plastics, fibers, rubbers, coatings, and composites. Additionally, the impact of sequence on the properties of cross-linked networks remains largely unknown. To address the need for synthetic methods to generate sequence-defined materials in gram quantities, we developed a strategy involving inexpensive and readily functional vanillin-based monomers to assemble sequence-defined polyurethane oligomers via sequential reductive amination and carbamation. Three oligomers were synthesized with monomer sequence precisely dictated by the placement of reactive side chains during the reductive amination reaction. Avoiding excessive chromatographic purification and solid- or liquid-phase supports enabled synthesis of sequence-defined oligomers on the gram-scale. Remarkably, sequence was shown to influence network topology upon cross-linking, as evidenced by sequence-dependent rubbery moduli values. This work provides one of the first examples of a scalable synthetic route toward sequence-defined thermosets that exhibit sequence-dependent properties.

A series of symmetric poly(methyl methacrylate- stat -styrene)- block -polylactide (P(MMA- s -S)- b -PLA) diblock terpolymers with nearly constant molar masses yet varying block interaction parameters were synthesized as a model system to probe the extent and utility of composition fluctuations in the disordered state. A combination of differential scanning calorimetry, dynamic mechanical analysis, and small-angle X-ray scattering revealed that a broad range of segregation strengths ranging from what we ascribe to essentially a mean-field disordered to a fluctuating disordered to an ordered system could be readily obtained by tuning the molar fraction of styrene in these diblocks. The P(MMA- s -S)- b -PLA diblocks were annealed above their order-disorder transition temperatures ( T ODT sorption analysis post-removal of PLA demonstrated that a transition from a very weakly structured, mean-field-like melt to a bicontinuous fluctuating disordered state occurred with increasing segregation strength. This work demonstrates that the extent of microphase segregation as well as the domain continuity of the disordered block polymer melt can be tuned using both synthetic design and thermal stimuli, guiding the design of disordered block polymers with targeted nanostructures that have potential technological utility.2 sorption analysis post-removal of PLA demonstrated that a transition from a very weakly structured, mean-field-like melt to a bicontinuous fluctuating disordered state occurred with increasing segregation strength. This work demonstrates that the extent of microphase segregation as well as the domain continuity of the disordered block polymer melt can be tuned using both synthetic design and thermal stimuli, guiding the design of disordered block polymers with targeted nanostructures that have potential technological utility.

Silicon quantum dots (Si QDs) are attractive, nontoxic luminophores for luminescent solar concentrators (LSCs). Here, we produced Si QD/poly(methyl methacrylate) (PMMA) films on glass by doctor-blading polymer solutions and achieved films with low light scattering at an order of magnitude higher Si QD weight fraction than has been achieved previously in the bulk. We suggest that the fast solidification rate of films as compared to slow bulk polymerization is an enabling factor in avoiding large agglomerates within the nanocomposites. Scanning electron microscopy confirmed that ∼100 nm or larger QD agglomerates exist in light-scattering films, and photoluminescence intensity measurements show that light scattering, if present, significantly reduces waveguiding efficiencies for LSCs. Nonscattering films fabricated in this work exhibit high ultraviolet absorption (>80%) paired with high visible transmission (>87%) and minimal visible haze (∼1%), making them well suited for semitransparent coatings for LSCs realized as solar harvesting windows.

Polyesters constitute around 10% of the global plastic market with aromatic polyesters, such as poly(ethylene terephthalate) (PET), being the most prevalent because of their attractive properties. As for most commercial plastics, polyesters are primarily derived from fossil resources and are not readily degradable, which raises a number of sustainability concerns. Designing polymers with competitive properties from sustainable feedstocks that rapidly degrade under mild conditions is an attractive strategy for addressing the current plastic waste problem. Here, the detailed synthesis and characterization of degradable, high molar mass aromatic polyesters derived from salicylic acid, poly(salicylic glycolide) (PSG), and poly(salicylic methyl glycolide) (PSMG) are described. The synthesis of polymers was investigated through mechanistic experiments and complementary computational studies. The glass transition temperature ( T g ≈ 85 °C) and Young's modulus ( E ≈ 2.3 GPa) of these polyesters are comparable to those of PET. In contrast to the poor hydrolytic degradability of PET, both PSG and PSMG are readily degradable in neutral aqueous solutions (e.g., complete degradation in seawater at 50 °C in 60 days). These aromatic polyesters derived from salicylic acid have potential as future high-performance, sustainable, and degradable plastics.

Solubility-enhancing amorphous solid dispersions can aid in the oral delivery of hydrophobic, poorly soluble drugs. Effective solid dispersion excipients enable high supersaturation drug concentrations over biologically relevant time scales. The critical characteristics of an excipient that allow it to work well in a solid dispersion system are not well understood. We prepared poly( N -isopropylacrylamide), poly( N , N -dimethylacrylamide), and poly( N -hydroxyethylacrylamide) excipients of varying molar mass and examined their ability to improve the aqueous solubility of phenytoin, a Biopharmaceutical Class System Class II drug. Binary and ternary solid dispersions of phenytoin and these excipients, along with hydroxypropyl methylcellulose acetate succinate and hydroxypropyl methylcellulose, were prepared at 10 wt % drug loading. Dissolution behavior was studied at early time points (<1 min) and over the course of 6 h. Performance of the ternary solid dispersions was largely a function of the concentration of poly( N -isopropylacrylamide) present in micellar structures and the concentration of PNiPAm micelles in the dissolution media. We present several systems that achieved significant improvement of phenytoin solubility over a wide composition range at enhancement factors among the highest seen to date for phenytoin., Competing Interests: The authors declare no competing financial interest., (Copyright © 2019 American Chemical Society.)

Polymers are an important class of materials that are used for a broad range of applications, from drug delivery to packaging. Given their widespread use, a major challenge in this area is the development of technology for their production from renewable sources and efforts to promote their efficient recycling and biodegradation. In this regard, the synthesis of polyesters based on the natural polyhydroxyalkanoate (PHA) pathway offers an attractive route for producing sustainable polymers. However, monomer diversity in naturally occurring polyesters can be limited with respect to the design of polymers with material properties suitable for various applications. In this work, we have engineered a pathway to produce α-methyl-branched PHA. In the course of this work, we have also identified a PHA polymerase (CapPhaEC) from activated sludge from wastewater treatment that demonstrates a higher capacity for incorporation of α-branched monomer units than those previously identified or engineered. Production in Escherichia coli allows the construction of microbial strains that produce the copolyesters with 21-36% branched monomers using glucose and propionate as carbon sources. These polymers have typical weight-average molar masses ( M w ) in the range (1.7-2.0) × 10 5 and display no observable melting transition, only relatively low glass transition temperatures from -13 to -20 °C. The lack of a melting transition indicates that these polymers are amorphous materials with no crystallinity, which is in contrast to the natural poly(hydroxybutyrate) homopolymer. Our results expand the utility of PHA-based pathways and provide biosynthetic access to α-branched polyesters to enrich the properties of bio-based sustainable polymers.-1 and display no observable melting transition, only relatively low glass transition temperatures from -13 to -20 °C. The lack of a melting transition indicates that these polymers are amorphous materials with no crystallinity, which is in contrast to the natural poly(hydroxybutyrate) homopolymer. Our results expand the utility of PHA-based pathways and provide biosynthetic access to α-branched polyesters to enrich the properties of bio-based sustainable polymers.

Many pharmaceutical drugs in the marketplace and discovery pipeline suffer from poor aqueous solubility, thereby limiting their effectiveness for oral delivery. The use of an amorphous solid dispersion (ASD), a mixture of an active pharmaceutical ingredient and a polymer excipient, greatly enhances the aqueous dissolution performance of a drug without the need for chemical modification. Although this method is versatile and scalable, deficient understanding of the interactions between drugs and polymers inhibits ASD rational design. This current Review details recent progress in understanding the mechanisms that control ASD performance. In the solid-state, the use of high-resolution theoretical, computational, and experimental tools resolved the influence of drug/polymer phase behavior and dynamics on stability during storage. During dissolution in aqueous media, novel characterization methods revealed that ASDs can form complex nanostructures, which maintain and improve supersaturation of the drug. The studies discussed here illustrate that nanoscale phenomena, which have been directly observed and quantified, strongly affect the stability and bioavailability of ASD systems, and provide a promising direction for optimizing drug/polymer formulations.

Efforts to create block-polymer-based templates with ultrasmall domain sizes has stimulated integrated experimental and theoretical work in an effort to design and prepare self-assembled systems that can achieve unprecedented domain sizes. We recently reported the utilization of molecular dynamics simulations with transferable force fields to identify amphiphilic oligomers capable of self-assembling into ordered layered and cylindrical morphologies with sub-3 nm domain sizes. Motivated by these predictions, we prepared a sugar-based amphiphile with a hydrocarbon tail that shows thermotropic self-assembly to give a lamellar mesophase with a 3.5 nm pitch and sub-2 nm nanodomains above the melting temperature and below the liquid-crystalline clearing temperature. Complementary atomistic simulations of the molecular assemblies gave morphologies and spacings that were in near-perfect agreement with the experimental results. The effective combination of molecular design, simulation, synthesis, and structural characterization demonstrates the power of this integrated approach for next-generation templating technologies.

Polylactide- block-poly(γ-methyl-ε-caprolactone)- block-polylactide (LML) is a sustainable thermoplastic elastomer (TPE) candidate that exhibits competitive mechanical properties as compared to traditional styrenic TPEs. The relatively low glass transition temperature of the polylactide endblocks, however, results in stress relaxation and low levels of elastic recovery. We report the synthesis and characterization of poly(γ-methyl-ε-caprolactone) (PMCL) and LML end-functionalized with ureidopyrimidinone (UPy) hydrogen-bonding moieties to improve the elastic performance of these polymers. Although UPy-functionalized PMCL shows dynamical mechanical behavior that is distinct from the unfunctionalized homopolymer, it does not exhibit elastomeric behavior at room temperature. The addition of UPy endgroups to LML increases the ultimate tensile strength, elongation at break, and tensile toughness compared to unfunctionalized LML. Stress relaxation studies at a fixed strain show reduced levels of stress relaxation in LML with UPy endgroups. The stress relaxation was further reduced by including semicrystalline poly(( S, S)-lactide) as endblocks with UPy endgroups.

Biodegradable polyesters are being increasingly used to replace conventional, nondegradable polymers in agricultural applications such as plastic film for mulching. For many of these applications, poly(butylene adipate- co-terephthalate) (PBAT) is a promising biodegradable material. However, PBAT is also susceptible to photochemical transformations. To better understand how photochemistry affects the biodegradability of PBAT, we irradiated blown, nonstabilized, transparent PBAT films and studied their enzymatic hydrolysis, which is considered the rate-limiting step in polyester biodegradation. In parallel, we characterized the irradiated PBAT films by dynamic mechanical thermal analysis. The rate of enzymatic PBAT hydrolysis decreased when the density of light-induced cross-links within PBAT exceeded a certain threshold. Mass-spectrometric analysis of the enzymatic hydrolysis products of irradiated PBAT films provided evidence for radical-based cross-linking of two terephthalate units that resulted in the formation of benzophenone-like molecules. In a proof-of-principle experiment, we demonstrated that the addition of photostabilizers to PBAT films mitigated the negative effect of UV irradiation on the enzymatic hydrolyzability of PBAT. This work advances the understanding of light-induced changes on the enzyme-mediated hydrolysis of aliphatic-aromatic polyesters and will therefore have important implications for the development of biodegradable plastics.

Cross-linked polymers are used in many commercial products and are traditionally incapable of recycling via melt reprocessing. Recently, tough and reprocessable cross-linked polymers have been realized by incorporating cross-links that undergo associative exchange reactions, such as transesterification, at elevated temperatures. Here we investigate how cross-linked polymers containing urethane linkages relax stress under similar conditions, which enables their reprocessing. Materials based on hydroxyl-terminated star-shaped poly(ethylene oxide) and poly((±)-lactide) were cross-linked with methylene diphenyldiisocyanate in the presence of stannous octoate catalyst. Polymers with lower plateau moduli exhibit faster rates of relaxation. Reactions of model urethanes suggest that exchange occurs through the tin-mediated exchange of the urethanes that does not require free hydroxyl groups. Furthermore, samples were incapable of elevated-temperature dissolution in a low-polarity solvent (1,2,4-trichlorobenzene) but readily dissolved in a high-polarity aprotic solvent (DMSO, 24 to 48 h). These findings indicate that urethane linkages, which are straightforward to incorporate, impart dynamic character to polymer networks of diverse chemical composition, likely through a urethane reversion mechanism.

A biannual chemistry demonstration-based show named "Energy and U" was created to extend the general outreach themes of science, technology, engineering, and mathematics (STEM) fields and a college education with a specific goal: to teach the first law of thermodynamics to elementary school students. The effectiveness of the program was analyzed using a clicker survey system for over 12 000 visiting students. The fraction of the students that correctly answered the question "Is it possible to create energy?" increased from 14% immediately before the show to 89% immediately after the show. Students who had seen the show at least 5 months prior were twice as likely to correctly answer at the beginning of the show, demonstrating longer-term lesson retention. Interestingly, similar trends were observed for the adult chaperones that accompanied the students and participated in the clicker survey. A statistically significant difference (>99% confidence interval) was noted between the students' responses to the questions "Can you create energy?" and "Can you destroy energy?", revealing a potential effect of word choice on the interpretation of the first law of thermodynamics despite the two questions representing complementary concepts. Student performance, measured interest in science, and desire to attend college were not correlated with standard economic indicators. This measurement is consistent with the postulate that economic biases surrounding interest in STEM fields are less pronounced in elementary school than later in high school., Competing Interests: The authors declare no competing financial interest.

Direct polymerization of allyl alcohol generally results in low molar mass oligomers or highly branched or cross-linked structures, and the properties and applications of linear, high molar mass poly(allyl alcohol) (PAA) are relatively unexplored. Such macromolecular materials that cannot otherwise be obtained directly can be accessed by postpolymerization modification strategies. Herein we describe the synthesis and characterization of linear, high molar mass PAA by borohydride reduction of a new activated polyacrylamide. The facile polymerization and mild reduction conditions enable the preparation of PAA of targeted molar masses and low dispersity, as well as PAA block polymers via chemoselective reduction of the activated amide moiety.

Diphenhydramine (DPH) has been used with ibuprofen (IBU) or naproxen (NAP) in combined therapies to provide better clinical efficacy as an analgesic and sleep aid. We discovered that DPH can form protic ionic liquids (PILs) with IBU and NAP, which opens the opportunity for a new delivery mode of these combination drugs. [DPH][IBU] and [DPH][NAP] PILs exhibit low ionicity, as confirmed by Fourier transform infrared and 1 H NMR spectroscopy, and accompanied by low diffusivity, high viscosity, and poor ionic conductivity. Evaluation of pharmaceutical properties of the two PILs showed that these PILs, despite high solubility and good wettability, exhibited low dissolution rates, owing to the poor dispersion of the PIL drops and the resultant small surface area during dissolution. However, when loaded into a mesoporous carrier, the PIL-carrier composites exhibited improved dissolution rates along with excellent flow properties and easy handling. Oral capsules of both PILs were developed using such composites. Such capsule products exhibited acceptable drug release and bioavailability as demonstrated by a predictive artificial stomach-duodenum dissolution test.

Molecular dynamics simulations are used to design a series of high-χ block oligomers (HCBOs) that can self-assemble into a variety of mesophases with domain sizes as small as 1 nm. The exploration of these oligomers with various chain lengths, volume fractions, and chain architectures at multiple temperatures reveals the presence of ordered lamellae, perforated lamellae, and hexagonally packed cylinders. The achieved periods are as small as 3.0 and 2.1 nm for lamellae and cylinders, respectively, which correspond to polar domains of approximately 1 nm. Interestingly, the detailed phase behavior of these oligomers is distinct from that of either solvent-free surfactants or block polymers. The simulations reveal that the behavior of these HCBOs is a product of an interplay between both "surfactant factors" (headgroup interactions, chain flexibility, and interfacial curvature) and "block polymer factors" (χ, chain length N, and volume fraction f). This insight promotes the understanding of molecular features pivotal for mesophase formation at the sub-5 nm length scale, which facilitates the design of HCBOs tailored toward particular desired morphologies.

The linear viscoelastic behavior of poly(norbornene)- graft -poly(±-lactide) was investigated as a function of grafting density and overall molar mass. Eight sets of polymers with grafting densities ranging from 0 to 100% were synthesized by living ring-opening metathesis copolymerization. Within each set, the graft chain molar mass and spacing between grafts were fixed, while the total backbone length was varied. Dynamic master curves reveal that these polymers display Rouse and reptation dynamics with a sharp transition in the zero-shear viscosity data, demonstrating that grafting density strongly impacts the entanglement molar mass. The entanglement modulus ( G e ) scales with inverse grafting density ( n g ) as G e in accordance with scaling theory in the high and low grafting density limits, respectively. However, a sharp transition between these limiting behaviors occurs, which does not conform to existing theoretical models for graft polymers. A molecular interpretation based on thin flexible chains at low grafting density and thick semiflexible chains at high grafting density anticipates the sharp transition between the limiting dynamical regimes.n g 1.2 and G e ∼ n g 0 in accordance with scaling theory in the high and low grafting density limits, respectively. However, a sharp transition between these limiting behaviors occurs, which does not conform to existing theoretical models for graft polymers. A molecular interpretation based on thin flexible chains at low grafting density and thick semiflexible chains at high grafting density anticipates the sharp transition between the limiting dynamical regimes.

Chemically cross-linked elastomers are an important class of polymeric materials with excellent temperature and solvent resistance. However, nearly all elastomers are petroleum-derived and persist in the environment or in landfills long after they are discarded; this work strives to address these issues by demonstrating the synthesis of renewable, enzymatically hydrolyzable, and mechanically competitive polyester elastomers. The elastomers described were synthesized using a novel bis(β-lactone) cross-linker and star-shaped, hydroxyl-terminated poly(γ-methyl-ε-caprolactone). Using model compounds, we determined that the bis(β-lactone) cross-linker undergoes acyl bond cleavage to afford β-hydroxyesters at the junctions. The mechanical properties of the cross-linked materials were tunable and competitive with a commodity rubber band. Furthermore, the elastomers demonstrated high thermal stability and a low glass transition (-50 °C), indicating a wide range of use temperatures. The polyester networks were also subjected to enzymatic hydrolysis experiments to investigate the potential for these materials to biodegrade in natural environments. We found that they readily hydrolyzed at neutral pH and environmentally relevant temperatures (2-40 °C); complete hydrolysis was achieved in all cases at temperature-dependent rates. The results presented in this work exemplify the development of high performance yet sustainable alternatives to conventional elastomers.

The displacement of an activated leaving group in polymeric repeat units is a powerful method of postpolymerization modification. This strategy enables the synthesis of polymers otherwise unobtainable by direct polymerization as well as the preparation of a diverse array of macromolecular structures. We demonstrate that the activation of acrylamide through the introduction of two tert -butyloxycarbamate (Boc) groups followed by radical polymerization leads to a new class of activated polyacrylamides analogous to well-known activated polyacrylates. Transamidation of poly(di(Boc)-acrylamide) utilizing primary amines proceeds to high conversion under mild conditions, and the products can be readily purified. Less nucleophilic secondary amines and alcohols require more forcing conditions. We demonstrate the utility of this approach by preparing copolymers capable of on-demand gel formation and the synthesis of block polymers using controlled radical polymerization.