Variations In Polymer Structure Research Articles

Lignin's complex role in lignocellulosic biomass Recalcitrance: A case study on bamboo

Lignin is widely recognized as a key factor influencing the recalcitrance of lignocellulosic biomass, yet the specifics of this relationship remain complex and not fully understood due to the complex interplay between lignin content variation and cell wall structure. Bamboo, which exhibits greater recalcitrance compared to wood in biorefinery processing, was chosen as the focus of investigation in this study. Three variants of Dendrocalamus farinosus with high, middle and low lignin contents were systematically analyzed and compared, in terms of molecular structure of lignin, hemicelluloses and cellulose, cell wall polymer spatial orientation, lignin-carbohydrate complex (LCC) linkages, cell wall geometrical size, as well as deconstruction efficiency, including delignification, alkaline extraction, and cellulose enzymatic hydrolysis efficiency. Findings reveal that an increase in lignin content generally lowers bamboo's deconstruction efficiency, but the mechanisms are more nuanced than previously thought. While lignin content variations do not significantly affect the molecular structure of xylan, cellulose and the chemical linkage type of LCC linkages, they do impact cellulose crystallinity, xylan orientation and notably, the thickness of fiber cell wall in the free fiber stands of bamboo. These findings highlight that lignin's role extends beyond mere physical protection of the cell wall, but also induces subtle variations in polymer structure and cell wall morphologies, which collectively influence the deconstruction efficiency of bamboo cell walls.

Drug-Polymer Miscibility and the Overlap Concentration (C*) as Measured by Rheology: Variation of Polymer Structure.

Amorphous solid dispersions (ASDs), wherein a drug is molecularly dispersed in a polymer, can improve physical stability and oral bioavailability of poorly soluble drugs. Risk of drug crystallization is usually averted using high polymer concentrations. However, we demonstrated recently that the overlap concentration, C*, of polymer in drug melt is the minimum polymer concentration required to maintain drug in the amorphous state following rapid quench. This conclusion was confirmed for several drugs mixed with poly(vinylpyrrolidone) (PVP). Here we assess the solid-state stability of ASDs formulated with a variety of polymers and drugs and at various polymer concentrations (C) and molecular weights (MWs). We further test the hypothesis that degree of drug crystallization decreases with increasing C/C* and vanishes when C>C*, where C* depends on polymer MW and strength of drug-polymer interaction. We test our hypothesis with ASDs consisting of ketoconazole admixed with polyacrylic acid, polymethacrylic acid and poly (methacrylic acid-co-ethyl acrylate); and felodipine admixed with PVP and poly (vinylpyrrolidone-co-vinyl acetate). Values of C* for polymers in molten drug are rheologically determined. Crystallization behavior is assessed by measuring enthalpy of fusion, ΔHf and by X-ray diffraction. We confirm that ΔHf/ΔHf, C = 0 = f(C/C∗), and essentially no crystallization occurs when C>C*. Our findings will aid researchers in designing or selecting appropriate polymers to inhibit crystallization of poorly soluble drugs. This research also suggests that C* as determined by rheology can be used to compare drug-polymer interactions for similar molecular weight polymers.

Conformation and Dynamics along the Chain Contours of Polymer-Grafted Nanoparticles.

Densely grafted polymer chains onto spherical nanoparticles produce a diverse range of conformations. At high grafting densities, the corona region near the nanoparticle surface undergoes intense confinement due to a high concentration of chains in the concentrated polymer brush (CPB) region, which results in strong stretching for portions of the chains located within. In contrast, a semi-dilute polymer brush (SDPB) forms farther away from the core and offers reduced confinement for the polymer and more ideal conformations. However, conventional experimental methods are limited in their ability to provide detailed information on individual segments of grafted polymers in these regions; hence, molecular dynamics (MD) simulations are essential for gaining comprehensive insights into the behavior of the grafted chains. This study aims to explore the variations in polymer structure and dynamics that occur along the contour of the grafted chains as influenced by spatial confinement. We focus on the motions and relative positions of each bead along grafted polymers. Our results show that only the initial few grafted beads near the nanoparticle surface exhibit the strong stretching attributed segments in the CPB region of the brush. Increased grafting density or decreased chain flexibility leads to more stretched grafted chains and more aligned bond vectors. As a result, the relaxation dynamics of local regions of the polymer are also strongly influenced by these parameters. Although the grafted beads in the interior of the CPB region are highly sensitive to these parameters, those farther from the nanoparticle core experience significantly diminished effects. In comparison to the Daoud-Cotton (DC) model's predictions of CPB size, beads near the nanoparticle surface show slower dynamic decay, especially in high grafting densities, aligning with the DC model's estimates. Finally, we compare our simulations to previous works for additional insight into polymer-grafted nanoparticles.

Membrane protein extraction and purification using styrene-maleic acid (SMA) copolymer: effect of variations in polymer structure.

The use of styrene-maleic acid (SMA) copolymers to extract and purify transmembrane proteins, while retaining their native bilayer environment, overcomes many of the disadvantages associated with conventional detergent-based procedures. This approach has huge potential for the future of membrane protein structural and functional studies. In this investigation, we have systematically tested a range of commercially available SMA polymers, varying in both the ratio of styrene and maleic acid and in total size, for the ability to extract, purify and stabilise transmembrane proteins. Three different membrane proteins (BmrA, LeuT and ZipA), which vary in size and shape, were used. Our results show that several polymers, can be used to extract membrane proteins, comparably to conventional detergents. A styrene:maleic acid ratio of either 2:1 or 3:1, combined with a relatively small average molecular mass (7.5-10 kDa), is optimal for membrane extraction, and this appears to be independent of the protein size, shape or expression system. A subset of polymers were taken forward for purification, functional and stability tests. Following a one-step affinity purification, SMA 2000 was found to be the best choice for yield, purity and function. However, the other polymers offer subtle differences in size and sensitivity to divalent cations that may be useful for a variety of downstream applications.

Silica Nanoparticles for Enhanced Carrier Transport in Polymer-Based Short Channel Transistors

Electronic disorder in conducting polymers represents a fundamental limit for developing high performance polymer-based transistors (TFTs). Nanoscaled manipulation of polymer morphology with electrically inert nanostructures is an interesting and flexible strategy to enhance ordering in polymer films. We show that blending poly[2-methoxy,5-(3′,7′-dimethyloctyloxy)]-1,4-phenylene vinylene (MDMO-PPV) with silica nanoparticles leads to an increase in TFT performance, including an increase in hole mobility by over 10 times. By means of Raman spectroscopy we correlate variations in polymer structure induced by the silica to improvements in the electrical properties. We compare these results to MDMO-PPV blended with the fullerene derivative [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). Although PCBM leads to similar results in longer channel TFTs, no improvement in short channel behavior is observed. These results demonstrate a simple way to realize short channel polymer TFTs with enhanced performance.

Triptycene‐containing polyetherolefins via acyclic diene metathesis polymerization

AbstractSeveral new triptycene‐containing polyetherolefins were synthesized via acyclic diene metathesis (ADMET) polymerization. The well‐established mechanism, high selectivity and specificity, mild reaction conditions, and well‐defined end‐groups make the ADMET polymerization a good choice for studying systematic variations in polymer structure. Two types of triptycene‐based monomer with varying connectivities were used in the synthesis of homopolymers, block copolymers, and random copolymers. In this way, the influence of the triptycene architecture and concentration in the polymer backbone on the thermal behavior of the polymers was studied. Inclusion of increasing amounts of triptycene were found to increase the glass transition temperature, from −44 °C in polyoctenamer to 59 °C in one of the hydrogenated triptycene homopolymers (H‐PT2). Varying the amounts and orientations of triptycene was found to increase the stiffness (H‐PT1), toughness (PT11‐b‐PO1) and ductility (PT11‐ran‐PO3) of the polymer at room temperature. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013

Tribophyiscal scaling effects in friction and wear of polymers on small‐ and large‐scale tests

AbstractCoefficients of friction and wear rates for polyacetal and polytetrafluoroethylene are measured on small‐scale cylinder‐on‐plate tests and large‐scale flat‐on‐flat tests. Three models for extrapolation between small‐ and large‐scale test results, which are based on experimental parameters, are presented: (i) one single mechanical parameter (normal load), (ii) the contact‐pressure–sliding‐velocity model (temperature limit), and (iii) a macroscopic geometry model. The last model is most extensively evaluated and considers thermal effects, sample geometry and contact conditions. After correction for the thermal sliding regime and viscoelastic deformation, the coefficients of friction can be extrapolated while the wear rates are more sensitive to the contact situation. High‐temperature tests on small scale are not representative for high‐load tests on large scale. Besides mechanical effects such as stress concentrations and debris mobility, variations in polymer structure under sliding (formation of rigid amorphous phase) and chemical interactions (wear debris polymerisation) also change with testing scale. The latter effects are explicitly illustrated from spectroscopic measurements on the worn surfaces. Copyright © 2008 John Wiley & Sons, Ltd.

Viscoelastic Properties of Fibrinogen Adsorbed to the Surface of Biomaterials Used in Blood-Contacting Medical Devices

The hemocompatibility of polymeric vascular implants is in part dependent on the propensity of fibrinogen to adsorb to the implant surface. Fibrinogen surface adsorption was measured in real time using a quartz crystal microbalance with dissipation monitoring (QCM-D). Six new, biodegradable tyrosine-derived polycarbonates were used as test surfaces. Stainless steel, poly(L-lactic acid), poly(D,L-lactide-co-glycolide), and poly(ethylene terephthalate) surfaces served as controls and provided a comparison of the test surfaces with those of commonly used biomaterials. Our study addressed the question regarding to which extent systematic variations in polymer structure can be used to optimize X-ray visibility and provide tunable degradation rates while generating protein-repellant surface properties that minimize fibrinogen adsorption. QCM-D revealed surface-dependent changes in fibrinogen layer thickness (2 to 37 nm), adsorbed wet mass (0.2 to 4.3 microg/cm2), and viscosity (0.001 to 0.005 kg/ms). While we did not find an overall correlation between surface air-water contact angle measurements and fibrinogen adsorption (R2 = 0.08), our data demonstrate that gradually increasing the poly(ethylene glycol) content within a subgroup of polymers having the same polymer backbone will lead to decreased fibrinogen adsorption. Within this subgroup of polymers, there was a strong correlation between decreasing air-water contact angles and decreasing fibrinogen adsorption (R2 = 0.95). We conclude that it is possible to minimize fibrinogen adsorption to tyrosine-derived polycarbonates while optimizing X-ray visibility and degradation rates. Some of the tyrosine-derived polycarbonates were identified as useful materials for the design of blood-contacting implants on the basis of their substantially lower levels of fibrinogen adsorption relative to the commonly used controls.

Steric Effects on the Controlled Potential Electro‐Oxidation of 3‐Methylthiophene and Thiophene Oligomers and the Properties of their Polymer Films

This investigation is concerned with the effect of thiophene monomer structures on the electrochemical behavior and physical characteristics of electropolymerized poly(thiophenes) and various poly(3‐methylthiophenes). These variations in polymer structure were achieved by employing thiophene and 3‐methylthiophene oligomers of different unit sizes and substitution patterns as the starting “monomers.” The relative redox characteristics of the “monomers” were deduced from the measured current maximum values of the electro‐oxidation potentials. Electrochemical oxidation of the monomer yields electrically conducting polymers that exhibit internal redox properties unique for each type of starting “monomer”. Scanning electron micrographs of the oxidized films are shown.

The Steric Course of the Cationic Polymerization of Vinyl and Related Monomers. The Counterion Effect

Abstract Polymerization with many triphenylmethyl salts was conducted for α-methylstyrene, isobutyl vinyl ether, t-butyl vinyl ether, and spiro[2,4]hepta-4,6-diene (SHD). The variation of polymer structure (the isotactic unit content for the first three monomer systems and the amount of the 1,4-addition structure for SHD) showed fairly simple correlations with the counteranion size. The results can be interpreted in terms of the tightness of the propagating ion pair within the framework of a theory of the cationic propagation which had been proposed. When the counteranion radius was greater than 3.5 A, the counteranion exerts a parallel influence on the tightness of the growing ion pair without regard to the monomer structure. However, in the case of smaller counterions, the tightness appears to be determined by the relative sizes of counteranion and monomer. The penta-coordinated counteranions gave rise to the polymer structure which would arise from tighter ion pairs than expected from their sizes alone...