Large Polymer Research Articles

Polymer-induced adhesion of endothelial cells

The effects of neutral dextran concentration and molecular mass on the adhesion of endothelial cells (EC) to siliclad-covered glass surfaces were studied using interference reflection microscopy (IRM). Results indicate that close contact of the EC to the glass slides is markedly enhanced in the presence of 500 kDa dextran, with this increase reflected by both the speed of forming close contact as well as the size of the contact area. This increased adhesion is attributed to the reduction in surface concentrations of large polymers and, therefore, to the attractive forces caused by depletion interaction. Our findings suggest that depletion could play an important role in cell-cell or cell-surface interactions via accelerating and enhancing close contacts. This interaction should thus be considered in vivo and in vitro for specific potential applications, such as cell culture and cell adhesion to biomimetic surfaces. It should therefore be of particular interest in a wide range of biomedical applications.

A general-purpose material property data extraction pipeline from large polymer corpora using natural language processing

The ever-increasing number of materials science articles makes it hard to infer chemistry-structure-property relations from literature. We used natural language processing methods to automatically extract material property data from the abstracts of polymer literature. As a component of our pipeline, we trained MaterialsBERT, a language model, using 2.4 million materials science abstracts, which outperforms other baseline models in three out of five named entity recognition datasets. Using this pipeline, we obtained ~300,000 material property records from ~130,000 abstracts in 60 hours. The extracted data was analyzed for a diverse range of applications such as fuel cells, supercapacitors, and polymer solar cells to recover non-trivial insights. The data extracted through our pipeline is made available at polymerscholar.org which can be used to locate material property data recorded in abstracts. This work demonstrates the feasibility of an automatic pipeline that starts from published literature and ends with extracted material property information.

Dynein Dysfunction Prevents Maintenance of High Concentrations of Slow Axonal Transport Cargos at the Axon Terminal: A Computational Study.

Here, we report computational studies of bidirectional transport in an axon, specifically focusing on predictions when the retrograde motor becomes dysfunctional. We are motivated by reports that mutations in dynein-encoding genes can cause diseases associated with peripheral motor and sensory neurons, such as type 2O Charcot-Marie-Tooth disease. We use two different models to simulate bidirectional transport in an axon: an anterograde-retrograde model, which neglects passive transport by diffusion in the cytosol, and a full slow transport model, which includes passive transport by diffusion in the cytosol. As dynein is a retrograde motor, its dysfunction should not directly influence anterograde transport. However, our modeling results unexpectedly predict that slow axonal transport fails to transport cargos against their concentration gradient without dynein. The reason is the lack of a physical mechanism for the reverse information flow from the axon terminal, which is required so that the cargo concentration at the terminal could influence the cargo concentration distribution in the axon. Mathematically speaking, to achieve a prescribed concentration at the terminal, equations governing cargo transport must allow for the imposition of a boundary condition postulating the cargo concentration at the terminal. Perturbation analysis for the case when the retrograde motor velocity becomes close to zero predicts uniform cargo distributions along the axon. The obtained results explain why slow axonal transport must be bidirectional to allow for the maintenance of concentration gradients along the axon length. Our result is limited to small cargo diffusivity, which is a reasonable assumption for many slow axonal transport cargos (such as cytosolic and cytoskeletal proteins, neurofilaments, actin, and microtubules) which are transported as large multiprotein complexes or polymers.

Using PCL oligomers to study the differences in melting behavior between polymers and small molecules crystals

Polymer crystals usually show a completely different melting behavior than small molecules. Instead of starting from the crystal growth front, the lamellar crystals within polymer spherulites always experience a successive thickening process upon heating before they simultaneously melt. However, a systematic comparative study of the different melting behavior of crystals formed by small and large polymer chains is still scarce. In this work, two PCL oligomers with similar molecular weight are selected to study their crystallization and melting behavior. The defect-free oligomer (PCL2.4) exhibits a similar melting behavior as polymeric crystals (where spherulites melt simultaneously). In contrast, the other oligomer (PCL2.0) with a mid-chain defect shows prominent surface melting starting at the spherulite growth front. SAXS, SSA thermal fractionation, and flash DSC results confirm that an extended chain-like crystal structure could form at relatively high crystallization temperatures. According to the Gibbs-Thomson equation, the melting temperature of PCL2.0 crystals at the spherulite growth front is relatively lower than in the inner part due to different surface free energies. On the other hand, the thermal stability of PCL2.4 is enhanced due to melting and recrystallization during heating, and the spherulites show identical melting points and lamellar thicknesses at their growth front centers.

Rapid Controlled Synthesis of Large Polymers by Frontal Ring-Opening Metathesis Polymerization

Tunable molecular weight and well-defined polydispersity are the hallmarks of a controlled polymerization. This process relies on vanishingly small termination rates, minimal chain transfer, and initiation rates faster than propagation rates. Ring-opening metathesis polymerization (ROMP) is a well-known controlled polymerization based on the opening of strained cyclic olefins. The exothermic nature of ROMP allows rapid conversion of neat monomers to polymers through frontal ROMP (FROMP). Unlike traditional ROMP, FROMP uses the exothermic heat from the opening of strained cyclic olefins to thermally activate the initiator that sustains the propagation of a cascading reaction front. Although the reaction mechanisms for ROMP and FROMP are the same, the reaction conditions differ greatly, especially in the temperature and monomer concentration. The ability to control the polymerization under FROMP conditions has yet to be investigated, as well as its potential in the synthesis of well-defined polymers without the use of solvents and with minimal energy input. Here, we show that FROMP rapidly transforms monomers into polymers of high-molecular weight (Mn) with good fidelity and low dispersity (Đ). Specifically, the synthesis of polymers with Mn up to 700 kg/mol and Đ of 1.5 was achieved with a rapid, solvent-free, and oxygen-tolerant frontal polymerization technique. Further control of the polymerization was possible with the addition of a phosphite ligand that lowered the Đ to 1.2. We anticipate that controlled FROMP will become a valuable macromolecular synthetic tool due to its reliability, speed, scalability, and simplicity.

Water is a powerful dynamic allosteric modulator in rhodopsin activation.

Rhodopsin is an archetype for G protein-coupled receptors (GPCRs) which are membrane proteins involved in cellular signal transduction. Although GPCR X-ray structures show the presence of structural water molecules, their physiological role in the signaling process remains uncertain. Our previous work has shown that in lipid membranes rhodopsin activation is coupled to bulk water movements into the protein to stabilize the effector binding conformation [1,2]. Here we extend the experimental approach to explore modulation of the conformational energetics of rhodopsin activation in lipid membranes. We hypothesized that the thermodynamic stability of conformational substates of photoactivated rhodopsin is hydration mediated. Accordingly, we changed the osmotic stress on rhodopsin using different hydrophilic polymers including polyethylene glycols (PEGs), dextrans, polyvinylpyrrolidones, and their monomers. Reversible shifting of the metarhodopsin equilibrium due to the osmotic stress was probed using UV-visible spectroscopy. We observed that the rhodopsin activation is associated with a bulk influx of water due to the osmotic dehydration by large, excluded polymers which inhibit GPCR activation. By contrast small penetrable osmolytes and monomers have lower conformational entropy and showed a nonosmotic trend in rhodopsin activation. Small osmolytes penetrate the receptor core and stabilize the more expanded active state of rhodopsin until reaching a quantifiable saturation point. Both PEGs and dextrans with very high molar masses deviated in their trends from other large polymers due to a crowding effect, whereby extremely large osmolytes induce steric forces on rhodopsin and restrict their volume occupancy. Further studies of hydration effects on binding of the G-protein and receptor catalyzed exchange of GTP for GDP are expected to provide significant clues on the complete mechanism of G-protein binding and release

Xylan glucuronic acid side chains fix suberin-like aliphatic compounds to wood cell walls.

Wood is the most important repository of assimilated carbon in the biosphere, in the form of large polymers (cellulose, hemicelluloses including glucuronoxylan, and lignin) that interactively form a composite, together with soluble extractives including phenolic and aliphatic compounds. Molecular interactions among these compounds are not fully understood. We have targeted the expression of a fungal α-glucuronidase to the wood cell wall of aspen (Populus tremula L. × tremuloides Michx.) and Arabidopsis (Arabidopsis thaliana (L.) Heynh), to decrease contents of the 4-O-methyl glucuronopyranose acid (mGlcA) substituent of xylan, to elucidate mGlcA's functions. The enzyme affected the content of aliphatic insoluble cell wall components having composition similar to suberin, which required mGlcA for binding to cell walls. Such suberin-like compounds have been previously identified in decayed wood, but here, we show their presence in healthy wood of both hardwood and softwood species. By contrast, γ-ester bonds between mGlcA and lignin were insensitive to cell wall-localized α-glucuronidase, supporting the intracellular formation of these bonds. These findings challenge the current view of the wood cell wall composition and reveal a novel function of mGlcA substituent of xylan in fastening of suberin-like compounds to cell wall. They also suggest an intracellular initiation of lignin-carbohydrate complex assembly.

Experimental Analysis of Large Active Area Polymer Electrolyte Membrane Fuel Cell Stack for Determining Optimal Operating Conditions

Experimental Analysis of Large Active Area Polymer Electrolyte Membrane Fuel Cell Stack for Determining Optimal Operating Conditions

NMR Characterization of Polyethylene Glycol Conjugates for Nanoparticle Functionalization.

The molecular weight, purity, and functionalization of polyethylene glycols are often characterized by 1H NMR spectroscopy. Oft-forgotten, the typical 1H NMR pulse sequence is not 13C decoupled. Hence, for large polymers, the 13C coupled 1H peaks arising from the repeating units have integrations comparable to that of the 1H of the terminal groups. Ignoring this coupling leads to erroneous assignments. Once correctly assigned, these 13C coupled 1H peaks can be used to determine both the molecular weight of the polymer and the efficacy of conjugation of a terminal moiety more accurately than the uncoupled 1H of the repeating unit.

Dimension of heterogeneous network architecture formed in emulsion cross‐linking copolymerization

AbstractThe mean‐square radius of gyration Rg2 and the graph diameter D of highly heterogeneous network polymers formed in emulsion vinyl/divinyl copolymerization are investigated to find a linear relationship, Rg2 = a D. The proportionality coefficient, a, is dominated by the cycle (circuit) rank, kc, or the number of intramolecular cross‐links. The magnitude of a is slightly larger than that for the random cross‐linked network polymers, but the functional form of a (kc) is simply proportional to that for the random networks proposed earlier. This relationship makes it possible to determine Rg2 based on D and kc, enabling quick estimation of Rg2 for large network polymers. It is found that the contraction factor g of the present heterogeneous network polymer is larger than that for the homogeneous networks formed through random cross‐linking of polymer chains. The ratio of these two contraction factors is kept constant, irrespective of the magnitude of kc.

Dilute polymer solutions under shear flow: Comprehensive qualitative analysis using a bead-spring chain model with a FENE-Fraenkel spring

Although the nonequilibrium behavior of polymer solutions is generally well understood, particularly in extensional flow, there remain several unanswered questions for dilute solutions in simple shear flow, and full quantitative agreement with experiments has not been achieved. For example, experimental viscosity data exhibit qualitative differences in shear-thinning exponents, the shear rate for the onset of shear-thinning, and high-shear Newtonian plateaus depending on polymer semiflexibility, contour length, and solvent quality. While polymer models are able to incorporate all of these effects through various spring force laws, bending potentials, excluded volume (EV) potentials, and hydrodynamic interaction (HI), the inclusion of each piece of physics has not been systematically matched to experimentally observed behavior. Furthermore, attempts to develop multiscale models (in the sense of representing an arbitrarily small or large polymer chain) which can make quantitative predictions are hindered by the lack of ability to fully match the results of bead-rod models, often used to represent a polymer chain at the Kuhn-step level, with bead-spring models, which take into account the entropic elasticity. In light of these difficulties, this work aims to develop a general model based on the so-called FENE-Fraenkel spring, originally formulated by Larson and co-workers [J. Chem. Phys. 124 (2006)], which can span the range from rigid rod to traditional entropic spring, as well as include a bending potential, EV, and HI. As we show, this model can reproduce, and smoothly move between, a wide range of previously observed polymer solution rheology in shear flow.

Dual Molecular Oxygen Activation Sites on Conjugated Microporous Polymers for Enhanced Photocatalytic Formation of Benzothiazoles

Oxidative formation of high value compounds involving active oxygen species using heterogeneous polymeric photocatalysts has become a useful tool in catalysis. Controlling the interaction between the active sites on polymer photocatalysts and oxygen molecules is still challenging due to the rather large polymer backbone structure. Here, we design a triazine-containing donor acceptor-type conjugated microporous polymer (CMP) containing dual major active sites at F and N atoms for molecular oxygen activation. Introducing fluorine atoms on the CMP backbone led to a combined effect of enhanced adsorption and electron transfer of oxygen. Time-resolved photoluminescence, electronic paramagnetic resonance spectra, and DFT calculation revealed favorable absorption energy and electron transfer kinetics between the CMP and oxygen molecules, thus efficiently generating superoxide radicals (O2•-) and singlet oxygen (1O2) as main active oxygen species. The photocatalytic activity, selectivity, and reusability of the CMP was demonstrated by the photocatalytic formation of a variety of benzothiazoles.

Informatics-Driven Selection of Polymers for Fuel-Cell Applications

Modern fuel cell technologies use Nafion as the material of choice for the proton exchange membrane (PEM) and as the binding material (ionomer), used to assemble the catalyst layers of the anode and cathode. These applications demand high proton conductivity as well as other requirements. For example, PEM is expected to block electrons, oxygen, and hydrogen from penetrating and diffusing while the anode/cathode ionomer should allow hydrogen/oxygen to move easily, so that they can reach the catalyst nanoparticles. Given some of the well-known limits of Nafion, such as low glass-transition temperature, the community is in the midst of an active search for Nafion replacements. In this work, we present an informatics-based scheme to search large polymer chemical spaces, which includes establishing a list of properties needed for the targeted applications, developing predictive machine-learning models for these properties, defining a search space, and using the developed models to screen the search space. Using the scheme, we have identified 60 new polymer candidates for PEM, anode ionomer, and cathode ionomer that we hope will be advanced to the next step, i.e., validating the designs through synthesis and testing. The proposed informatics scheme is generic, and can be used to select polymers for multiple applications in the future.

Approximation of hindered zonal settling rates for flocculated inorganic/organic composite suspensions in inertial flow conditions

Inorganic/organic composite nuclear wastes have poor settling properties which hinder major UK decommissioning operations. Improving the settling properties of these wastes and the accurate prediction of settling rates is therefore key. However, constricted access and limited monitoring capability in radioactive environments limits the use of primary material, necessitating the use of surrogate test materials. Herein, an organic laden nuclear waste test material was characterised by examining the surface chemistry, morphology and settling behaviour. A large molecular weight polyacrylamide polymer was deployed to aggregate the organic laden nuclear waste test material. The polyacrylamide successfully flocculated the test material, increasing the zonal settling rate and decreasing the turbidity by one and two orders of magnitude respectively at optimum polymer dose conditions. Whilst displaying steric stabilisation beyond the performance maxima, reductions in flocculant performance were small with no indication of permanent stabilisation at five times the optimum dose. To mitigate risk, it is critical to understand the dynamics of the settling process. Given the porous, fractal nature of the agglomerates, fractal modified hindered settling models were assessed in order to improve predictions at low solids concentrations. In particular, predictive models using drag coefficients compatible with creeping and inertia flow regimes were utilised in tandem with structural and size data to quantify the impact of neglecting inertia drag as favoured by previous literature. It was found that at low solids concentrations, the inter-particulate spacing was significant and that inertial flow conditions were integral considerations to achieve close first-order approximations of zonal settling rate.

Ultra-expanded interlayer spacing of vanadium oxide nanowires intercalated with poly(3,4-ethylene dioxythiophene) in organic ammonium ion batteries.

Rechargeable batteries employing ammonium (NH4+) ions have attracted widespread interest owing to the abundant resources, eco-friendliness, and sustainability of NH4+ ions. Herein, an organic-inorganic hybrid is applied to organic NH4+ ion batteries. A poly (3,4-ethylene dioxythiophene) (PEDOT)-intercalated vanadium oxide nanowire (noted as VO-P-x) is applied for organic NH4+ ion storage. VO-P-x with the optimal content of PEDOT showed an interlayer spacing (d-spacing) expanded to 1.82 nm, exhibiting an ultrahigh initial coulombic efficiency of 91% and a reversible capacity of 163 mA h g-1. A significant improvement in NH4+ ion storage was achieved due to the large interlayer spacing and conductive polymer PEDOT. Combining ex situ X-ray photoelectron spectroscopy (XPS) and multi-sweep cyclic voltammetry tests, the NH4+ ion storage mechanism of VO-P-x was clearly revealed. This study provides a new strategy for designing high-performance organic ammonium batteries.

Production and Optimization of Exopolysaccharide from Thermophilic Bacteria

Exopolysaccharides (EPS) are the large molecular weight carbohydrate polymers extracted from higher plants, algae, fungi and bacteria. The thermophilic Bacillus zhangzhounesis 2CA and Bacillus licheniformis 2CS used in the present study were isolated from Çermik hot springs. The growth conditions of the strains designated as 2CA and 2CS in different basal media (M1, M2 and M3), different carbon sources and different concentrations of yeast extract (%w v-1: 0.05, 0.1, 0.15 and 0.2) and the amount of EPS produced were investigated. In addition, the phenol-sulfuric acid method and the Lowry method were used to determine the amount of carbohydrates and proteins within the EPS produced by the bacteria, respectively. The highest total EPS dry weight for B. licheniformis 2ÇS was obtained as 121 mg in M3 medium (0.2% yeast extract + 1% sucrose), carbohydrate content in EPS was 333.28 µg mL-1 and protein content was 0.19 µg mL-1. When these two bacteria were compared in terms of the amount of carbohydrates in the EPS produced, the highest amount of carbohydrates was found in EPS of B. zhangzhounesis 2CA (1087.03 µg mL-1). The antibacterial effects of EPS were investigated against pathogenic microorganisms (E. coli, S. aureus, K. pneumoniae and P. aeruginosa). It was determined that the highest antibacterial activity against E. coli (with 16 mm zone diameter) was obtained with EPS produced by B. licheniformis 2ÇS bacteria in M3 medium (0.2% yeast extract + 1% sucrose).

Experimental study on the seismic behavior of RC columns with high axial compression ratios retrofitted by large rupture strain fiber-reinforced polymer

Fiber-reinforced polymer (FRP) composites being utilized to retrofit reinforced concrete (RC) columns has been well documented. However, the axial compression load of the FRP retrofitting RC columns was relatively limited. Aiming to analyze the applicability of FRP retrofitting RC columns with higher axial compression loads, this paper presents an experimental study on the seismic performance of RC columns retrofitted by the Polyethylene Terephthalate (PET) FRP composites. A total of twelve 1/3 scale RC columns were fabricated, including four control specimens and eight PET FRP retrofitting columns with two retrofit schemes. All the columns were tested under combined high axial compression load and cyclic lateral displacement excursions, and the maximum axial compression ratio reaches 1.1. The seismic performance of RC columns retrofitted by PET FRP was analyzed detailedly from the failure mode, shear force and deformation capacity, energy dissipation and ductility. The test results showed that PET FRP retrofitting changed the failure mode of RC columns from brittle to more ductile. The post-peak strength degradation of the columns was more rapid with the increase of axial compression ratio, but the strength degradation of the PET FRP retrofitting columns was more gradual. PET FRP retrofitting significantly improved the ductility and lateral deformation capacity of the columns even under the high axial compression ratio. PET FRP retrofitting can be applied for the RC columns with serous demand of deformation capacity due to the lighter change of shear-loading capacity and stiffness. Contrastively, the improvement of the seismic capacity of the RC columns retrofitted by the laterally wrapped scheme is higher than that of the striped wrapped scheme. Conclusions from this study provide useful references for the seismic retrofitting of RC structures.

Scalable Synthetic Route to PDMS Ring Polymers in High Yields from Commercially Available Materials Using the Piers-Rubinsztajn Reaction.

While cyclic polymers have intrigued researchers for their novel set of architecture-driven rheological interactions, the possibility of incorporating them in topological systems has been limited by the availability of large ring polymers. Thus, the need for scalable methods to produce ring polymers has become apparent. Here, a facile method to prepare polysiloxane ring polymers by means of Piers-Rubinsztajn chemistry is presented. The one-pot nature and commercial availability of reagents additionally confirm the applicability of the method for large-scale production. Furthermore, a highly efficient yet simple purification method was developed for the isolation of pure ring polymers without linear side products.

High efficiency, lossless, large free-standing photonic bandgap polymer films

ABSTRACT Polarization selective photonic bandgaps are demonstrated as free-standing flexible films of chiral structure. Capability of large sizes, absence of defects and related high optical quality make the films adequate for imaging, optical communication, display, and other applications.

Large area polymer semiconductor sub-microwire arrays by coaxial focused electrohydrodynamic jet printing for high-performance OFETs

Large area and highly aligned polymer semiconductor sub-microwires were fabricated using the coaxial focused electrohydrodynamic jet printing technology. As indicated by the results, the sub-microwire arrays have smooth morphology, well reproducibility and controllable with a width of ~110 nm. Analysis shows that the molecular chains inside the sub-microwires mainly exhibited edge-on arrangement and the π-stacking direction (010) of the majority of crystals is parallel to the long axis of the sub-microwires. Sub-microwires based organic field effect transistors showed high mobility with an average of 1.9 cm2 V−1 s−1, approximately 5 times higher than that of thin film based organic field effect transistors. In addition, the number of sub-microwires can be conveniently controlled by the printing technique, which can subsequently concisely control the performance of organic field effect transistors. This work demonstrates that sub-microwires fabricated by the coaxial focused electrohydrodynamic jet printing technology create an alternative path for the applications of high-performance organic flexible device.