Molecular Dynamics Simulations of Strain-Induced Phase Transition of Poly(ethylene oxide) in Water.

PubMed

Donets, Sergii; Sommer, Jens-Uwe

2018-01-11

We study the dilute aqueous solutions of poly(ethylene oxide) (PEO) oligomers that are subject to an elongating force dipole acting on both chain ends using atomistic molecular dynamics. By increasing the force, liquid-liquid demixing can be observed at room temperature far below the lower critical solution temperature. For forces above 35 pN, fibrillar nanostructures are spontaneously formed related to a decrease in hydrogen bonding between PEO and water. Most notable is a rapid decrease in the bifurcated hydrogen bonds during stretching, which can also be observed for isolated single chains. The phase-segregated structures display signs of chain ordering, but a clear signature of the crystalline order is not obtained during the simulation time, indicating a liquid-liquid phase transition induced by chain stretching. Our results indicate that the solvent quality of the aqueous solution of PEO depends on the conformational state of the chains, which is most likely related to the specific hydrogen-bond-induced solvation of PEO in water. The strain-induced demixing of PEO opens the possibility to obtain polymer fibers with low energy costs because crystallization starts via the strain-induced demixing in the extended state only.

Catalytic Hydroxylation of Polyethylenes

PubMed Central

2017-01-01

Polyolefins account for 60% of global plastic consumption, but many potential applications of polyolefins require that their properties, such as compatibility with polar polymers, adhesion, gas permeability, and surface wetting, be improved. A strategy to overcome these deficiencies would involve the introduction of polar functionalities onto the polymer chain. Here, we describe the Ni-catalyzed hydroxylation of polyethylenes (LDPE, HDPE, and LLDPE) in the presence of mCPBA as an oxidant. Studies with cycloalkanes and pure, long-chain alkanes were conducted to assess precisely the selectivity of the reaction and the degree to which potential C–C bond cleavage of a radical intermediate occurs. Among the nickel catalysts we tested, [Ni(Me4Phen)3](BPh4)2 (Me4Phen = 3,4,7,8,-tetramethyl-1,10-phenanthroline) reacted with the highest turnover number (TON) for hydroxylation of cyclohexane and the highest selectivity for the formation of cyclohexanol over cyclohexanone (TON, 5560; cyclohexanol/(cyclohexanone + ε-caprolactone) ratio, 10.5). The oxidation of n-octadecane occurred at the secondary C–H bonds with 15.5:1 selectivity for formation of an alcohol over a ketone and 660 TON. Consistent with these data, the hydroxylation of various polyethylene materials by the combination of [Ni(Me4Phen)3](BPh4)2 and mCPBA led to the introduction of 2.0 to 5.5 functional groups (alcohol, ketone, alkyl chloride) per 100 monomer units with up to 88% selectivity for formation of alcohols over ketones or chloride. In contrast to more classical radical functionalizations of polyethylene, this catalytic process occurred without significant modification of the molecular weight of the polymer that would result from chain cleavage or cross-linking. Thus, the resulting materials are new compositions in which hydroxyl groups are located along the main chain of commercial, high molecular weight LDPE, HDPE, and LLDPE materials. These hydroxylated polyethylenes have improved wetting properties and serve as macroinitiators to synthesize graft polycaprolactones that compatibilize polyethylene–polycaprolactone blends. PMID:28852704

Molecular dynamics simulation study of solvent effects on conformation and dynamics of polyethylene oxide and polypropylene oxide chains in water and in common organic solvents.

PubMed

Hezaveh, Samira; Samanta, Susruta; Milano, Giuseppe; Roccatano, Danilo

2012-03-28

In this paper, the conformation and dynamics properties of polyethylene oxide (PEO) and polypropylene oxide (PPO) polymer chains at 298 K have been studied in the melt and at infinite dilution condition in water, methanol, chloroform, carbon tetrachloride, and n-heptane using molecular dynamics simulations. The calculated density of PEO melt with chain lengths of n = 2, 3, 4, 5 and, for PPO, n = 7 are in good agreement with the available experimental data. The conformational properties of PEO and PPO show an increasing gauche preference for the O-C-C-O dihedral in the following order water>methanol>chloroform>carbon tetrachloride = n-heptane. On the contrary, the preference for trans conformation has a maximum in carbon tetrachloride and n-heptane followed in the order by chloroform, methanol, and water. The PEO conformational preferences are in qualitative agreement with results of NMR studies. PEO chains formed different types of hydrogen bonds with polar solvent molecules. In particular, the occurrence of bifurcated hydrogen bonding in chloroform was also observed. Radii of gyration of PEO chains of length larger than n = 9 monomers showed a good agreement with light scattering data in water and in methanol. For the shorter chains the observed deviations are probably due to the enhanced hydrophobic effects caused by the terminal methyl groups. For PEO the fitting of end-to-end distance distributions with the semi-flexible chain model at 298 K provided persistence lengths of 0.375 and 0.387 nm in water and methanol, respectively. Finally, the radius of gyration of Pluronic P85 turned out to be 2.25 ± 0.4 nm at 293 K in water in agreement with experimental data.

Molecular dynamics simulation study of solvent effects on conformation and dynamics of polyethylene oxide and polypropylene oxide chains in water and in common organic solvents

NASA Astrophysics Data System (ADS)

Hezaveh, Samira; Samanta, Susruta; Milano, Giuseppe; Roccatano, Danilo

2012-03-01

In this paper, the conformation and dynamics properties of polyethylene oxide (PEO) and polypropylene oxide (PPO) polymer chains at 298 K have been studied in the melt and at infinite dilution condition in water, methanol, chloroform, carbon tetrachloride, and n-heptane using molecular dynamics simulations. The calculated density of PEO melt with chain lengths of n = 2, 3, 4, 5 and, for PPO, n = 7 are in good agreement with the available experimental data. The conformational properties of PEO and PPO show an increasing gauche preference for the O-C-C-O dihedral in the following order water>methanol>chloroform>carbon tetrachloride = n-heptane. On the contrary, the preference for trans conformation has a maximum in carbon tetrachloride and n-heptane followed in the order by chloroform, methanol, and water. The PEO conformational preferences are in qualitative agreement with results of NMR studies. PEO chains formed different types of hydrogen bonds with polar solvent molecules. In particular, the occurrence of bifurcated hydrogen bonding in chloroform was also observed. Radii of gyration of PEO chains of length larger than n = 9 monomers showed a good agreement with light scattering data in water and in methanol. For the shorter chains the observed deviations are probably due to the enhanced hydrophobic effects caused by the terminal methyl groups. For PEO the fitting of end-to-end distance distributions with the semi-flexible chain model at 298 K provided persistence lengths of 0.375 and 0.387 nm in water and methanol, respectively. Finally, the radius of gyration of Pluronic P85 turned out to be 2.25 ± 0.4 nm at 293 K in water in agreement with experimental data.

Kinetics and mechanism for the sonochemical degradation of a nonionic surfactant.

PubMed

Singla, Ritu; Grieser, Franz; Ashokkumar, Muthupandian

2009-03-26

The sonolytic degradation of the nonionic surfactant, octaethylene glycol monododecyl ether (C(12)E(8)), has been studied at various initial concentrations below and above its critical micelle concentration (CMC). It has been observed that the degradation rate increases with an increase in the initial concentration of the surfactant until the CMC is reached. Above the CMC an almost constant degradation rate is observed, suggesting that the surfactant in its monomer form is involved in the degradation process. The degradation process of C(12)E(8) involves two distinct primary processes occurring at the bubble/solution interface: (a) hydroxylation/oxidation of the surfactant and (b) pyrolytic fragmentation of the surfactant. The oxidative cleavage of ethylene oxide units provides evidence for OH radical attack. Hydroxylation of the ethoxy chain gives rise to various short-chain carboxyalkyl-polyethylene glycol intermediates. The polyethylene glycol chain formed, due to the scission of the C(12)E(8) molecule, undergoes rapid hydroxylation/oxidation to yield simple compounds that have the potential to undergo further degradation. The detection of multiple intermediates indicates that several processes affect the complete degradation pathways of the surfactant molecule. TOC analysis, however, indicates that the sonolytic mineralization of the surfactant is difficult to achieve at reasonable rates due to the relatively low surface activity of the degradation products formed during sonolysis.

Molecular dynamics simulation study of the role of evenly spaced poly(ethylene oxide) tethers on the aggregation of C60 fullerenes in water.

PubMed

Bedrov, Dmitry; Smith, Grant D; Li, Liwei

2005-06-07

The aggregation behavior of C60 fullerenes and C60 fullerenes with six symmetrically tethered poly(ethylene oxide) oligomers [(PEO)-6-C60] in aqueous solutions has been studied using implicit solvent molecular dynamics simulations. Our simulations reveal that while the attraction between two (PEO)-6-C60 fullerenes in aqueous solution is stronger and longer range than that between two bare C60 fullerenes, the (PEO)-6-C60 fullerenes do not phase-separate in water but rather aggregate in chain-like clusters at concentrations where unmodified fullerenes completely phase-separate.

Effect of Chain Conformation on the Single-Molecule Melting Force in Polymer Single Crystals: Steered Molecular Dynamics Simulations Study.

PubMed

Feng, Wei; Wang, Zhigang; Zhang, Wenke

2017-02-28

Understanding the relationship between polymer chain conformation as well as the chain composition within the single crystal and the mechanical properties of the corresponding single polymer chain will facilitate the rational design of high performance polymer materials. Here three model systems of polymer single crystals, namely poly(ethylene oxide) (PEO), polyethylene (PE), and nylon-66 (PA66) have been chosen to study the effects of chain conformation, helical (PEO) versus planar zigzag conformation (PE, PA66), and chain composition (PE versus PA66) on the mechanical properties of a single polymer chain. To do that, steered molecular dynamics simulations were performed on those polymer single crystals by pulling individual polymer chains out of the crystals. Our results show that the patterns of force-extension curve as well as the chain moving mode are closely related to the conformation of the polymer chain in the single crystal. In addition, hydrogen bonds can enhance greatly the force required to stretch the polymer chain out of the single crystal. The dynamic breaking and reformation of multivalent hydrogen bonds have been observed for the first time in PA66 at the single molecule level.

Surface chemistry changes and microstructure evaluation of low density nanocluster polyethylene under natural weathering: A spectroscopic investigation

NASA Astrophysics Data System (ADS)

Hamzah, M.; Khenfouch, M.; Rjeb, A.; Sayouri, S.; Houssaini, D. S.; Darhouri, M.; Srinivasu, VV

2018-03-01

Polyethylene is the most commonly used plastic in daily life, covering wide areas of application e.g. this polymer is used as a greenhouses covering material. This article investigates the effect of photo-oxidation on commercial unstabilised Low Density Polyethylene (uLDPE), as result of outdoor weathering factors. In this study, the samples were exposed for four months to the natural weather. The physico-chemical effects of natural ageing were studied by attenuated total reflection Fourier transform infrared (ATR-FTIR) and X-ray photoelectron (XPS) spectroscopy to elucidate the chemical composition, the nature of chemical bonds established and further to interrogate the changes that occur on the surface of the uLDPE samples. The main chemical change of uLDPE results in the formation of different kinds of carbonyl and vinyl groups identifiable in the ATR-FTIR and XPS spectra. The degree of crystallinity for these samples was calculated in terms of time exposure. An increase in the degree of crystallinity due to chemicrystallization was observed, which we indicative of the occurrences of chain scission. During outdoor exposure it was found that the photo-oxidation results in the formation of chain scission occurrences via Norrish type II reactions.

Atomistic simulation of CO2 solubility in poly(ethylene oxide) oligomers

NASA Astrophysics Data System (ADS)

Hong, Bingbing; Panagiotopoulos, Athanassios Z.

2014-06-01

We have performed atomistic molecular dynamics simulations coupled with thermodynamic integration to obtain the excess chemical potential and pressure-composition phase diagrams for CO2 in poly(ethylene oxide) oligomers. Poly(ethylene oxide) dimethyl ether, CH3O(CH2CH2O)nCH3 (PEO for short) is a widely applied physical solvent that forms the major organic constituent of a class of novel nanoparticle-based absorbents. Good predictions were obtained for pressure-composition-density relations for CO2 + PEO oligomers (2 ≤ n ≤ 12), using the Potoff force field for PEO [J. Chem. Phys. 136, 044514 (2012)] together with the TraPPE model for CO2 [AIChE J. 47, 1676 (2001)]. Water effects on Henry's constant of CO2 in PEO have also been investigated. Addition of modest amounts of water in PEO produces a relatively small increase in Henry's constant. Dependence of the calculated Henry's constant on the weight percentage of water falls on a temperature-dependent master curve, irrespective of PEO chain length.

Determination of the surface area of smectite in water by ethylene oxide chain adsorption.

PubMed

Yuang, Paul-Cheng; Shen, Yun-Hwei

2005-05-15

This study investigates the feasibility of using ethylene oxide (EO) chain adsorption to determine the surface area of smectite in water. Experimental results indicate that high-molecular-weight poly(ethylene oxide) (PEO) should be used to provide reasonable estimations for monolayer capacity of PEO on smectite. The surface areas of smectites in water are calculated from the monolayer capacity of PEO adsorbed on smectite by taking the area per EO unit as 8.05 A(2). The method measures the actual surface area of smectite exposed when dispersed in water, which is important to applications of smectite under aqueous conditions.

Poly(organo phosphazene) nanoparticles surface modified with poly(ethylene oxide).

PubMed

Vandorpe, J; Schacht, E; Stolnik, S; Garnett, M C; Davies, M C; Illum, L; Davis, S S

1996-10-05

The use of biodegradable derivatives of poly(organo phosphazenes) for the preparation of nanoparticles and their surface modification with the novel poly(ethylene oxide) derivative of poly(organo phosphazene) has been assessed using a range of in vitro characterization methods. The nanoparticles were produced by the precipitation solvent evaporation method from the derivative co-substituted with phenylalanine and glycine ethyl ester side groups. A reduction in particle size to less than 200 nm was achieved by an increase in pH of the preparation medium. The formation (and colloidal stability) of these nanoparticles seems to be controlled by two opposite effects: attractive hydrophobic interactions between phenylalanine ester groups and electrostatic repulsions arising from the carboxyl groups formed due to (partial) hydrolysis of the ester bond(s) at the high pH of the preparation medium. The poly[(glycine ethyl ester)phosphazene] derivative containing 5000-Da poly(ethylene oxide) as 5% of the side groups was used for the surface modification of nanoparticles. Adsorbed onto the particles, the polymer produced a thick coating layer of approximately 35 nm. The coated nanoparticles exhibited reduced surface negative potential and improved colloidal stability toward electrolyte-induced flocculation, relative to the uncoated system. However, the steric stabilization provided was less effective than that of a Poloxamine 908 coating. This difference in effectiveness of the steric stabilization might indicate that, although both the stabilizing polymers possess a 5000-Da poly(ethylene oxide) moiety, there is a difference in the arrangements of these poly(ethylene oxide) chains at the particle surface. (c) 1996 John Wiley & Sons, Inc.

Pyrolysis result of polyethylene waste as fuel for solid oxide fuel cell with samarium doped-ceria (SDC)-carbonate as electrolyte

NASA Astrophysics Data System (ADS)

Syahputra, R. J. E.; Rahmawati, F.; Prameswari, A. P.; Saktian, R.

2017-02-01

In this research, the result of pyrolysis on polyethylene was used as fuel for a solid oxide fuel cell (SOFC). The pyrolysis result is a liquid which consists of hydrocarbon chains. According to GC-MS analysis, the hydrocarbons mainly consist of C7 to C20 hydrocarbon chain. Then, the liquid was applied to a single cell of NSDC-L | NSDC | NSDC-L. NSDC is a composite SDC (samarium doped-ceria) with sodium carbonate. Meanwhile, NSDC-L is a composite of NSDC with LiNiCuO (LNC). NSDC and LNC were analyzed by X-ray diffraction to understand their crystal structure. The result shows that presence of carbonate did not change the crystal structure of SDC. SEM EDX analysis for fuel cell before and after being loaded with polyethylene oil to get information of element diffusion to the electrolyte. Meanwhile, the conductivity properties were investigated through impedance measurement. The presence of carbonate even increases the electrical conductivity. The single cell test with the pyrolysis result of polyethylene at 300 - 600 °C, found that the highest power density is at 600 °C with the maximum power density of 0.14 mW/cm2 and open circuit voltage of 0.4 Volt. Elemental analysis at three point spots of single cell NDSC-L |NSDC|NSDC-L found that a migration of ions was occurred during fuel operation at 300 - 600 °C.

Chemically Realistic Tetrahedral Lattice Models for Polymer Chains: Application to Polyethylene Oxide.

PubMed

Dietschreit, Johannes C B; Diestler, Dennis J; Knapp, Ernst W

2016-05-10

To speed up the generation of an ensemble of poly(ethylene oxide) (PEO) polymer chains in solution, a tetrahedral lattice model possessing the appropriate bond angles is used. The distance between noncovalently bonded atoms is maintained at realistic values by generating chains with an enhanced degree of self-avoidance by a very efficient Monte Carlo (MC) algorithm. Potential energy parameters characterizing this lattice model are adjusted so as to mimic realistic PEO polymer chains in water simulated by molecular dynamics (MD), which serves as a benchmark. The MD data show that PEO chains have a fractal dimension of about two, in contrast to self-avoiding walk lattice models, which exhibit the fractal dimension of 1.7. The potential energy accounts for a mild hydrophobic effect (HYEF) of PEO and for a proper setting of the distribution between trans and gauche conformers. The potential energy parameters are determined by matching the Flory radius, the radius of gyration, and the fraction of trans torsion angles in the chain. A gratifying result is the excellent agreement of the pair distribution function and the angular correlation for the lattice model with the benchmark distribution. The lattice model allows for the precise computation of the torsional entropy of the chain. The generation of polymer conformations of the adjusted lattice model is at least 2 orders of magnitude more efficient than MD simulations of the PEO chain in explicit water. This method of generating chain conformations on a tetrahedral lattice can also be applied to other types of polymers with appropriate adjustment of the potential energy function. The efficient MC algorithm for generating chain conformations on a tetrahedral lattice is available for download at https://github.com/Roulattice/Roulattice .

Polyethylene composites containing a phase change material having a C14 straight chain hydrocarbon

DOEpatents

Salyer, Ival O.

1987-01-01

A composite useful in thermal energy storage, said composite being formed of a polyethylene matrix having a straight chain alkyl hydrocarbon incorporated therein, said polyethylene being crosslinked to such a degree that said polyethylene matrix is form stable and said polyethylene matrix is capable of absorbing at least 10% by weight of said straight chain alkyl hydrocarbon; the composite is useful in forming pellets or sheets having thermal energy storage characteristics.

Li + transport in poly(ethylene oxide) based electrolyte: A combined study of neutron scattering, dielectric spectroscopy, and MD simulation

NASA Astrophysics Data System (ADS)

Do, Changwoo; Lunkenheimer, Peter; Diddens, Diddo; Götz, Marion; Weiß, Matthias; Loidl, Alois; Sun, Xiao-Guang; Allgaier, Jürgen; Ohl, Michael

2013-03-01

Dynamics of Li + transport in polyethylene oxide (PEO) and lithium bis(trifluoromethanesulfonyl)imde (LiTFSI) mixtures are investigated by combining various experimental techniques (neutron spin-echo and dielectric spectroscopy) with molecular dynamics (MD) simulations. Our results suggest that the characteristic live times within the cages formed by oxygens are mainly determined by the alpha-relaxation which corresponds to local segmental motions of polymers, to a much lesser extent by the main chain relaxation, and not at all by the beta-relaxation or any other faster processes. The significant contribution of Li + hopping process to the ion conductivity is also identified. Subsequently, detailed characteristic length and time scales of various Li + transport processes in solid polymer electrolytes are presented and interpreted.

Membranes of Polymers of Intrinsic Microporosity (PIM-1) Modified by Poly(ethylene glycol).

PubMed

Bengtson, Gisela; Neumann, Silvio; Filiz, Volkan

2017-06-05

Until now, the leading polymer of intrinsic microporosity PIM-1 has become quite famous for its high membrane permeability for many gases in gas separation, linked, however, to a rather moderate selectivity. The combination with the hydrophilic and low permeable poly(ethylene glycol) (PEG) and poly(ethylene oxides) (PEO) should on the one hand reduce permeability, while on the other hand enhance selectivity, especially for the polar gas CO₂ by improving the hydrophilicity of the membranes. Four different paths to combine PIM-1 with PEG or poly(ethylene oxide) and poly(propylene oxide) (PPO) were studied: physically blending, quenching of polycondensation, synthesis of multiblock copolymers and synthesis of copolymers with PEO/PPO side chain. Blends and new, chemically linked polymers were successfully formed into free standing dense membranes and measured in single gas permeation of N₂, O₂, CO₂ and CH₄ by time lag method. As expected, permeability was lowered by any substantial addition of PEG/PEO/PPO regardless the manufacturing process and proportionally to the added amount. About 6 to 7 wt % of PEG/PEO/PPO added to PIM-1 halved permeability compared to PIM-1 membrane prepared under similar conditions. Consequently, selectivity from single gas measurements increased up to values of about 30 for CO₂/N₂ gas pair, a maximum of 18 for CO₂/CH₄ and 3.5 for O₂/N₂.

Molecular dynamics simulations of poly (ethylene oxide) hydration and conformation in solutions

NASA Astrophysics Data System (ADS)

Dahal, Udaya; Dormidontova, Elena

Polyethylene oxide (PEO) is one of the most actively used polymers, especially in biomedical applications due to its high hydrophilicity, biocompatibility and potency to inhibit protein adsorption. PEO solubility and conformation in water depends on its capability to form hydrogen bonds. Using atomistic molecular dynamics simulations we investigated the details of water packing around PEO chain and characterized the type and lifetime of hydrogen bonds in aqueous and mixed solvent solutions. The observed polymer chain conformation varies from an extended coil in pure water to collapsed globule in hexane and a helical-like conformation in pure isobutyric acid or isobutyric acid -water mixture in agreement with experimental observations. We'll discuss the implications of protic solvent arrangement and stability of hydrogen bonds on PEO chain conformation and mobility. This research is supported by NSF (DMR-1410928).

Field Effect Transistor Behavior in Electrospun Polyaniline/Polyethylene Oxide Nanofibers

NASA Technical Reports Server (NTRS)

Miranda, Felix A.; Theofylaktos, Noulie; Mueller, Carl H.; Pinto, Nicholas J.

2004-01-01

Novel transistors and logic devices based on nanotechnology concepts are under intense development. The potential for ultra-low-power circuitry makes nanotechnology attractive for applications such as digital electronics and sensors. For NASA applications, nanotechnology offers tremendous opportunities for increased onboard data processing, and thus autonomous decision-making ability, and novel sensors that detect and respond to environmental stimuli with little oversight requirements. Polyaniline (PANi) is an intriguing material because its electrical conductivity can be changed from insulating to metallic by varying the doping levels and conformations of the polymer chain, and when combined with polyethylene oxide (PEO), can be formed into nanofibers with diameters ranging from approximately 50 to 500 nm (depending on the deposition conditions). The initial goal of this work was to demonstrate transistor behavior in these nanofibers, thus creating a foundation for future logic devices.

In vitro and in vivo metabolism of N-adamantyl substituted urea-based soluble epoxide hydrolase inhibitors.

PubMed

Liu, Jun-Yan; Tsai, Hsing-Ju; Morisseau, Christophe; Lango, Jozsef; Hwang, Sung Hee; Watanabe, Takaho; Kim, In-Hae; Hammock, Bruce D

2015-12-15

N,N'-disubstituted urea-based soluble epoxide hydrolase (sEH) inhibitors are promising therapeutics for hypertension, inflammation, and pain in multiple animal models. The drug absorption and pharmacological efficacy of these inhibitors have been reported extensively. However, the drug metabolism of these inhibitors is not well described. Here we reported the metabolic profile and associated biochemical studies of an N-adamantyl urea-based sEH inhibitor 1-adamantan-1-yl-3-(5-(2-(2-ethoxyethoxy)ethoxy)pentyl)urea (AEPU) in vitro and in vivo. The metabolites of AEPU were identified by interpretation of liquid chromatography-mass spectrometry (LC-MS), liquid chromatography-tandem mass spectrometry (LC-MS/MS) and/or NMR. In vitro, AEPU had three major positions for phase I metabolism including oxidations on the adamantyl moiety, urea nitrogen atoms, and cleavage of the polyethylene glycol chain. In a rodent model, the metabolites from the hydroxylation on the adamantyl group and nitrogen atom were existed in blood while the metabolites from cleavage of polyethylene glycol chain were not found in urine. The major metabolite found in rodent urine was 3-(3-adamantyl-ureido)-propanoic acid, a presumably from cleavage and oxidation of the polyethylene glycol moiety. All the metabolites found were active but less potent than AEPU at inhibiting human sEH. Furthermore, cytochrome P450 (CYP) 3A4 was found to be a major enzyme mediating AEPU metabolism. In conclusion, the metabolism of AEPU resulted from oxidation by CYP could be shared with other N-adamantyl-urea-based compounds. These findings suggest possible therapeutic roles for AEPU and new strategies for drug design in this series of possible drugs. Copyright © 2015 Elsevier Inc. All rights reserved.

Raman spectroscopy of biomedical polyethylenes.

PubMed

Pezzotti, Giuseppe

2017-06-01

With the development of three-dimensional Raman algorithms for local mapping of oxidation and plastic strain, and the ability to resolve molecular orientation patterns with microscopic spatial resolution, there is an opportunity to re-examine many of the foundations on which our understanding of biomedical grade ultra-high molecular weight polyethylenes (UHMWPEs) are based. By implementing polarized Raman spectroscopy into an automatized tool with an improved precision in non-destructively resolving Euler angles, oxidation levels, and microscopic strain, we become capable to make accurate and traceable measurements of the in vitro and in vivo tribological responses of a variety of commercially available UHMWPE bearings for artificial hip and knee joints. In this paper, we first review the foundations and the main algorithms for Raman analyses of oxidation and strain of biomedical polyethylene. Then, we critically re-examine a large body of Raman data previously collected on different polyethylene joint components after in vitro testing or in vivo service, in order to shed new light on an area of particular importance to joint orthopedics: the microscopic nature of UHMWPE surface degradation in the human body. A complex scenario of physical chemistry appears from the Raman analyses, which highlights the importance of molecular-scale phenomena besides mere microstructural changes. The availability of the Raman microscopic probe for visualizing oxidation patterns unveiled striking findings related to the chemical contribution to wear degradation: chain-breaking and subsequent formation of carboxylic acid sites preferentially occur in correspondence of third-phase regions, and they are triggered by emission of dehydroxylated oxygen from ceramic oxide counterparts. These findings profoundly differ from more popular (and simplistic) notions of mechanistic tribology adopted in analyzing joint simulator data. Statement of Significance This review was dedicated to the theoretical and experimental evaluation of the commercially available biomedical polyethylene samples by Raman spectroscopy with regard to their molecular textures, oxidative patterns, and plastic strain at the microscopic level in the three dimensions of the Euclidean space. The main achievements could be listed, as follow: (i) visualization of molecular patterns at the surface of UHMWPE bearings operating against metallic components; (ii) differentiation between wear and creep deformation in retrievals; (iii) non-destructive mapping of oxidative patterns; and, (iv) the clarification of chemical interactions between oxide/non-oxide ceramic heads and advanced UHMWPE liners. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

High-concentration graphene dispersion stabilized by block copolymers in ethanol.

PubMed

Perumal, Suguna; Lee, Hyang Moo; Cheong, In Woo

2017-07-01

This article describes a comprehensive study for the preparation of graphene dispersions by liquid-phase exfoliation using amphiphilic diblock copolymers; poly(ethylene oxide)-block-poly(styrene) (PEO-b-PS), poly(ethylene oxide)-block-poly(4-vinylpyridine) (PEO-b-PVP), and poly(ethylene oxide)-block-poly(pyrenemethyl methacrylate) (PEO-b-PPy) with similar block lengths. Block copolymers were prepared from PEO using the Steglich coupling reaction followed by reversible addition-fragmentation chain transfer (RAFT) polymerization. Graphite platelets (G) and reduced graphene oxide (rGO) were used as graphene sources. The dispersion stability of graphene in ethanol was comparatively investigated by on-line turbidity, and the graphene concentration in the dispersions was determined gravimetrically. Our results revealed that the graphene dispersions with PEO-b-PVP were much more stable and included graphene with fewer defects than that with PEO-b-PS or PEO-b-PPy, as confirmed by turbidity and Raman analyses. Gravimetry confirmed that graphene concentrations up to 1.7 and 1.8mg/mL could be obtained from G and rGO dispersions, respectively, using PEO-b-PVP after one week. Distinctions in adhesion forces of PS, VP, PPy block units with graphene surface and the variation in solubility of the block copolymers in ethanol medium significantly affected the stability of the graphene dispersion. Copyright © 2017 Elsevier Inc. All rights reserved.

Molecular dynamics studies of polyethylene oxide and polyethylene glycol: hydrodynamic radius and shape anisotropy.

PubMed

Lee, Hwankyu; Venable, Richard M; Mackerell, Alexander D; Pastor, Richard W

2008-08-01

A revision (C35r) to the CHARMM ether force field is shown to reproduce experimentally observed conformational populations of dimethoxyethane. Molecular dynamics simulations of 9, 18, 27, and 36-mers of polyethylene oxide (PEO) and 27-mers of polyethylene glycol (PEG) in water based on C35r yield a persistence length lambda = 3.7 A, in quantitative agreement with experimentally obtained values of 3.7 A for PEO and 3.8 A for PEG; agreement with experimental values for hydrodynamic radii of comparably sized PEG is also excellent. The exponent upsilon relating the radius of gyration and molecular weight (R(g) proportional, variantM(w)(upsilon)) of PEO from the simulations equals 0.515 +/- 0.023, consistent with experimental observations that low molecular weight PEG behaves as an ideal chain. The shape anisotropy of hydrated PEO is 2.59:1.44:1.00. The dimension of the middle length for each of the polymers nearly equals the hydrodynamic radius R(h)obtained from diffusion measurements in solution. This explains the correspondence of R(h) and R(p), the pore radius of membrane channels: a polymer such as PEG diffuses with its long axis parallel to the membrane channel, and passes through the channel without substantial distortion.

Molecular dynamics simulation of polymer electrolytes based on poly(ethylene oxide) and ionic liquids. I. Structural properties.

PubMed

Costa, Luciano T; Ribeiro, Mauro C C

2006-05-14

Molecular dynamics (MD) simulations have been performed for prototype models of polymer electrolytes in which the salt is an ionic liquid based on 1-alkyl-3-methylimidazolium cations and the polymer is poly(ethylene oxide), PEO. The MD simulations were performed by combining the previously proposed models for pure ionic liquids and polymer electrolytes containing simple inorganic ions. A systematic investigation of ionic liquid concentration, temperature, and the 1-alkyl- chain length, [1,3-dimethylimidazolium]PF6, and [1-butyl-3-methylimidazolium]PF6, effects on resulting equilibrium structure is provided. It is shown that the ionic liquid is dispersed in the polymeric matrix, but ionic pairs remain in the polymer electrolyte. Imidazolium cations are coordinated by both the anions and the oxygen atoms of PEO chains. Probability density maps of occurrences of nearest neighbors around imidazolium cations give a detailed physical picture of the environment experienced by cations. Conformational changes on PEO chains upon addition of the ionic liquid are identified. The equilibrium structure of simulated systems is also analyzed in reciprocal space by using the static structure factor, S(k). Calculated S(k) display a low wave-vector peak, indicating that spatial correlation in an extended-range order prevail in the ionic liquid polymer electrolytes. Long-range correlations are assigned to nonuniform distribution of ionic species within the simulation box.

Dielectric and mechanical investigations on the hydrophilicity and hydrophobicity of polyethylene oxide modified on a silicon surface

DOE PAGES

Shang, Jing; Hong, Kunlun; Wang, Tao; ...

2016-10-02

Here, polyethylene oxide (PEO) has been widely used in biomedical fields. The antibiofouling property of the PEO-modified surface has been extensively investigated but is far from being fully understood. A series of PEOs with narrowly distributed molecular weight (M w), synthesized with the technique of high vacuum anionic polymerization, have been successfully grafted onto the surface of silicon wafers. The power-law relationship between the thickness of the monolayer versus the M w of the grafted PEO shows a scaling of 0.3, indicating compact condensing of the chains. The static contact angles show higher hydrophobicity for the layer of PEO withmore » higher M w, which can be attributed to the closely packed conformation of the chains with high density. The frequency shift of the contact resonance indicates that the Young’s modulus decreases and the loss factor increases with the increase in the M w of PEO and the thickness of the PEO layers. Dielectric spectroscopy of bare or PEO-grafted wafers in the aqueous solutions reveals an interfacial polarization, which results from compositional and structural changes in the interface layer and depends on temperatures and salt concentrations. At a given grafting density, the PEO chains are swollen in pure water, demonstrating hydrophilic behavior, whereas they collapse in salt solutions, showing hydrophobic characteristics.« less

Biomimetic porous high-density polyethylene/polyethylene- grafted-maleic anhydride scaffold with improved in vitro cytocompatibility.

PubMed

Sharma, Swati; Bhaskar, Nitu; Bose, Surjasarathi; Basu, Bikaramjit

2018-05-01

A major challenge for tissue engineering is to design and to develop a porous biocompatible scaffold, which can mimic the properties of natural tissue. As a first step towards this endeavour, we here demonstrate a distinct methodology in biomimetically synthesized porous high-density polyethylene scaffolds. Co-extrusion approach was adopted, whereby high-density polyethylene was melt mixed with polyethylene oxide to form an immiscible binary blend. Selective dissolution of polyethylene oxide from the biphasic system revealed droplet-matrix-type morphology. An attempt to stabilize such morphology against thermal and shear effects was made by the addition of polyethylene- grafted-maleic anhydride as a compatibilizer. A maximum ultimate tensile strength of 7 MPa and elastic modulus of 370 MPa were displayed by the high-density polyethylene/polyethylene oxide binary blend with 5% maleated polyethylene during uniaxial tensile loading. The cell culture experiments with murine myoblast C2C12 cell line indicated that compared to neat high-density polyethylene and high-density polyethylene/polyethylene oxide, the high-density polyethylene/polyethylene oxide with 5% polyethylene- grafted-maleic anhydride scaffold significantly increased muscle cell attachment and proliferation with distinct elongated threadlike appearance and highly stained nuclei, in vitro. This has been partly attributed to the change in surface wettability property with a reduced contact angle (∼72°) for 5% PE- g-MA blends. These findings suggest that the high-density polyethylene/polyethylene oxide with 5% polyethylene- grafted-maleic anhydride can be treated as a cell growth substrate in bioengineering applications.

Insights on Li-TFSI diffusion in polyethylene oxide for battery applications

NASA Astrophysics Data System (ADS)

Molinari, Nicola; Mailoa, Jonathan; Kozinsky, Boris; Robert Bosch LLC Collaboration

Improving the energy density, safety and efficiency of lithium-ion (Li-ion) batteries is crucial for the future of energy storage and applications such as electric cars. A key step in the research of next-generation solid polymeric electrolyte materials is understanding the diffusion mechanism of Li-ion in polyethylene oxide (PEO) in order to guide the design of electrolytes materials with high Li-ion diffusion while, ideally, suppress counter-anion movement. In this work we use computer simulations to investigate this long-standing problem at a fundamental level. The system under study has Li-TFSI concentration and PEO chain length that are representative of practical application specifications; the interactions of the molecular model are described via the PCFF+ all-atom force-field. Validation of the model is performed by comparing trends against experiments for diffusivity and conductivity as a function of salt concentration. The analysis of Li-TFSI molecular dynamics trajectories reveals that 1. for high Li-TFSI concentration a significant fraction of Li-ion is coordinated by only TFSI and consistently move less than PEO-coordinated Li-ion, 2. PEO chain motion is key in enabling Li-ion movement. Robert Bosch LLC.

Coarse grained study of pluronic F127: Comparison with shorter co-polymers in its interaction with lipid bilayers and self-aggregation in water

NASA Astrophysics Data System (ADS)

Wood, I.; Martini, M. F.; Albano, J. M. R.; Cuestas, M. L.; Mathet, V. L.; Pickholz, M.

2016-04-01

The aim of this work is to understand the interactions of the poloxamer Pluronic F127, with lipid bilayers and its ability to self-associate in an aqueous environment. Molecular dynamics simulations at the coarse-grain scale were performed to address the behavior of single Pluronic F127 and shorter poloxamers unimers in palmitoyl-oleoyl-phosphatidyl-choline model membranes. According to the initial conditions and the poly-ethylene oxide/poly-propylene oxide composition, in water phase the unimer chain collapses into a coil conformation or adopts an interphacial U-shaped - or membrane spanning - distribution. A combination of poly-propylene oxide length, and the poly-ethylene oxide ability to cover poly-propylene oxide, is determinant for the conformation adopted by the unimer in each phase. Results of the simulations showed molecular evidence of strong interaction between Pluronic F127 and model membranes both in stable U-shaped and span conformations. The knowledge of this interaction could contribute to improve drug permeation. Additionally, we investigated the aggregation of one hundred Pluronic F127 unimers in water forming a micelle-like structure, suitable to be used as drug delivery system models.

Polyethylene oxide hydration in grafted layers

NASA Astrophysics Data System (ADS)

Dormidontova, Elena; Wang, Zilu

Hydration of water soluble polymers is one of the key-factors defining their conformation and properties, similar to biopolymers. Polyethylene oxide (PEO) is one of the most important biomedical-applications polymers and is known for its reverse temperature solubility due to hydrogen bonding with water. As in many practical applications PEO chains are grafted to surfaces, e.g. of nanoparticles or planar surfaces, it is important to understand PEO hydration in such grafted layers. Using atomistic molecular dynamic simulations we investigate the details of molecular conformation and hydration of PEO end-grafted to gold surfaces. We analyze polymer and water density distribution as a function of distance from the surface for different grafting densities. Based on a detailed analysis of hydrogen bonding between polymer and water in grafted PEO layers, we will discuss the extent of PEO hydration and its implication for polymer conformation, mobility and layer properties. This research is supported by NSF (DMR-1410928).

Molecular dynamics simulation of the polymer electrolyte poly(ethylene oxide)/LiClO(4). II. Dynamical properties.

PubMed

Siqueira, Leonardo J A; Ribeiro, Mauro C C

2006-12-07

The dynamical properties of the polymer electrolyte poly(ethylene oxide) (PEO)LiClO(4) have been investigated by molecular dynamics simulations. The effect of changing salt concentration and temperature was evaluated on several time correlation functions. Ionic displacements projected on different directions reveal anisotropy in short-time (rattling) and long-time (diffusive) dynamics of Li(+) cations. It is shown that ionic mobility is coupled to the segmental motion of the polymeric chain. Structural relaxation is probed by the intermediate scattering function F(k,t) at several wave vectors. Good agreement was found between calculated and experimental F(k,t) for pure PEO. A remarkable slowing down of polymer relaxation is observed upon addition of the salt. The ionic conductivity estimated by the Nernst-Einstein equation is approximately ten times higher than the actual conductivity calculated by the time correlation function of charge current.

Interchain coupled chain dynamics of poly(ethylene oxide) in blends with poly(methyl methacrylate): coupling model analysis.

PubMed

Ngai, K L; Wang, Li-Min

2011-11-21

Quasielastic neutron scattering and molecular dynamics simulation data from poly(ethylene oxide) (PEO)/poly(methyl methacrylate) (PMMA) blends found that for short times the self-dynamics of PEO chain follows the Rouse model, but at longer times past t(c) = 1-2 ns it becomes slower and departs from the Rouse model in dependences on time, momentum transfer, and temperature. To explain the anomalies, others had proposed the random Rouse model (RRM) in which each monomer has different mobility taken from a broad log-normal distribution. Despite the success of the RRM, Diddens et al. [Eur. Phys. Lett. 95, 56003 (2011)] extracted the distribution of friction coefficients from the MD simulations of a PEO/PMMA blend and found that the distribution is much narrower than expected from the RRM. We propose a simpler alternative explanation of the data by utilizing alone the observed crossover of PEO chain dynamics at t(c). The present problem is just a special case of a general property of relaxation in interacting systems, which is the crossover from independent relaxation to coupled many-body relaxation at some t(c) determined by the interaction potential and intermolecular coupling/constraints. The generality is brought out vividly by pointing out that the crossover also had been observed by neutron scattering from entangled chains relaxation in monodisperse homopolymers, and from the segmental α-relaxation of PEO in blends with PMMA. The properties of all the relaxation processes in connection with the crossover are similar, despite the length scales of the relaxation in these systems are widely different.

Interchain coupled chain dynamics of poly(ethylene oxide) in blends with poly(methyl methacrylate): Coupling model analysis

NASA Astrophysics Data System (ADS)

Ngai, K. L.; Wang, Li-Min

2011-11-01

Quasielastic neutron scattering and molecular dynamics simulation data from poly(ethylene oxide) (PEO)/poly(methyl methacrylate) (PMMA) blends found that for short times the self-dynamics of PEO chain follows the Rouse model, but at longer times past tc = 1-2 ns it becomes slower and departs from the Rouse model in dependences on time, momentum transfer, and temperature. To explain the anomalies, others had proposed the random Rouse model (RRM) in which each monomer has different mobility taken from a broad log-normal distribution. Despite the success of the RRM, Diddens et al. [Eur. Phys. Lett. 95, 56003 (2011)] extracted the distribution of friction coefficients from the MD simulations of a PEO/PMMA blend and found that the distribution is much narrower than expected from the RRM. We propose a simpler alternative explanation of the data by utilizing alone the observed crossover of PEO chain dynamics at tc. The present problem is just a special case of a general property of relaxation in interacting systems, which is the crossover from independent relaxation to coupled many-body relaxation at some tc determined by the interaction potential and intermolecular coupling/constraints. The generality is brought out vividly by pointing out that the crossover also had been observed by neutron scattering from entangled chains relaxation in monodisperse homopolymers, and from the segmental α-relaxation of PEO in blends with PMMA. The properties of all the relaxation processes in connection with the crossover are similar, despite the length scales of the relaxation in these systems are widely different.

Tissue response to intraperitoneal implants of polyethylene oxide-modified polyethylene terephthalate.

PubMed

Desai, N P; Hubbell, J A

1992-01-01

Polyethylene terephthalate films surface modified with polyethylene oxide of mol wt 18,500 g/mol (18.5 k) by a previously described technique, were implanted in the peritoneal cavity of mice, along with their respective untreated controls, for periods of 1-28 d. The implants were retrieved and examined for tissue reactivity and cellular adherence. The control polyethylene terephthalate surfaces showed an initial inflammatory reaction followed by an extensive fibrotic response with a mean thickness of 60 microns at 28 d. By contrast, polyethylene oxide-modified polyethylene terephthalate showed only a mild inflammatory response and no fibrotic encapsulation throughout the implantation period: at 28 d a cellular monolayer was observed. Apparently either the polyethylene oxide-modified surface was stimulating less inflammation, which was in turn stimulating less fibroblastic overgrowth, or the cellular adhesion to the polyethylene oxide-modified surface was too weak to support cellular multilayers.

An evaluation of the effects of PEO/PEG molecular weights on extruded alumina rods

NASA Astrophysics Data System (ADS)

Bolger, Nancy Beth

1998-12-01

Alumina rods were piston extruded from bodies containing polyethylene glycols (PEGs) and polyethylene oxides (PEOs) with molecular weights ranging from 1,300 to 3,800,000 g/mol. A blend of aluminas possessing different particle size distributions was evaluated with regard to its extrusion pressure by varying the amount of PEG/PEO addition. Behavior exhibited by the alumina blend was dependent upon the additive that was used. The higher molecular weight binders with average molecular weight of 200,000 g/mol and 3,350,000 g/mol displayed the most severe behaviors of near dilatant and dilatant respectively. Physical properties of the green and fired states, as well as the binder burnout, were investigated with the changing additions. Correlation between the green and fired strengths and the changing molecular weights were examined. The additive present influenced the surface properties of the rods, which affected the green strengths. The highest average molecular weight polyethylene glycols showed higher green strengths, while the lowest green strengths were observed for the high molecular weight polyethylene oxides. Fired strengths generally ranged from approximately 12,000 psi to 16,000 psi for additive batches. Alumina pellets containing twelve separate combinations of polyethylene glycol with polyethylene oxide were dry pressed. Physical properties of the green and fired states were examined. Statistical analysis was performed upon the data and seven combinations of polyethylene glycol with polyethylene oxide were deemed significant. These combinations in conjunction with the same alumina blend were then piston extruded. The addition of polyethylene glycol reduced the near dilatant behavior exhibited by the 200,000 g/mol average molecular weight polyethylene oxide. Dilatant behavior was completely eliminated from the 3,350,000 g/mol average molecular weight polyethylene oxide batches. Physical properties of the green and fired states were again investigated with the changing additions. Polyethylene oxide, in combination with polyethylene glycol, did show an increase in green strength versus the polyethylene oxide alone. Strengths were still lower than those displayed by the polyethylene glycols alone. Reductions or degradations in molecular weight of the polymers due to mixing and extrusion processes may account for lower green strength of bodies, especially those containing polyethylene oxides.

Reactivity assay of surface carboxyl chain-ends of poly(ethylene terephthalate) (PET) film and track-etched microporous membranes using fluorine labelled- and/or 3H-labelled derivatization reagents: tandem analysis by X-ray photoelectron spectroscopy (XPS) and liquid scintillation counting (LSC)

NASA Astrophysics Data System (ADS)

Deldime, Michèle; Dewez, Jean-Luc; Schneider, Yves-Jacques; Marchand-Brynaert, Jacqueline

1995-09-01

Poly(ethylene terephthalate) (PET) films and track-etched microporous membranes of two different porosities were pretreated by hydrolysis and/or oxidation in order to enhance the amount of carboxyl chain-ends displayed on their surface. The reactivity of these carboxyl functions was determined by derivatization assays in which the reactions were carried out under conditions likely to be encountered in the coupling of water-soluble biochemical signals on the surface of biomaterials. Original reagents, fluorine-labelled and/or 3H-labelled aminoacid compounds, were used. The derivatized PET samples were examined by X-ray photoelectron spectroscopy (XPS) to characterize their apparent surfaces, and by liquid scintillation counting (LSC) to quantify the amount of tags fixed on their open surfaces. Using this dual assay technique, we analyzed the surface of microporous membranes which are currently used as substrates for cell culture systems.

Resistance of poly(ethylene oxide)-silane monolayers to the growth of polyelectrolyte multilayers.

PubMed

Buron, Cédric C; Callegari, Vincent; Nysten, Bernard; Jonas, Alain M

2007-09-11

The ability of poly(ethylene oxide)-silane (PEO-silane) monolayers grafted onto silicon surfaces to resist the growth of polyelectrolyte multilayers under various pH conditions is assessed for different pairs of polyelectrolytes of varying molar mass. For acidic conditions (pH 3), the PEO-silane monolayers exhibit good polyelectrolyte repellency provided the polyelectrolytes bear no moieties that are able to form hydrogen bonds with the ether groups of the PEO chains. At basic pH, PEO-silane monolayers undergo substantial hydrolysis leading to the formation of negatively charged defects in the monolayers, which then play the role of adsorption sites for the polycation. Once the polycation is adsorbed, multilayer growth ensues. Because this is defect-driven growth, the multilayer is not continuous and is made of blobs or an open network of adsorbed strands. For such conditions, the molar mass of the polyelectrolyte plays a key role, with polyelectrolyte chains of larger molar mass adsorbing on a larger number of defects, resulting in stronger anchoring of the polyelectrolyte complex on the surfaces and faster subsequent growth of the multilayer. For polyelectrolytes of sufficiently low molar mass at pH 9, the growth of the multilayer can nevertheless be prevented for as much as five cycles of deposition.

Surface recrystallization of polyethylene extended-chain crystals.

PubMed

Wunderlich, B; Melillo, L

1966-12-09

Rough fracture surfaces of extended-chain polyethylene crystals become unstable at temperatures below the bulk melting point. There is no way for the extended chains, which are up to 20,000 methylene units long, to change position without collapse. As a result, the rough surfaces smooth out on heating by covering themselves with oriented folded-chain lamellae.

Influence of different factors on the destruction of films based on polylactic acid and oxidized polyethylene

NASA Astrophysics Data System (ADS)

Podzorova, M. V.; Tertyshnaya, Yu. V.; Pantyukhov, P. V.; Shibryaeva, L. S.; Popov, A. A.; Nikolaeva, S.

2016-11-01

Influence of different environmental factors on the degradation of film samples based on polylactic acid and low density polyethylene with the addition of oxidized polyethylene was studied in this work. Different methods were used to find the relationship between degradation and ultraviolet, moisture, oxygen. It was found that the addition of oxidized polyethylene, used as a model of recycled polyethylene, promotes the degradation of blends.

Thiolated polyethylene oxide as a non-fouling element for nano-patterned bio-devices

NASA Astrophysics Data System (ADS)

Lisboa, Patrícia; Valsesia, Andrea; Colpo, Pascal; Gilliland, Douglas; Ceccone, Giacomo; Papadopoulou-Bouraoui, Andri; Rauscher, Hubert; Reniero, Fabiano; Guillou, Claude; Rossi, François

2007-03-01

This work describes the synthesis of a thiolated polyethylene oxide that self-assembles on gold to create a non-fouling surface. Thiolated polyethylene oxide was synthesised by reacting 16-mercaptohexadecanoic acid with polyethylene glycol mono methyl ether. The coverage of the thiolated polyethylene oxide on gold was studied by cyclic voltammetry, and the modified surfaces were characterised by X-ray photoelectron spectroscopy and ellipsometry. Protein resistance was assessed using quartz crystal microbalance. Results showed a non-fouling character produced by the thiolated polyethylene oxide. The synthesised product was used as the passivation layer on nano-patterned surfaces consisting of arrayed nano-spots, fabricated by plasma based colloidal lithography. The specific adsorption of anti-bovine serum albumin in the mercaptohexadecanoic acid spots was verified by atomic force microscopy.

Polydispersity-Driven Block Copolymer Amphiphile Self-Assembly into Prolate-Spheroid Micelles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schmitt, Andrew L.; Repollet-Pedrosa, Milton H.; Mahanthappa, Mahesh K.

The aqueous self-assembly behavior of polydisperse poly(ethylene oxide-b-1,4-butadiene-b-ethylene oxide) (OBO) macromolecular triblock amphiphiles is examined to discern the implications of continuous polydispersity in the hydrophobic block on the resulting aqueous micellar morphologies of otherwise monodisperse polymer surfactants. The chain length polydispersity and implicit composition polydispersity of these samples furnishes a distribution of preferred interfacial curvatures, resulting in dilute aqueous block copolymer dispersions exhibiting coexisting spherical and rod-like micelles with vesicles in a single sample with a O weight fraction, w{sub O}, of 0.18. At higher w{sub O} = 0.51-0.68, the peak in the interfacial curvature distribution shifts and we observemore » the formation of only American football-shaped micelles. We rationalize the formation of these anisotropically shaped aggregates based on the intrinsic distribution of preferred curvatures adopted by the polydisperse copolymer amphiphiles and on the relief of core block chain stretching by chain-length-dependent intramicellar segregation.« less

Biodegradation of polyethylene by the thermophilic bacterium Brevibacillus borstelensis.

PubMed

Hadad, D; Geresh, S; Sivan, A

2005-01-01

To select a polyethylene-degrading micro-organism and to study the factors affecting its biodegrading activity. A thermophilic bacterium Brevibaccillus borstelensis strain 707 (isolated from soil) utilized branched low-density polyethylene as the sole carbon source and degraded it. Incubation of polyethylene with B. borstelensis (30 days, 50 degrees C) reduced its gravimetric and molecular weights by 11 and 30% respectively. Brevibaccillus borstelensis also degraded polyethylene in the presence of mannitol. Biodegradation of u.v. photo-oxidized polyethylene increased with increasing irradiation time. Fourier Transform Infra-Red (FTIR) analysis of photo-oxidized polyethylene revealed a reduction in carbonyl groups after incubation with the bacteria. This study demonstrates that polyethylene--considered to be inert--can be biodegraded if the right microbial strain is isolated. Enrichment culture methods were effective for isolating a thermophilic bacterium capable of utilizing polyethylene as the sole carbon and energy source. Maximal biodegradation was obtained in combination with photo-oxidation, which showed that carbonyl residues formed by photo-oxidation play a role in biodegradation. Brevibaccillus borstelensis also degraded the CH2 backbone of nonirradiated polyethylene. Biodegradation of polyethylene by a single bacterial strain contributes to our understanding of the process and the factors affecting polyethylene biodegradation.

Exploring the folding pattern of a polymer chain in a single crystal by combining single-molecule force spectroscopy and steered molecular dynamics simulations.

PubMed

Song, Yu; Feng, Wei; Liu, Kai; Yang, Peng; Zhang, Wenke; Zhang, Xi

2013-03-26

Understanding the folding pattern of a single polymer chain within its single crystal will shed light on the mechanism of crystallization. Here, we use the combined techniques of atomic force microscopy (AFM)-based single-molecule force spectroscopy (SMFS) and steered molecular dynamics (SMD) simulations to study the folding pattern of a polyethylene oxide (PEO) chain in its single crystal. Our results show that the folding pattern of a PEO chain in the crystal formed in dilute solution follows the adjacent re-entry folding model. While in the crystal obtained from the melt, the nonadjacent folding with large and irregular loops contributes to big force fluctuations in the force-extension curves. The method established here can offer a novel strategy to directly unravel the chain-folding pattern of polymer single crystals at single-molecule level.

Peroxide-mediated desulfurization of phosphorothioate oligonucleotides and its prevention.

PubMed

Krotz, Achim H; Mehta, Rahul C; Hardee, Gregory E

2005-02-01

Desulfurization at the internucleotide phosphorothioate linkage of antisense oligonucleotides (ASOs) in dermatological formulations has been investigated using strong ion exchange chromatography and mass spectroscopy. The formation of phosphate diester linkages appeared to arise from a reaction between the phosphorothioate oligonucleotide and a potent oxidizing agent. Screening of excipients used in the formulation indicated that the cause of desulfurization was related to the presence of polyethylene glycol-derived nonionic surfactants MYRJ 52 or BRIJ 58. Autoxidation of the polyethylene glycol chain is suggested as the probable origin for the observed incompatibility. The ability of various antioxidants to prevent oxidative degradation of ASO-1 in simple test systems and in oil-in-water emulsions is described. It is found that in test systems both lipophilic and hydrophilic antioxidants are effective. However, in cream formulation (oil-in-water emulsions) of ASO-1 the addition of hydrophilic antioxidants L-cysteine or DL-alpha-lipoic acid has been shown to be superior in protecting the oligonucleotide from desulfurization upon storage. Copyright 2004 Wiley-Liss, Inc.

Probing the Conformational Landscape of Polyether Building Blocks in Supersonic Jets

NASA Astrophysics Data System (ADS)

Bocklitz, Sebastian; Hewett, Daniel M.; Zwier, Timothy S.; Suhm, Martin A.

2016-06-01

Polyethylene oxides (Polyethylene glycoles) and their phenoxy-capped analogs represent a prominent class of important polymers that are highly used as precursor molecules in supramolecular reactions. After a detailed study on the simplest representative (1,2-dimethoxyethane) [1], we present results on oligoethylene oxides with increasing chain lengths obtained by spontaneous Raman scattering in a supersonic jet. Through variation of stagnation pressure, carrier gas, nozzle distance and temperature we gain information on the conformational landscape as well as the mutual interconversion of low energy conformers. The obtained results are compared to state-of-the-art quantum chemical calculations. Additionally, we present UV as well as IR-UV and UV-UV double resonance studies on 1-methoxy-2-phenoxyethane in a supersonic jet. These complementary techniques allow for conformationally selective electronic and vibrational spectra in a closely related conformational landscape. [1] S. Bocklitz, M. A. Suhm, Constraining the Conformational Landscape of a Polyether Building Block by Raman Jet Spectroscopy, Z. Phys. Chem. 2015, 229, 1625-1648.

Stability and effectiveness against bacterial adhesion of poly(ethylene oxide) coatings in biological fluids.

PubMed

Roosjen, Astrid; de Vries, Joop; van der Mei, Henny C; Norde, Willem; Busscher, Henk J

2005-05-01

Poly(ethylene oxide) (PEO) coatings have been shown to reduce the adhesion of different microbial strains and species and thus are promising as coatings to prevent biomaterial-centered infection of medical implants. Clinically, however, PEO coatings are not yet applied, as little is known about their stability and effectiveness in biological fluids. In this study, PEO coatings coupled to a glass substratum through silyl ether bonds were exposed for different time intervals to saliva, urine, or phosphate-buffered saline (PBS) as a reference at 37 degrees C. After exposure, the effectiveness of the coatings against bacterial adhesion was assessed in a parallel plate flow chamber. The coatings appeared effective against Staphylococcus epidermidis adhesion for 24, 48, and 0.5 h in PBS, urine, and saliva, respectively. Using XPS and contact-angle measurements, the variations in effectiveness could be attributed to conditioning film formation. The overall short stability results from hydrolysis of the coupling of the PEO chains to the substratum. (c) 2005 Wiley Periodicals, Inc.

Magnetic Nanocomposites and Their Incorporation into Higher Order Biosynthetic Functional Architectures

DOE PAGES

Watt, John; Collins, Aaron M.; Vreeland, Erika C.; ...

2018-01-17

A magnetically active Fe 3O 4/poly(ethylene oxide)-block-poly(butadiene) (PEO-b-PBD) nanocomposite is formed by the encapsulation of magnetite nanoparticles with a short-chain amphiphilic block copolymer. This material is then incorporated into the self-assembly of higher order polymer architectures, along with an organic pigment, to yield biosynthetic, bifunctional optical and magnetically active Fe 3O 4/bacteriochlorophyll c/PEO-b-PBD polymeric chlorosomes.

21 CFR 172.260 - Oxidized polyethylene.

Code of Federal Regulations, 2013 CFR

2013-04-01

... FOR HUMAN CONSUMPTION (CONTINUED) FOOD ADDITIVES PERMITTED FOR DIRECT ADDITION TO FOOD FOR HUMAN CONSUMPTION Coatings, Films and Related Substances § 172.260 Oxidized polyethylene. Oxidized polyethylene may... by high temperature vapor pressure osmometry; contains a maximum of 5 percent by weight of total...

21 CFR 172.260 - Oxidized polyethylene.

Code of Federal Regulations, 2011 CFR

2011-04-01

... FOR HUMAN CONSUMPTION (CONTINUED) FOOD ADDITIVES PERMITTED FOR DIRECT ADDITION TO FOOD FOR HUMAN CONSUMPTION Coatings, Films and Related Substances § 172.260 Oxidized polyethylene. Oxidized polyethylene may... by high temperature vapor pressure osmometry; contains a maximum of 5 percent by weight of total...

21 CFR 172.260 - Oxidized polyethylene.

Code of Federal Regulations, 2012 CFR

2012-04-01

... FOR HUMAN CONSUMPTION (CONTINUED) FOOD ADDITIVES PERMITTED FOR DIRECT ADDITION TO FOOD FOR HUMAN CONSUMPTION Coatings, Films and Related Substances § 172.260 Oxidized polyethylene. Oxidized polyethylene may... by high temperature vapor pressure osmometry; contains a maximum of 5 percent by weight of total...

Molecular dynamics simulation of interactions between a sodium dodecyl sulfate micelle and a poly(ethylene oxide) polymer.

PubMed

Shang, Barry Z; Wang, Zuowei; Larson, Ronald G

2008-03-13

We have performed atomistic molecular dynamics simulations of an anionic sodium dodecyl sulfate (SDS) micelle and a nonionic poly(ethylene oxide) (PEO) polymer in aqueous solution. The micelle consisted of 60 surfactant molecules, and the polymer chain lengths varied from 20 to 40 monomers. The force field parameters for PEO were adjusted by using 1,2-dimethoxymethane (DME) as a model compound and matching its hydration enthalpy and conformational behavior to experiment. Excellent agreement with previous experimental and simulation work was obtained through these modifications. The simulated scaling behavior of the PEO radius of gyration was also in close agreement with experimental results. The SDS-PEO simulations show that the polymer resides on the micelle surface and at the hydrocarbon-water interface, leading to a selective reduction in the hydrophobic contribution to the solvent-accessible surface area of the micelle. The association is mainly driven by hydrophobic interactions between the polymer and surfactant tails, while the interaction between the polymer and sulfate headgroups on the micelle surface is weak. The 40-monomer chain is mostly wrapped around the micelle, and nearly 90% of the monomers are adsorbed at low PEO concentration. Simulations were also performed with multiple 20-monomer chains, and gradual addition of polymer indicates that about 120 monomers are required to saturate the micelle surface. The stoichiometry of the resulting complex is in close agreement with experimental results, and the commonly accepted "beaded necklace" structure of the SDS-PEO complex is recovered by our simulations.

Thermoresponsive complex amphiphilic block copolymer micelles investigated by laser light scattering.

PubMed

Zhao, Fang; Xie, Dinghai; Zhang, Guangzhao; Pispas, Stergios

2008-05-22

Poly(isoprene)-block-poly(ethylene oxide) (PI-b-PEO) diblock copolymers form micelles in water. The introduction of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (PEO-b-PPO-b-PEO) triblock copolymer leads to the formation of mixed micelles through hydrophobic interaction. The dimension of the mixed micelles varies with the weight ratio (r) of PEO-b-PPO-b-PEO to PI-b-PEO. By use of laser light scattering, we have investigated the temperature dependence of the structural evolution of the micelles at different r. At r<10, the size of the mixed micelles decreases with temperature. At r>10, due to the excessive PEO-b-PPO-b-PEO chains in solution, as temperature increases, the mixed micelles aggregate into larger micelle clusters.

Insight into fast ion migration kinetics of a new hybrid single Li-ion conductor based on aluminate complexes for solid-state Li-ion batteries.

PubMed

Feng, Yancong; Tan, Rui; Zhao, Yan; Gao, Rongtan; Yang, Luyi; Yang, Jinlong; Li, Hao; Zhou, Guofu; Chen, Haibiao; Pan, Feng

2018-03-29

A novel hybrid single Li-ion conductor (SLIC) for a Li-ion solid electrolyte was prepared by mixing aluminate complexes-polyethylene glycol (LiAl-PEG) and polyethylene oxide (PEO) for solid-state Li-ion batteries. The LiAl-PEG/PEO blend possesses high thermal stability and electrochemical stability with an oxidation decomposition voltage up to 4.8 V. Notably, this hybrid SLIC exhibits not only excellent Li-ion migration kinetics, but also good ionic conductivity as high as 4.0 × 10-5 and 2.6 × 10-4 S cm-1 at 30 and 100 °C, respectively, which is much higher than previously reported SLICs. Importantly, by the combination of molecular dynamics simulations and experiment measurements, the mechanisms of Li-ion migration across the SLIC (LiAl-PEG), the salt-in-polymer (LiClO4/PEO) and the optimized SLIC (LiAl-PEG/PEO) were systematically investigated for the first time. The new hopping transport mechanism was verified for the SLIC system at the nanoscale. As for the hybrid SLIC, PEO chains enhance the segmental mobility of the ether-chains bonded with Al atoms, improve the ionicity, and provide extra ionic paths for Li transfer, resulting in the optimized Li-ion migration kinetics of LiAl-PEG/PEO.

Organic-inorganic random copolymers from methacrylate-terminated poly(ethylene oxide) with 3-methacryloxypropylheptaphenyl polyhedral oligomeric silsesquioxane: synthesis via RAFT polymerization and self-assembly behavior.

PubMed

Wei, Kun; Li, Lei; Zheng, Sixun; Wang, Ge; Liang, Qi

2014-01-14

In this contribution, we report the synthesis of organic-inorganic random polymers from methacrylate-terminated poly(ethylene oxide) (MAPEO) (Mn = 950) and 3-methacryloxypropylheptaphenyl polyhedral oligomeric silsesquioxane (MAPOSS) macromers via reversible addition-fragmentation chain transfer (RAFT) polymerization with 4-cyano-4-(thiobenzoylthio) valeric acid (CTBTVA) as the chain transfer agent. The organic-inorganic random copolymers were characterized by means of (1)H NMR spectroscopy, gel permeation chromatography (GPC) and differential scanning calorimetry (DSC). The results of GPC indicate that the polymerizations were carried out in a controlled fashion. Transmission electron microscopy (TEM) showed that the organic-inorganic random copolymers in bulk were microphase-separated and the POSS microdomains were formed via POSS-POSS interactions. In aqueous solutions the organic-inorganic random copolymers were capable of self-assembling into spherical nanoobjects as evidenced by transmission electron microscopy (TEM) and dynamic laser scattering (DLS). The self-assembly behavior of the organic-inorganic random copolymers was also found to occur in the mixtures with the precursors of epoxy. The nanostructures were further fixed via subsequent curing reaction and thus the organic-inorganic nanocomposites were obtained. The formation of nanophases in epoxy thermosets was confirmed by transmission electron microscopy (TEM) and dynamic mechanical thermal analysis (DMTA). The organic-inorganic nanocomposites displayed the enhanced surface hydrophobicity as evidenced by surface contact angle measurements.

Poly[(ethylene oxide)-co-(methylene ethylene oxide)]: A hydrolytically-degradable poly(ethylene oxide) platform.

PubMed

Lundberg, Pontus; Lee, Bongjae F; van den Berg, Sebastiaan A; Pressly, Eric D; Lee, Annabelle; Hawker, Craig J; Lynd, Nathaniel A

2012-11-20

A facile method for imparting hydrolytic degradability to poly(ethylene oxide) (PEO), compatible with current PEGylation strategies, is presented. By incorporating methylene ethylene oxide (MEO) units into the parent PEO backbone, complete degradation was defined by the molar incorporation of MEO, and the structure of the degradation byproducts was consistent with an acid-catalyzed vinyl-ether hydrolysis mechanism. The hydrolytic degradation of poly[(ethylene oxide)-co-(methylene ethylene oxide)] was pH-sensitive, with degradation at pH 5 being significantly faster than at pH 7.4 at 37 °C in PBS buffer while long-term stability could be obtained in either the solid-state or at pH 7.4 at 6 °C.

Controlling the Formation of Ionic-Liquid-based Aqueous Biphasic Systems by Changing the Hydrogen-Bonding Ability of Polyethylene Glycol End Groups.

PubMed

Pereira, Jorge F B; Kurnia, Kiki A; Freire, Mara G; Coutinho, João A P; Rogers, Robin D

2015-07-20

The formation of aqueous biphasic systems (ABS) when mixing aqueous solutions of polyethylene glycol (PEG) and an ionic liquid (IL) can be controlled by modifying the hydrogen-bond-donating/-accepting ability of the polymer end groups. It is shown that the miscibility/immiscibility in these systems stems from both the solvation of the ether groups in the oxygen chain and the ability of the PEG terminal groups to preferably hydrogen bond with water or the anion of the salt. The removal of even one hydrogen bond in PEG can noticeably affect the phase behavior, especially in the region of the phase diagram in which all the ethylene oxide (EO) units of the polymeric chain are completely solvated. In this region, removing or weakening the hydrogen-bond-donating ability of PEG results in greater immiscibility, and thus, in a higher ability to form ABS, as a result of the much weaker interactions between the IL anion and the PEG end groups. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Radiation induced deposition of copper nanoparticles inside the nanochannels of poly(acrylic acid)-grafted poly(ethylene terephthalate) track-etched membranes

NASA Astrophysics Data System (ADS)

Korolkov, Ilya V.; Güven, Olgun; Mashentseva, Anastassiya A.; Atıcı, Ayse Bakar; Gorin, Yevgeniy G.; Zdorovets, Maxim V.; Taltenov, Abzal A.

2017-01-01

Poly(ethylene terephthalate) PET, track-etched membranes (TeMs) with 400 nm average pore size were UV-grafted with poly(acrylic acid) (PAA) after oxidation of inner surfaces by H2O2/UV system. Carboxylate groups of grafted PAA chains were easily complexed with Cu2+ ions in aqueous solutions. These ions were converted into metallic copper nanoparticles (NPs) by radiation-induced reduction of copper ions in aqueous-alcohol solution by gamma rays in the dose range of 46-250 kGy. Copper ions chelating with -COOH groups of PAA chains grafted on PET TeMs form polymer-metal ion complex that prevent the formation of agglomerates during reduction of copper ions to metallic nanoparticles. The detailed analysis by X-Ray diffraction technique (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX) confirmed the deposition of copper nanoparticles with the average size of 70 nm on the inner surface of nanochannels of PET TeMs. Samples were also investigated by FTIR, ESR spectroscopies to follow copper ion reduction.

Solubilization of docetaxel in poly(ethylene oxide)-block-poly(butylene/styrene oxide) micelles.

PubMed

Elsabahy, Mahmoud; Perron, Marie-Eve; Bertrand, Nicolas; Yu, Ga-Er; Leroux, Jean-Christophe

2007-07-01

Poly(ethylene oxide)-block-poly(styrene oxide) (PEO-b-PSO) and PEO-b-poly(butylene oxide) (PEO-b-PBO) of different chain lengths were synthesized and characterized for their self-assembling properties in water by dynamic/static light scattering, spectrofluorimetry, and transmission electron microscopy. The resulting polymeric micelles were evaluated for their ability to solubilize and protect the anticancer drug docetaxel (DCTX) from degradation. The drug release kinetics as well as the cytotoxicity of the loaded micelles were assessed in vitro. All polymers formed micelles with a highly viscous core at low critical association concentrations (<10 mg/L). Micelle morphology depended on the nature of the hydrophobic block, with PBO- and PSO-based micelles yielding monodisperse spherical and cylindrical nanosized aggregates, respectively. The maximum solubilization capacity for DCTX ranged from 0.7 to 4.2% and was the highest for PSO micelles exhibiting the longest hydrophobic segment. Despite their high affinity for DCTX, PEO-b-PSO micelles were not able to efficiently protect DCTX against hydrolysis under accelerated stability testing conditions. Only PEO-b-PBO bearing 24 BO units afforded significant protection against degradation. In vitro, DCTX was released slower from the latter micelles, but all formulations possessed a similar cytotoxic effect against PC-3 prostate cancer cells. These data suggest that PEO-b-P(SO/BO) micelles could be used as alternatives to conventional surfactants for the solubilization of taxanes.

Microscopic Chain Motion in Polymer Nanocomposites with Dynamically Asymmetric Interphases

PubMed Central

Senses, Erkan; Faraone, Antonio; Akcora, Pinar

2016-01-01

Dynamics of the interphase region between matrix and bound polymers on nanoparticles is important to understand the macroscopic rheological properties of nanocomposites. Here, we present neutron scattering investigations on nanocomposites with dynamically asymmetric interphases formed by a high-glass transition temperature polymer, poly(methyl methacrylate), adsorbed on nanoparticles and a low-glass transition temperature miscible matrix, poly(ethylene oxide). By taking advantage of selective isotope labeling of the chains, we studied the role of interfacial polymer on segmental and collective dynamics of the matrix chains from subnanoseconds to 100 nanoseconds. Our results show that the Rouse relaxation remains unchanged in a weakly attractive composite system while the dynamics significantly slows down in a strongly attractive composite. More importantly, the chains disentangle with a remarkable increase of the reptation tube size when the bound polymer is vitreous. The glassy and rubbery states of the bound polymer as temperature changes underpin the macroscopic stiffening of nanocomposites. PMID:27457056

Rheological characterization of thermal, thermo-oxidative and photo-oxidative degradation of LDPE

NASA Astrophysics Data System (ADS)

Rolón-Garrido, Víctor Hugo; Wagner, Manfred Hermann

2015-04-01

Rheology has been used to study thermal degradation (V. H. Rolón-Garrido et al., Rheol. Acta 50, 519-535, 2011), thermo-oxidative degradation (V. H. Rolón-Garrido et al., Rheol. Acta 50, 519-535, 2011; V. H. Rolón-Garrido et al., J. Rheol. 57, 105-129, 2013) and photo-oxidative degradation (V. H. Rolón-Garrido and M. H. Wagner, Polym. Degrad. Stab. 99, 136-145, 2014; V. H. Rolón-Garrido and M. H. Wagner, J. Rheol. 58, 199-22 2, 2014; V. H. Rolón-Garrido et al., Polym. Degrad. Stab. 111, 46-54, 2015) of low-density polyethylene (LDPE). This contribution presents the analogies and differences between these types of degradations of LDPE on the linear (by use of van-Gurp Palmen plots) and non-linear viscoelastic properties (by use of the parameters of the MSF model, fmax2 and β), as well as on the failure mode of the samples (through the maximum strain and stress achieved experimentally). In contrast to thermal and thermo-oxidative degradation, the linear viscoelastic properties of photo-oxidated samples were more affected by degradation. In the non-linear regime, for thermal and thermo-oxidative treated samples, the elongational measurements elucidated the role of chain scission and long-chain branching (LCB) formation, while for photo-oxidated LDPE even the competition between chain scission, LCB formation, and gel formation was demonstrated. The failure behavior was found to be determined by a constant maximum strain in thermo-oxidative degradation, if the LDPE has high content in branching points, or in photo-oxidative degraded LDPE, if a considerable portion of gel structure is present. Otherwise, either the maximum strain or stress measured was found to be strain-rate dependent.

Dynamical behavior of a single polymer chain under nanometric confinement

NASA Astrophysics Data System (ADS)

Lagrené, K.; Zanotti, J.-M.; Daoud, M.; Farago, B.; Judeinstein, P.

2010-10-01

We address the dynamical behavior of a single polymer chain under nanometric confinement. We consider a polymer melt made of a mixture of hydrogenated and deuterated high molecular mass Poly(Ethylene Oxide) (PEO). The confining material is a membrane of Anodic Aluminum Oxide (AAO), a macroscopically highly ordered confining system made of parallel cylindrical channels. We use Neutron Spin-Echo (NSE) under the Zero Average Contrast (ZAC) condition to, all at once, i) match the intense porous AAO detrimental elastic SANS (Small Angle Neutron Scattering) contribution to the total intermediate scattering function I(Q,t) and ii) measure the Q dependence of the dynamical modes of a single chain under confinement. The polymer dynamics is probed on an extremely broad spacial ([2.2 10-2 Å-1, 0.2 Å-1]) and temporal ([0.1 ns, 600 ns]) ranges. We do not detect any influence of confinement on the polymer dynamics. This result is discussed in the framework of the debate on the existence of a "corset effect" recently suggested by NMR relaxometry data.

Highly CO2-Selective Gas Separation Membranes Based on Segmented Copolymers of Poly(Ethylene oxide) Reinforced with Pentiptycene-Containing Polyimide Hard Segments.

PubMed

Luo, Shuangjiang; Stevens, Kevin A; Park, Jae Sung; Moon, Joshua D; Liu, Qiang; Freeman, Benny D; Guo, Ruilan

2016-01-27

Poly(ethylene oxide) (PEO)-containing polymer membranes are attractive for CO2-related gas separations due to their high selectivity toward CO2. However, the development of PEO-rich membranes is frequently challenged by weak mechanical properties and a high crystallization tendency of PEO that hinders gas transport. Here we report a new series of highly CO2-selective, amorphous PEO-containing segmented copolymers prepared from commercial Jeffamine polyetheramines and pentiptycene-based polyimide. The copolymers are much more mechanically robust than the nonpentiptycene containing counterparts due to the molecular reinforcement mechanism of supramolecular chain threading and interlocking interactions induced by the pentiptycene structures, which also effectively suppresses PEO crystallization leading to a completely amorphous structure even at 60% PEO weight content. Membrane transport properties are sensitively affected by both PEO weight content and PEO chain length. A nonlinear correlation between CO2 permeability with PEO weight content was observed due to the competition between solubility and diffusivity contributions, whereby the copolymers change from being size-selective to solubility-selective when PEO content reaches 40%. CO2 selectivities over H2 and N2 increase monotonically with both PEO content and chain length, indicating strong CO2-philicity of the copolymers. The copolymer film with the longest PEO sequence (PEO2000) and highest PEO weight content (60%) showed a measured CO2 pure gas permeability of 39 Barrer, and ideal CO2/H2 and CO2/N2 selectivities of 4.1 and 46, respectively, at 35 °C and 3 atm, making them attractive for hydrogen purification and carbon capture.

In vivo oxidation in remelted highly cross-linked retrievals.

PubMed

Currier, B H; Van Citters, D W; Currier, J H; Collier, J P

2010-10-20

Elimination of free radicals to prevent oxidation has played a major role in the development and product differentiation of the latest generation of highly cross-linked ultra-high molecular weight polyethylene bearing materials. In the current study, we (1) examined oxidation in a series of retrieved remelted highly cross-linked ultra-high molecular weight polyethylene bearings from a number of device manufacturers and (2) compared the retrieval results with findings for shelf-stored control specimens. The hypothesis was that radiation-cross-linked remelted ultra-high molecular weight polyethylene would maintain oxidative stability in vivo comparable with the stability during shelf storage and in published laboratory aging tests. Fifty remelted highly cross-linked ultra-high molecular weight polyethylene acetabular liners and nineteen remelted highly cross-linked ultra-high molecular weight polyethylene tibial inserts were received after retrieval from twenty-one surgeons from across the U.S. Thirty-two of the retrievals had been in vivo for two years or more. Each was measured for oxidation with use of Fourier transform infrared spectroscopy. A control series of remelted highly cross-linked ultra-high molecular weight polyethylene acetabular liners from three manufacturers was analyzed with electron paramagnetic resonance spectroscopy to measure free radical content and with Fourier transform infrared spectroscopy to measure oxidation initially and after eight to nine years of shelf storage in air. The never-implanted, shelf-aged controls had no measurable free-radical content initially or after eight to nine years of shelf storage. The never-implanted controls showed no increase in oxidation during shelf storage. Oxidation measurements showed measurable oxidation in 22% of the retrieved remelted highly cross-linked liners and inserts after an average of two years in vivo. Because never-implanted remelted highly cross-linked ultra-high molecular weight polyethylene materials had no measurable free-radical concentration and no increase in oxidation during shelf storage, these materials were expected to be oxidation-resistant in vivo. However, some remelted highly cross-linked ultra-high molecular weight polyethylene retrievals showed measurable oxidation after an average of more than two years in vivo. This apparent departure from widely expected behavior requires continued study of the process of in vivo oxidation of ultra-high molecular weight polyethylene materials.

Effects of Congo red on the drag reduction properties of poly(ethylene oxide) in aqueous solution based on drop impact images.

PubMed

Alkschbirs, Melissa I; Bizotto, Vanessa C; de Oliveira, Marcelo G; Sabadini, Edvaldo

2004-12-21

The presence of very small amounts (ppm) of high-MW polymers in solution produces high levels of drag reduction in a turbulent flow. This phenomenon, often termed as the Toms effect, is highly dependent not only on MW, but also on the flexibility of the macromolecular chain. The Toms effect can be studied through the images of the structures produced after the drop impact against shallow solution surfaces. The splash structures composed of crown, cavity, and Rayleigh jet are highly dependent on the elongational properties of the solution. This work presents the effects of Congo red on the drag reduction properties of poly(ethylene oxide) in aqueous solutions through the analysis of splash structures. Results obtained in this analysis indicate that Congo red molecules act as physical cross-linking agents, decreasing the polymer elasticity and its drag reduction capacity. It was observed that the maximum height of the Rayleigh jet can be used as a sensitive parameter to the complexation between the dye and the polymer molecules.

Study of the dynamics of poly(ethylene oxide) by combining molecular dynamic simulations and neutron scattering experiments

NASA Astrophysics Data System (ADS)

Brodeck, M.; Alvarez, F.; Arbe, A.; Juranyi, F.; Unruh, T.; Holderer, O.; Colmenero, J.; Richter, D.

2009-03-01

We performed quasielastic neutron scattering experiments and atomistic molecular dynamics simulations on a poly(ethylene oxide) (PEO) homopolymer system above the melting point. The excellent agreement found between both sets of data, together with a successful comparison with literature diffraction results, validates the condensed-phase optimized molecular potentials for atomistic simulation studies (COMPASS) force field used to produce our dynamic runs and gives support to their further analysis. This provided direct information on magnitudes which are not accessible from experiments such as the radial probability distribution functions of specific atoms at different times and their moments. The results of our simulations on the H-motions and different experiments indicate that in the high-temperature range investigated the dynamics is Rouse-like for Q-values below ≈0.6 Å-1. We then addressed the single chain dynamic structure factor with the simulations. A mode analysis, not possible directly experimentally, reveals the limits of applicability of the Rouse model to PEO. We discuss the possible origins for the observed deviations.

Study of the dynamics of poly(ethylene oxide) by combining molecular dynamic simulations and neutron scattering experiments.

PubMed

Brodeck, M; Alvarez, F; Arbe, A; Juranyi, F; Unruh, T; Holderer, O; Colmenero, J; Richter, D

2009-03-07

We performed quasielastic neutron scattering experiments and atomistic molecular dynamics simulations on a poly(ethylene oxide) (PEO) homopolymer system above the melting point. The excellent agreement found between both sets of data, together with a successful comparison with literature diffraction results, validates the condensed-phase optimized molecular potentials for atomistic simulation studies (COMPASS) force field used to produce our dynamic runs and gives support to their further analysis. This provided direct information on magnitudes which are not accessible from experiments such as the radial probability distribution functions of specific atoms at different times and their moments. The results of our simulations on the H-motions and different experiments indicate that in the high-temperature range investigated the dynamics is Rouse-like for Q-values below approximately 0.6 A(-1). We then addressed the single chain dynamic structure factor with the simulations. A mode analysis, not possible directly experimentally, reveals the limits of applicability of the Rouse model to PEO. We discuss the possible origins for the observed deviations.

pH responsiveness of dendrimer-like poly(ethylene oxide)s.

PubMed

Feng, Xiaoshuang; Taton, Daniel; Borsali, Redouane; Chaikof, Elliot L; Gnanou, Yves

2006-09-06

Poly(ethylene oxide) (PEO) and poly(acrylic acid) (PAA), two polymers known to form pH-sensitive aggregates through noncovalent interactions, were assembled in purposely designed architecture -a dendrimer-like PEO scaffold carrying short inner PAA chains-to produce unimolecular systems that exhibit pH responsiveness. Because of the particular placement of the PAA chains within the dendrimer-like structure, intermolecular complexation between acrylic acid (AA) and ethylene oxide (EO) units-and thus macroscopic aggregation or even mesoscopic micellization-could be avoided in favor of the sole intramolecular complexation. The sensitivity of such interactions to pH was exploited to generate dendrimer-like PEOs that reversibly shrink and expand with the pH. Such PAA-carrying dendrimer-like PEOs were synthesized in two main steps. First, a fifth-generation dendrimer-like PEO was obtained by combining anionic ring-opening polymerization (AROP) of ethylene oxide from a tris-hydroxylated core and selective branching reactions of PEO chain ends. To this end, an AB(2)C-type branching agent was designed: the latter includes a chloromethyl (A) group for its covalent attachment to the arm ends, two geminal hydroxyls (B(2)) protected in the form of a ketal ring for the growth of subsequent PEO generations by AROP, and a vinylic (C) double bonds for further functionalization of the interior of dendrimer-like PEOs. Reiteration of AROP and derivatization of PEO branches allowed us to prepare a dendrimer-like PEO of fourth generation with a total molar mass of 52,000 g x mol(-1), containing 24 external hydroxyl functions and 21 inner vinylic groups in the interior. A fifth generation of PEO chains was generated from this parent dendrimer-like PEO of fourth generation using a "conventional" AB(2)-type branching agent, and 48 PEO branches could be grown by AROP. The 48 outer hydroxy-end groups of the fifth-generation dendrimer-like PEO obtained were subsequently quantitatively converted into inert benzylic groups using benzyl bromide. The 21 internal vinylic groups carried by the PEO scaffold were then chemically modified in a two-step sequence into bromoester groups. The latter which are atom transfer radical polymerization (ATRP) initiating sites thus served to grow poly(tert-butylacrylate) chains. After a final step of hydrolysis of the tert-butyl ester groups, double, hydrophilic, dendrimer-like PEOs comprising 21 internal junction-attached poly(acrylic acid) (PAA) blocks could be obtained. Dynamic light scattering was used to determine the size of these dendrimer-like species in water and to investigate their response to pH variation: in particular, how the pH-sensitive complexation of EO and AA units affects their overall behavior.

Mesoscopic simulation of a micellar poly(N-isopropyl acrylamide)-b-(polyethylene oxide) copolymer system

NASA Astrophysics Data System (ADS)

Bautista-Reyes, Rubén; Soto-Figueroa, César; Vicente, Luis

2016-05-01

In this article we studied the micellar formation of poly(N-isopropyl acrylamide)-b-polyethylene oxide (PNIPAM-b-PEO) copolymers in an aqueous system. From molecular simulations the dependence on temperature of the Flory-Huggins interaction parameter χ for PNIPAM and PEO in water is obtained and compared with available experimental results and values from other theoretical calculations. By means of dissipative particle dynamics (DPD) we then simulated the coil-globule transition for PNIPAM chains in water with a transition temperature of around 305 K. The simulations for PNIPAM-b-PEO copolymers showed that at room temperature the chains are miscible in an aqueous phase but with a temperature increase the system turns into micelles at T  =  305 K. The change in micelle anisotropy due to a different ratio PNIPAM/PEO of chains is also analyzed. What is observed is that for large PEO the large number of dissolved PEO chains gives a large corona size and the micelle is not spherical but obloide and as the number of PNIPAM is increased the micelle acquires a spherical shape. As an important application we considered the system micelle-water/anionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate [BMIM]+[PF6]-). By increasing the temperature of the system from 306 K it is shown that at T  =  345 K there is a transfer of the micelle from water to the ionic liquid phase and this was due to the change in the relative affinity of PEO to water and ionic liquid expressed by the change in χ. All the simulation outcomes are qualitatively consistent with experimental results and thus to our knowledge we give the first set of χ values for the interaction between PNIPAM and water in a wide range of temperature values.

Synthetic polymers and biomembranes. How do they interact? Atomistic molecular dynamics simulation study of PEO in contact with a DMPC lipid bilayer.

PubMed

Pal, Sandeep; Milano, Giuseppe; Roccatano, Danilo

2006-12-28

The understanding of interactions of poly(ethylene glycol) (PEG) or poly(ethylene oxide) (PEO) with biological interfaces has important technological application in industry and in medicine. In this paper, structural and dynamical properties of PEO at the dimyristoylphospatidylcholine (DMPC) bilayer/water interface have been investigated by molecular dynamics (MD) and steered molecular dynamics (SMD) simulations. The structural properties of a PEO chain in bulk water, at the water/vacuum interface, and in the presence of the membrane were compared with available experimental data. The presence of a barrier for the PEO penetration into the DMPC bilayer has been found. A qualitative estimation of the barrier provided a value equal to approximately 19 kJ/mol, that is, 7 times the value of kT at 310 K.

Multidentate oligomeric ligands to enhance the biocompatibility of iron oxide and other metal nanoparticles

NASA Astrophysics Data System (ADS)

Wang, Wentao; Palui, Goutam; Ji, Xin; Aldeek, Fadi; Mattoussi, Hedi

2014-03-01

We prepared a set of multi-coordinating and reactive amphiphilic polymer ligands and used them for surface-functionalizing magnetic iron oxide nanoparticles. The amphiphilic oligomers were prepared by coupling (via one step nucleophilic addition) several dopamine anchoring groups, polyethylene glycol moieties and reactive groups onto a poly(isobutylene-alt-maleic anhydride) chain. The availability of several anchoring groups in the same ligand greatly enhances the ligand affinity to the nanoparticle surfaces, via multiplecoordination, while the hydrophilic and reactive groups promote colloidal stability in buffer media and allow subsequent conjugation to target biomolecules. The hydrophilic nanoparticles capped with these polymers maintain compact size and exhibit great long term colloidal stability.

High-resolution Kendrick Mass Defect Analysis of Poly(ethylene oxide)-based Non-ionic Surfactants and Their Degradation Products.

PubMed

Fouquet, Thierry; Shimada, Haruo; Maeno, Katsuyuki; Ito, Kanako; Ozeki, Yuka; Kitagawa, Shinya; Ohtani, Hajime; Sato, Hiroaki

2017-09-01

Matrix assisted laser desorption ionization (MALDI) high-resolution mass spectrometry (HRMS) and the recently introduced high-resolution Kendrick mass defect (HRKMD) analysis are combined to thoroughly characterize non-ionic surfactants made of a poly(ethylene oxide) (PEO) core capped by esters of fatty acids. A PEO monostearate surfactant is first analyzed as a proof of principle of the HRKMD analysis conducted with a fraction of EO as the base unit (EO/X with X being an integer) in lieu of EO for a regular KMD analysis. Data visualization is greatly enhanced and the distributions detected in the MALDI mass spectrum are assigned to a pristine (H, OH)-PEO as well as mono- and di-esterified PEO chains with palmitate and stearate end-groups in HRKMD plots computed with EO/45. The MALDI-HRMS/HRKMD analysis is then successfully applied to the more complex case of ethoxylated hydrogenated castor oil (EHCO) found to contain a large number of hydrogenated ricinoleate moieties (up to 14) in its HRKMD plot computed with EO/43, departing from the expected triglyceride structure. The exhaustiveness of the MALDI-HRMS/HRKMD strategy is validated by comparing the so-obtained fingerprints with results from alternative techniques (electrospray ionization MS, size exclusion and liquid adsorption chromatography, ion mobility spectrometry). Finally, aged non-ionic surfactants formed upon hydrolytic degradation are analyzed by MALDI-HRMS/HRKMD to easily assign the degradation products and infer the associated degradation routes. In addition to the hydrolysis of the ester groups observed for EHCO, chain scissions and new polar end-groups are observed in the HRKMD plot of PEO monostearate arising from a competitive oxidative ageing.

Effects of nanoparticles on the compatibility of PEO-PMMA block copolymers.

PubMed

Mu, Dan; Li, Jian-Quan; Li, Wei-Dong; Wang, Song

2011-12-01

The compatibility of six kinds of designed poly(ethylene oxide)-block-poly(methyl methacrylate) (PEO-b-PMMA) copolymers was studied at 270, 298 and 400 K via mesoscopic modeling. The values of the order parameters depended on both the structures of the block copolymers and the simulation temperature, while the values of the order parameters of the long chains were higher than those of the short ones; temperature had a more obvious effect on long chains than on the short ones. Plain copolymers doped with poly(ethylene oxide) (PEO) or poly(methyl methacrylate) (PMMA) homopolymer showed different order parameter values. When a triblock copolymer had the same component at both ends and was doped with one of its component polymers as a homopolymer (such as A5B6A5 doped with B6 or A5 homopolymer), the value of its order parameter depended on the simulation temperature. The highest order parameter values were observed for A5B6A5 doped with B6 at 400 K and for A5B6A5 doped with A5 at 270 K. A study of copolymers doped with nanoparticles showed that the mesoscopic phase was influenced by not only the properties of the nanoparticles, such as the size and density, but also the compositions of the copolymers. Increasing the size of the nanoparticles used as a dopant had the most significant effect on the phase morphologies of the copolymers.

Molecular dynamics simulation of polymer electrolytes based on poly(ethylene oxide) and ionic liquids. II. Dynamical properties.

PubMed

Costa, Luciano T; Ribeiro, Mauro C C

2007-10-28

Dynamical properties of polymer electrolytes based on poly(ethylene oxide) (PEO) and ionic liquids of 1-alkyl-3-methylimidazolium cations were calculated by molecular dynamics simulations with previously proposed models [L. T. Costa and M. C. Ribeiro, J. Chem. Phys. 124, 184902 (2006)]. The effect of changing the ionic liquid concentration, temperature, and the 1-alkyl-chain lengths, [1,3-dimethylimidazolium]PF(6) and [1-butyl-3-methylimidazolium]PF(6) ([dmim]PF(6) and [bmim]PF(6)), was investigated. Cation diffusion coefficient is higher than those of anion and oxygen atoms of PEO chains. Ionic mobility in PEO[bmim]PF(6) is higher than in PEO[dmim]PF(6), so that the ionic conductivity kappa of the former is approximately ten times larger than the latter. The ratio between kappa and its estimate from the Nernst-Einstein equation kappa/kappa(NE), which is inversely proportional to the strength of ion pairs, is higher in ionic liquid polymer electrolytes than in polymer electrolytes based on inorganic salts with Li(+) cations. Calculated time correlation functions corroborate previous evidence from the analysis of equilibrium structure that the ion pairs in ionic liquid polymer electrolytes are relatively weak. Structural relaxation at distinct spatial scales is revealed by the calculation of the intermediate scattering function at different wavevectors. These data are reproduced with stretched exponential functions, so that temperature and wavevector dependences of best fit parameters can be compared with corresponding results for polymer electrolytes containing simpler ions.

Li+ transport in poly(ethylene oxide) based electrolytes: neutron scattering, dielectric spectroscopy, and molecular dynamics simulations.

PubMed

Do, Changwoo; Lunkenheimer, Peter; Diddens, Diddo; Götz, Marion; Weiss, Matthias; Loidl, Alois; Sun, Xiao-Guang; Allgaier, Jürgen; Ohl, Michael

2013-07-05

The dynamics of Li(+) transport in polyethylene oxide (PEO) and lithium bis(trifluoromethanesulfonyl)imde mixtures are investigated by combining neutron spin-echo (NSE) and dielectric spectroscopy with molecular dynamics (MD) simulations. The results are summarized in a relaxation time map covering wide ranges of temperature and time. The temperature dependence of the dc conductivity and the dielectric α relaxation time is found to be identical, indicating a strong coupling between both. The relaxation times obtained from the NSE measurements at 0.05 Å(-1)

Li+ Transport in Poly(Ethylene Oxide) Based Electrolytes: Neutron Scattering, Dielectric Spectroscopy, and Molecular Dynamics Simulations

NASA Astrophysics Data System (ADS)

Do, Changwoo; Lunkenheimer, Peter; Diddens, Diddo; Götz, Marion; Weiß, Matthias; Loidl, Alois; Sun, Xiao-Guang; Allgaier, Jürgen; Ohl, Michael

2013-07-01

The dynamics of Li+ transport in polyethylene oxide (PEO) and lithium bis(trifluoromethanesulfonyl)imde mixtures are investigated by combining neutron spin-echo (NSE) and dielectric spectroscopy with molecular dynamics (MD) simulations. The results are summarized in a relaxation time map covering wide ranges of temperature and time. The temperature dependence of the dc conductivity and the dielectric α relaxation time is found to be identical, indicating a strong coupling between both. The relaxation times obtained from the NSE measurements at 0.05Å-1

Degradation of ethylene glycol and polyethylene glycols by methanogenic consortia.

PubMed Central

Dwyer, D F; Tiedje, J M

1983-01-01

Methanogenic enrichments capable of degrading polyethylene glycol and ethylene glycol were obtained from sewage sludge. Ethanol, acetate, methane, and (in the case of polyethylene glycols) ethylene glycol were detected as products. The sequence of product formation suggested that the ethylene oxide unit [HO-(CH2-CH2-O-)xH] was dismutated to acetate and ethanol; ethanol was subsequently oxidized to acetate by a syntrophic association that produced methane. The rates of degradation for ethylene, diethylene, and polyethylene glycol with molecular weights of 400, 1,000, and 20,000, respectively, were inversely related to the number of ethylene oxide monomers per molecule and ranged from 0.84 to 0.13 mM ethylene oxide units degraded per h. The enrichments were shown to best metabolize glycols close to the molecular weight of the substrate on which they were enriched. The anaerobic degradation of polyethylene glycol (molecular weight, 20,000) may be important in the light of the general resistance of polyethylene glycols to aerobic degradation. PMID:6614903

No difference in in vivo polyethylene wear particles between oxidized zirconium and cobalt-chromium femoral component in total knee arthroplasty.

PubMed

Minoda, Yukihide; Hata, Kanako; Iwaki, Hiroyoshi; Ikebuchi, Mitsuhiko; Hashimoto, Yusuke; Inori, Fumiaki; Nakamura, Hiroaki

2014-03-01

Polyethylene wear particle generation is one of the most important factors affecting mid- to long-term results of total knee arthroplasties. Oxidized zirconium was introduced as a material for femoral components to reduce polyethylene wear generation. However, an in vivo advantage of oxidized zirconium on polyethylene wear particle generation is still controversial. The purpose of this study was to compare in vivo polyethylene wear particles between oxidized zirconium total knee prosthesis and conventional cobalt-chromium (Co-Cr) total knee prosthesis. Synovial fluid was obtained from the knees of 6 patients with oxidized zirconium total knee prosthesis and from 6 patients with conventional cobalt-chromium (Co-Cr) total knee prosthesis 12 months after the operation. Polyethylene particles were isolated and examined using a scanning electron microscope and image analyser. Total number of particles in each knee was 3.3 ± 1.3 × 10(7) in the case of oxidized zirconium (mean ± SD) and 3.4 ± 1.2 × 10(7) in that of Co-Cr (n.s.). The particle size (equivalent circle diameter) was 0.8 ± 0.3 μm in the case of oxidized zirconium and 0.6 ± 0.1 μm in that of Co-Cr (n.s.). The particle shape (aspect ratio) was 1.4 ± 0.0 in the case of oxidized zirconium and 1.4 ± 0.0 in that of metal Co-Cr (n.s). Although newly introduced oxidized zirconium femoral component did not reduce the in vivo polyethylene wear particles in early clinical stage, there was no adverse effect of newly introduced material. At this moment, there is no need to abandon oxidized zirconium femoral component. However, further follow-up of polyethylene wear particle generation should be performed to confirm the advantage of the oxidized zirconium femoral component. Therapeutic study, Level III.

Formyl-ended heterobifunctional poly(ethylene oxide): synthesis of poly(ethylene oxide) with a formyl group at one end and a hydroxyl group at the other end.

PubMed

Nagasaki, Y; Kutsuna, T; Iijima, M; Kato, M; Kataoka, K; Kitano, S; Kadoma, Y

1995-01-01

Well-defined poly(ethylene oxide) (PEO) with a formyl group at one end and a hydroxyl group at the other terminus was synthesized by the anionic ring opening polymerization of ethylene oxide (EO) with a new organometallic initiator possessing an acetal moiety, potassium 3,3-diethoxypropyl alkoxide. Hydrolysis of the acetal moiety produced a formyl group-terminated heterobifunctional PEO with a hydroxyl group at the other end.

Photografting of perfluoroalkanes onto polyethylene surfaces via azide/nitrene chemistry

NASA Astrophysics Data System (ADS)

Siegmann, Konstantin; Inauen, Jan; Villamaina, Diego; Winkler, Martin

2017-02-01

The purpose of this study is to render polyethylene surfaces strongly and permanently hydrophobic. Polyethylene is a common plastic and, because of its inertness, difficult to graft. We chose polyethylene as example because of its ubiquity and model character. As graft chains linear perfluoroalkyl residues (-C4F9, -C6F13, -C8F17 and -C10F21) were chosen, and photografting was selected as grafting method. Photolytically generated nitrenes can insert into carbon-hydrogen bonds and are therefore suited for binding to polyethylene. Hydrophobic photo reactive surface modifiers based on azide/nitrene chemistry are designed, synthesized in high yield and characterized. Four new molecules are described. Water contact angles exceeding 110° were achieved on grafted polyethylene. One problem is to demonstrate that the photografted surface modifiers are bound covalently to the polyethylene. Abrasion tests show that all new molecules, when photografted to polyethylene, have a higher abrasion resistance than a polyethylene surface coated with a long-chain perfluoroalkane. Relative abrasion resitances of 1.4, 2.0, 2.1 and 2.5 compared to the fluoroalkane coating were obtained for the four compounds. An abrasion model using ice is developed. Although all four compounds have the same λmax of 266 nm in acetonitrile solution, their molar extincition coefficients increase from 1.6·104 to 2.2·104 with increasing length of the fluorotelomer chain. Exitonic coupling of the chromophores of the surface modifiers is observed for specific molecules in the neat state. A linear correlation of water contact angle with fluorine surface content, as measured by photoelectron spectroscopy, in grafted polyethylene surfaces is established.

Small Particle Driven Chain Disentanglements in Polymer Nanocomposites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Senses, Erkan; Ansar, Siyam M.; Kitchens, Christopher L.

2017-04-01

Using neutron spin-echo spectroscopy, X-ray photon correlation spectroscopy and bulk rheology, we studied the effect of particle size on the single chain dynamics, particle mobility, and bulk viscosity in athermal polyethylene oxide-gold nanoparticle composites. The results reveal an ≈ 25 % increase in the reptation tube diameter with addition of nanoparticles smaller than the entanglement mesh size (≈ 5 nm), at a volume fraction of 20 %. The tube diameter remains unchanged in the composite with larger (20 nm) nanoparticles at the same loading. In both cases, the Rouse dynamics is insensitive to particle size. These results provide a directmore » experimental observation of particle size driven disentanglements that can cause non-Einstein-like viscosity trends often observed in polymer nanocomposites.« less

Molecular dynamics simulations of amphiphilic graft copolymer molecules at a water/air interface.

PubMed

Anderson, Philip M; Wilson, Mark R

2004-11-01

Fully atomistic molecular dynamics simulations of amphiphilic graft copolymer molecules have been performed at a range of surface concentrations at a water/air interface. These simulations are compared to experimental results from a corresponding system over a similar range of surface concentrations. Neutron reflectivity data calculated from the simulation trajectories agrees well with experimentally acquired profiles. In particular, excellent agreement in neutron reflectivity is found for lower surface concentration simulations. A simulation of a poly(ethylene oxide) (PEO) chain in aqueous solution has also been performed. This simulation allows the conformational behavior of the free PEO chain and those tethered to the interface in the previous simulations to be compared. (c) 2004 American Institute of Physics.

Molecular Dynamics in the Crystalline Regions of Poly(ethylene oxide) Containing a Well-Defined Point Defect in the Middle of the Polymer Chain.

PubMed

Golitsyn, Yury; Pulst, Martin; Kressler, Jörg; Reichert, Detlef

2017-05-04

The chain mobility in crystals of a homopolymer of poly(ethylene oxide) (PEO) with 22 monomer units (PEO 22 ) is compared with that of a PEO having the identical number of monomer units but additionally a 1,4-disubstituted 1,2,3-triazole (TR) point defect in the middle of the chain (PEO 11 -TR-PEO 11 ). In crystals of PEO 22 , the characteristic α c -relaxation (helix jumps) is detected and the activation energy of this process is calculated from the pure crystalline 1 H FIDs to 67 kJ/mol. PEO 11 -TR-PEO 11 exhibits a more complex behavior, i.e. a transition into the high temperature phase HTPh is noticed during heating in the temperature range between -5 and 10 °C which is attributed to the incorporation of the TR ring into the crystalline lamellae. The crystal mobility of the low temperature phase LTPh of PEO 11 -TR-PEO 11 is in good agreement with PEO 22 since helical jump motions could also be detected by analysis of the 1 H FIDs and the corresponding values of their second moments M 2 . In contrast, the high temperature phase of PEO 11 -TR-PEO 11 shows a completely different behavior of the crystal mobility. The crystalline PEO chains are rigid in this HTPh on the time scale of both, the 1 H time-domain technique and in 13 C MAS CODEX NMR spectroscopy, i.e. the α c -mobility of PEO in the HTPh of PEO 11 -TR-PEO 11 is completely suppressed and the PEO 11 chains are converted into a crystal-fixed polymer due to the incorporation of the TR rings into the crystal structure. However, the TR defect of PEO 11 -TR-PEO 11 shows in the HTPh characteristic π-flip motions with an Arrhenius type activation energy of 223 kJ/mol measured by dielectric relaxation spectroscopy. This motion cannot be observed by corresponding 13 C MAS CODEX NMR measurements due to an interfering spin-dynamic effect.

Nanoscale amphiphilic macromolecules with variable lipophilicity and stereochemistry modulate inhibition of oxidized low-density lipoprotein uptake.

PubMed

Poree, Dawanne E; Zablocki, Kyle; Faig, Allison; Moghe, Prabhas V; Uhrich, Kathryn E

2013-08-12

Amphiphilic macromolecules (AMs) based on carbohydrate domains functionalized with poly(ethylene glycol) can inhibit the uptake of oxidized low density lipoprotein (oxLDL) and counteract foam cell formation, a key characteristic of early atherogenesis. To investigate the influence of lipophilicity and stereochemistry on the AMs' physicochemical and biological properties, mucic acid-based AMs bearing four aliphatic chains (2a) and tartaric acid-based AMs bearing two (2b and 2l) and four aliphatic chains (2g and 2k) were synthesized and evaluated. Solution aggregation studies suggested that both the number of hydrophobic arms and the length of the hydrophobic domain impact AM micelle sizes, whereas stereochemistry impacts micelle stability. 2l, the meso analogue of 2b, elicited the highest reported oxLDL uptake inhibition values (89%), highlighting the crucial effect of stereochemistry on biological properties. This study suggests that stereochemistry plays a critical role in modulating oxLDL uptake and must be considered when designing biomaterials for potential cardiovascular therapies.

Microscopic mechanism for the effect of adding salt on electrospinning by molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Wang, Bing-Bing; Wang, Xiao-Dong; Wang, Tian-Hu

2014-09-01

Adding salts into polymer solution has been found to modulate the fiber structure and significantly improve the solution spinnability in electrospinning. However, the mechanisms have not been fully understood. This work adopted molecular dynamics method to investigate the dynamic behavior of poly(ethylene oxide) (PEO)/water droplet with or without dissolved NaCl salt under high-voltage electric field. Our simulation results agreed with the previous experimental reports well. We observed that some daughter droplets detach from the mother droplet due to the ions evaporation and hydration effect, which significantly accelerates the water evaporation and hence improves the solution spinnability. We also observed that some sodium ions are always coordinated with the ether oxygen group in the PEO chain. When these ions are accelerated by the electric field, the PEO chain segments follow the motion of the ions, inevitably stretching the chain and improving the fiber morphology.

Enhanced adherence of mouse fibroblast and vascular cells to plasma modified polyethylene.

PubMed

Reznickova, Alena; Novotna, Zdenka; Kolska, Zdenka; Kasalkova, Nikola Slepickova; Rimpelova, Silvie; Svorcik, Vaclav

2015-01-01

Since the last decade, tissue engineering has shown a sensational promise in providing more viable alternatives to surgical procedures for harvested tissues, implants and prostheses. Biomedical polymers, such as low-density polyethylene (LDPE), high-density polyethylene (HDPE) and ultra-high molecular weight polyethylene (UHMWPE), were activated by Ar plasma discharge. Degradation of polymer chains was examined by determination of the thickness of ablated layer. The amount of an ablated polymer layer was measured by gravimetry. Contact angle, measured by goniometry, was studied as a function of plasma exposure and post-exposure aging times. Chemical structure of modified polymers was characterized by angle resolved X-ray photoelectron spectroscopy. Surface chemistry and polarity of the samples were investigated by electrokinetic analysis. Changes in surface morphology were followed using atomic force microscopy. Cytocompatibility of plasma activated polyethylene foils was studied using two distinct model cell lines; VSMCs (vascular smooth muscle cells) as a model for vascular graft testing and connective tissue cells L929 (mouse fibroblasts) approved for standardized material cytotoxicity testing. Specifically, the cell number, morphology, and metabolic activity of the adhered and proliferated cells on the polyethylene matrices were studied in vitro. It was found that the plasma treatment caused ablation of the polymers, resulting in dramatic changes in their surface morphology and roughness. ARXPS and electrokinetic measurements revealed oxidation of the polymer surface. It was found that plasma activation has a positive effect on the adhesion and proliferation of VSMCs and L929 cells. Copyright © 2015 Elsevier B.V. All rights reserved.

Preparative crystallization of a single chain antibody using an aqueous two-phase system.

PubMed

Huettmann, Hauke; Berkemeyer, Matthias; Buchinger, Wolfgang; Jungbauer, Alois

2014-11-01

A simultaneous crystallization and aqueous two-phase extraction of a single chain antibody was developed, demonstrating process integration. The process conditions were designed to form an aqueous two-phase system, and to favor crystallization, using sodium sulfate and PEG-2000. At sufficiently high concentrations of PEG, a second phase was generated in which the protein crystallization occurred simultaneously. The single chain antibody crystals were partitioned to the top, polyethylene glycol-rich phase. The crystal nucleation took place in the sodium sulfate-rich phase and at the phase boundary, whereas crystal growth was progressing mainly in the polyethylene glycol-rich phase. The crystals in the polyethylene glycol-rich phase grew to a size of >50 µm. Additionally, polyethylene glycol acted as an anti-solvent, thus, it influenced the crystallization yield. A phase diagram with an undersaturation zone, crystallization area, and amorphous precipitation zone was established. Only small differences in polyethylene glycol concentration caused significant shifts of the crystallization yield. An increase of the polyethylene glycol content from 2% (w/v) to 4% (w/v) increased the yield from approximately 63-87%, respectively. Our results show that crystallization in aqueous two-phase systems is an opportunity to foster process integration. © 2014 Wiley Periodicals, Inc.

New iron catalyst for preparation of polymethylene from synthesis gas

DOEpatents

Sapienza, R.S.; Slegeir, W.A.

1988-03-31

This invention relates to a process for synthesizing hydrocarbons; more particularly, the invention relates to a process for synthesizing long-chain hydrocarbons known as polymethylene from carbon monoxide and hydrogen or from carbon monoxide and water or mixtures thereof in the presence of a catalyst comprising iron and platinum or palladium or mixtures thereof which may be supported on a solid material, preferably an inorganic refractory oxide. This process may be used to convert a carbon monoxide containing gas to a product which could substitute for high density polyethylene.

Iron catalyst for preparation of polymethylene from synthesis gas

DOEpatents

Sapienza, Richard S.; Slegeir, William A.

1990-01-01

This invention relates to a process for synthesizing hydrocarbons; more particularly, the invention relates to a process for synthesizing long-chain hydrocarbons known as polymethylene from carbon monoxide and hydrogen or from carbon monoxide and water or mixtures thereof in the presence of a catalyst comprising iron and platinum or palladium or mixtures thereof which may be supported on a solid material, preferably an inorganic refractory oxide. This process may be used to convert a cabon monoxide containing gas to a product which could substitute for high density polyethylene.

Exploring the Molecular Origins of Bio(in)compatibility: Adhesion Between Proteins and Individual Chains of Poly(ethylene oxide)

NASA Astrophysics Data System (ADS)

Rixman, Monica A.; Ortiz, Christine

2002-03-01

A critical determinant of the biocompatibility of implanted blood-contacting devices is the initial noncovalent adsorption of blood plasma proteins onto the biomaterial surface. Using high-resolution force spectroscopy, we have measured the complex intermolecular interaction forces between individual end-grafted PEO chains and a probe tip covalently bound with human serum albumin, the most abundant blood plasma protein in the human body. On approach, a long-range, nonlinear repulsive force is observed. Upon retraction, however, adhesion between the HSA probe tip and PEO chain occurs, which in many cases is strong enough to allow long-range adhesion and stretching of the individual PEO chains. The known PEO strain-induced conformational transition from the helical (ttg) to the planar (ttt) conformation is clearly observed and seen to shift to lower force values. Statistical analysis of adhesion data, comparison to a variety of control experiments, and theoretical modeling enable us to interpret these experimental results in terms of electrostatic interactions, hydrogen bonding, and steric forces.

The alterations in high density polyethylene properties with gamma irradiation

NASA Astrophysics Data System (ADS)

Zaki, M. F.; Elshaer, Y. H.; Taha, Doaa. H.

2017-10-01

In the present investigation, high density polyethylene (HDPE) polymer has been used to study the alterations in its properties under gamma-irradiation. Physico-chemical properties have been investigated with different spectroscopy techniques, Fourier Transform Infrared spectroscopy (FTIR), X-ray diffraction (XRD), biocompatibility properties, as well as, mechanical properties change. The FT-IR analysis shows the formation of new band at 1716 cm-1 that is attributed to the oxidation of irradiated polymer chains, which is due to the formation of carbonyl groups (C˭O). XRD patterns show that a decrease in the crystallite size and increase in the Full Width at Half Maximum (FWHM). This means that the crystallinity of irradiated samples is decreased with increase in gamma dose. The contact angle measurements show an increase in the surface free energy as the gamma irradiation increases. The measurements of mechanical properties of irradiated HDPE samples were discussed.

Solution rheology of polyelectrolytes and polyelectrolyte-surfactant systems

NASA Astrophysics Data System (ADS)

Plucktaveesak, Nopparat

The fundamental understanding of polyelectrolytes in aqueous solutions is an important branch of polymer research. In this work, the rheological properties of polyelectrolytes and polyelectrolyte/surfactant systems are studied. Various synthetic poly electrolytes are chosen with varied hydrophobicity. We discuss the effects of adding various surfactants to aqueous solutions of poly(ethylene oxide)-b-poly(propylene oxide)- b-polyethylene oxide)-g-poly(acrylic acid) (PEO-PPO-PAA) in the first chapter. Thermogelation in aqueous solutions of PEO-PPO-PAA is due to micellization caused by aggregation of poly(propylene oxide) (PPO) blocks resulting from temperature-induced dehydration of PPO. When nonionic surfactants with hydrophilic-lipophilic balance (HLB) parameter exceeding 11 or Cn alkylsulfates; n-octyl (C8), n-decyl (C 10) and n-dodecyl (C12) sulfates are added, the gelation threshold temperature (Tgel) of 1.0wt% PEO-PPO-PAA in aqueous solutions increases. In contrast, when nonionic surfactants with HLB below 11 are added, the gelation temperature decreases. On the other hand, alkylsulfates with n = 16 or 18 and poly(ethylene oxide) (PEO) do not affect the Tgel. The results imply that both hydrophobicity and tail length of the added surfactant play important roles in the interaction of PEO-PPO-PAA micelles and the surfactant. In the second chapter, the solution behavior of alternating copolymers of maleic acid and hydrophobic monomer is studied. The alternating structure of monomers with two-carboxylic groups and hydrophobic monomers make these copolymers unique. Under appropriate conditions, these carboxylic groups dissociate leaving charges on the chain. The potentiometric titrations of copolymer solutions with added CaCl2 reveal two distinct dissociation processes corresponding to the dissociation of the two adjacent carboxylic acids. The viscosity data as a function of polymer concentration of poly(isobutylene-alt-sodium maleate), poly(styrene-alt-sodium maleate) and poly(diisobutylene- alt-sodium maleate) show the polyelectrolyte behavior as predicted. However, the viscosity as a function of concentration of sodium maleate based copolymers with 1-alkenes; 1-octene (C8), 1-decene (C10), 1-dodecene (C12) and 1-hexene (C14) exhibit an abnormal scaling power, which might be caused by aggregation of the alkene tails to form micelles. In the last chapter, we report the rheological properties of aqueous solutions of poly(acrylic acid) and oppositely charged surfactant, dodecyl trimethylammonium bromide (C12TAB). The solution viscosity decreases as surfactant is added, partly because the polyelectrolyte wraps around the surface of the spherical surfactant micelles, shortening the effective chain length. The effects of polymer molecular weight, polymer concentration, and polymer charge have been studied with no added salt. The results are compared with the predictions of a simple model based on the scaling theory for the viscosity of dilute and unentangled semidilute polyelectrolyte solutions in good solvent. This model takes into account two effects of added surfactant. The effective chain length of the polyelectrolyte is shortened when a significant fraction of the chain wraps around micelles. Another effect is the change of solution ionic strength resulting from surfactant addition that further lowers the viscosity. The parameters used in this model are independently determined, allowing the model to make a quantitative prediction of solution viscosity with no adjustable parameters. The model is also applied to predict the decrease in viscosity of various polyelectrolyte/oppositely charged surfactant systems reported in literature. The results are in good agreement with experimental data, proving that our model applies to all polyelectrolytes mixed with oppositely charged surfactants that form spherical micelles.

Incipient microphase separation in short chain perfluoropolyether-block-poly(ethylene oxide) copolymers.

PubMed

Chintapalli, Mahati; Timachova, Ksenia; Olson, Kevin R; Banaszak, Michał; Thelen, Jacob L; Mecham, Sue J; DeSimone, Joseph M; Balsara, Nitash P

2017-06-07

Incipient microphase separation is observed by wide angle X-ray scattering (WAXS) in short chain multiblock copolymers consisting of perfluoropolyether (PFPE) and poly(ethylene oxide) (PEO) segments. Two PFPE-PEO block copolymers were studied; one with dihydroxyl end groups and one with dimethyl carbonate end groups. Despite having a low degree of polymerization (N ∼ 10), these materials exhibited significant scattering intensity, due to disordered concentration fluctuations between their PFPE-rich and PEO-rich domains. The disordered scattering intensity was fit to a model based on a multicomponent random phase approximation to determine the value of the interaction parameter, χ, and the radius of gyration, R g . Over the temperature range 30-90 °C, the values of χ were determined to be very large (∼2-2.5), indicating a high degree of immiscibility between the PFPE and PEO blocks. In PFPE-PEO, due to the large electron density contrast between the fluorinated and non-fluorinated block and the high value of χ, disordered scattering was detected at intermediate scattering angles, (q ∼ 2 nm -1 ) for relatively small polymer chains. Our ability to detect concentration fluctuations was enabled by both a relatively large value of χ and significant scattering contrast.

Oxide ceramic femoral heads contribute to the oxidation of polyethylene liners in artificial hip joints.

PubMed

Pezzotti, Giuseppe; Zhu, Wenliang; Sugano, Nobuhiko; Marin, Elia; Yamamoto, Kengo; Nishiike, Naomichi; Hori, Tsubasa; Rondinella, Alfredo; McEntire, Bryan J; Bock, Ryan; Sonny Bal, B

2018-06-01

Experimental evidence demonstrates that a loss of stoichiometry at the surface of oxide bioceramic femoral heads enhances the oxidation rate of polyethylene acetabular liners in artificial hip joints. Contradicting the common notion that ceramics are bioinert, three independent experiments confirmed substantial chemical interactions between the ceramic femoral heads and their polyethylene counterparts. The experiments reported herein included hydrothermal tests, frictional tests, and hip-simulator experiments. It was discovered that oxide and non-oxide femoral heads differently affected the oxidation processes at the surface of the polyethylene liners, all other testing parameters being equal. Analytical data from X-ray photoelectron (XPS), cathodoluminescence (CL), Fourier-transform infrared (FTIR), and Raman spectroscopies unequivocally and consistently showed that the oxidation rate of polyethylene liners was greater when coupled with oxide as opposed to non-oxide ceramic heads. XPS analyses of O-Al-O bond fractions at the surface of a zirconia-toughened alumina (ZTA) short-term (20 months in vivo) femoral heads retrieval showed a ~50% reduction in favor of oxygen vacancy O-Al-V O and hydroxylated Al-O-H bonds. Off-stoichiometry drifts were confirmed in vitro under both static and dynamic conditions. They triggered oxidation and tangibly affected an advanced highly cross-linked sequentially irradiated and annealed ultra-high molecular weight polyethylene (UHMWPE) liner (increase in oxidation index up to ΔOI~1.2 after 5 × 10 5 cycles under dynamic swing conditions). Second-generation UHMWPE liners infused with vitamin E were also affected by the free flow of oxygen from the oxide femoral heads, although to a lesser extent. The fundamental findings of this study, which were also confirmed on retrievals, call for revised standards in material design and testing. Adopting these new criteria will provide an improved understanding of the importance of off-stoichiometry at the head/liner interface and may lead to significant extensions in artificial joint lifetimes. Copyright © 2018 Elsevier Ltd. All rights reserved.

Raman analysis of polyethylene glycols and polyethylene oxides

NASA Astrophysics Data System (ADS)

Sagitova, E. A.; Prokhorov, K. A.; Nikolaeva, G. Yu; Baimova, A. V.; Pashinin, P. P.; Yarysheva, A. Yu; Mendeleev, D. I.

2018-04-01

We present Raman study of commercial liquids and powders of polyethylene glycols and polyethylene oxides with the average molecular weight from 400 Da to 10000 kDa. The most significant spectral changes were observed for the range of the molecular weights, where the liquid/semisolid transition has occurred. For the powders we revealed increase in the content of the molecules in the helical conformation and in the content of the monoclinic crystalline phase with growth of the molecular weight.

Oxidation-Resistant Coating For Bipolar Lead/Acid Battery

NASA Technical Reports Server (NTRS)

Bolstad, James J.

1993-01-01

Cathode side of bipolar substrate coated with nonoxidizable conductive layer. Coating prepared as water slurry of aqueous dispersion of polyethylene copolymer plus such conductive fillers as tin oxide, titanium, tantalum, or tungsten oxide. Applied easily to substrate of polyethylene carbon plastic. As slurry dries, conductive, oxidation-resistant coating forms on positive side of substrate.

Processing and characterization of recycled poly(ethylene terephthalate) blends with chain extenders, thermoplastic elastomer, and/or poly(butylene adipate-co-terephthalate)

Treesearch

Yottha Srithep; Alireza Javadi; Srikanth Pilla; Lih-Sheng Turng; Shaoqin Gong; Craig Clemons; Jun Peng

2011-01-01

Poly(ethylene terephthalate) (PET) resin is one of the most widely used thermoplastics, especially in packaging. Because thermal and hydrolytic degradations, recycled PET (RPET) exhibits poor mechanical properties and lacks moldability. The effects of adding elastomeric modifiers, chain extenders (CE), and poly(butylenes adipate-co-terephthalate), PBAT, as a toughener...

Chemically specific coarse-grained models to investigate the structure of biomimetic membranes

DOE PAGES

Kowalik, Ma?gorzata; Schantz, Allen B.; Naqi, Abdullah; ...

2017-11-29

Biomimetic polymer/protein membranes are promising materials for DNA sequencing, sensors, drug delivery and water purification. These self-assembled structures are made from low molecular weight amphiphilic block copolymers (N hydrophobic < 40 for a diblock copolymer), including poly(ethylene oxide)–1,2-polybutadiene (EO–1,2-BD) and poly(ethylene oxide)–poly(ethyl ethylene) (EO–EE). To examine these membranes' nanoscale structure, we developed a coarse-grained molecular dynamics (CG MD) model for EO–1,2-BD and assembled a CG MD model for EO–EE using parameters from two published force fields. We observe that the polymers' hydrophobic core blocks are slightly stretched compared to the random coil configuration seen at higher molecular weights. We alsomore » observe an increase in the interdigitation of the hydrophobic leaflets with increasing molecular weight (consistent with literature). The hydration level of the EO corona (which may influence protein incorporation) is higher for membranes with a larger area/chain, regardless of whether EE or 1,2-BD forms the hydrophobic block. Our results provide a molecular-scale view of membrane packing and hydrophobicity, two important properties for creating polymer–protein biomimetic membranes.« less

Chemically specific coarse-grained models to investigate the structure of biomimetic membranes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kowalik, Ma?gorzata; Schantz, Allen B.; Naqi, Abdullah

Biomimetic polymer/protein membranes are promising materials for DNA sequencing, sensors, drug delivery and water purification. These self-assembled structures are made from low molecular weight amphiphilic block copolymers (N hydrophobic < 40 for a diblock copolymer), including poly(ethylene oxide)–1,2-polybutadiene (EO–1,2-BD) and poly(ethylene oxide)–poly(ethyl ethylene) (EO–EE). To examine these membranes' nanoscale structure, we developed a coarse-grained molecular dynamics (CG MD) model for EO–1,2-BD and assembled a CG MD model for EO–EE using parameters from two published force fields. We observe that the polymers' hydrophobic core blocks are slightly stretched compared to the random coil configuration seen at higher molecular weights. We alsomore » observe an increase in the interdigitation of the hydrophobic leaflets with increasing molecular weight (consistent with literature). The hydration level of the EO corona (which may influence protein incorporation) is higher for membranes with a larger area/chain, regardless of whether EE or 1,2-BD forms the hydrophobic block. Our results provide a molecular-scale view of membrane packing and hydrophobicity, two important properties for creating polymer–protein biomimetic membranes.« less

Effect of radiation, heat, and aging on in vitro wear resistance of polyethylene.

PubMed

Muratoglu, Orhun K; Merrill, Edward W; Bragdon, Charles R; O'Connor, Daniel; Hoeffel, Daniel; Burroughs, Brian; Jasty, Murali; Harris, William H

2003-12-01

Radiation cross-linking increases the wear resistance of polyethylene used in total hip replacement. Radiation also generates residual free radicals, which are detrimental to long-term properties of polyethylene. Two approaches are used to stabilize the residual free radicals and terminally sterilize the components. One is postirradiation annealing with gas sterilization and the other is postirradiation melting with gamma sterilization in nitrogen. The hypothesis of the current study is that postirradiation annealing followed by gamma sterilization in nitrogen will result in more free radicals in polyethylene than gamma sterilization either in air or in nitrogen alone. To test this hypothesis, concentration of residual free radicals was quantified in polyethylene that was annealed and gamma sterilized in nitrogen and control polyethylenes gamma sterilized in air versus in nitrogen. Three crosslinked polyethylenes that were melted and gas sterilized also were included in the study. The effects of residual free radicals were studied by accelerated aging. Oxidation levels and weight loss in bidirectional pin-on-disk tests were determined before and after aging. Polyethylene that was subjected to postirradiation annealing and gamma sterilization resulted in 58% more residual free radicals than control polyethylenes. Weight loss of the annealed polyethylene increased by 16-fold on accelerated aging and had three times higher oxidation levels than that measured in control polyethylenes after aging. In contrast, polyethylenes that were stabilized with postirradiation melting and terminally gas sterilized showed no detectable residual free radicals. Accelerated aging did not affect the weight loss and oxidation levels of melted polyethylenes.

Biodegradable materials containing recycled polymers

NASA Astrophysics Data System (ADS)

Podzorova, M. V.; Tertyshnaya, Yu V.; Popov, A. A.

2018-04-01

The work is devoted to study the effects of different environmental factors such as water, oxygen and, light composition based on polylactide and polyethylene of low density with the addition of oxidized polyethylene, as an analog of recycled materials. Established that in the composition polylactide – polyethylene at the first stage the significant impact of moisture and UV light. The influence of UV radiation on polylactide destruction was proved by differential scanning calorimetry (DSC). It is found that polylactic acid is oxidized slower than polyethylene.

Weight of Polyethylene Wear Particles is Similar in TKAs with Oxidized Zirconium and Cobalt-chrome Prostheses

PubMed Central

Kim, Jun-Shik; Huh, Wansoo; Lee, Kwang-Hoon

2009-01-01

Background The greater lubricity and resistance to scratching of oxidized zirconium femoral components are expected to result in less polyethylene wear than cobalt-chrome femoral components. Questions/purposes We examined polyethylene wear particles in synovial fluid and compared the weight, size (equivalent circle diameter), and shape (aspect ratio) of polyethylene wear particles in knees with an oxidized zirconium femoral component with those in knees with a cobalt-chrome femoral component. Patients and Methods One hundred patients received an oxidized zirconium femoral component in one knee and a cobalt-chrome femoral component in the other. There were 73 women and 27 men with a mean age of 55.6 years (range, 44–60 years). The minimum followup was 5 years (mean, 5.5 years; range, 5–6 years). Polyethylene wear particles were analyzed using thermogravimetric methods and scanning electron microscopy. Results The weight of polyethylene wear particles produced at the bearing surface was 0.0223 ± 0.0054 g in 1 g synovial fluid in patients with an oxidized zirconium femoral component and 0.0228 ± 0.0062 g in patients with a cobalt-chrome femoral component. Size and shape of polyethylene wear particles were 0.59 ± 0.05 μm and 1.21 ± 0.24, respectively, in the patients with an oxidized zirconium femoral component and 0.52 ± 0.03 μm and 1.27 ± 0.31, respectively, in the patients with a cobalt-chrome femoral component. Knee Society knee and function scores, radiographic results, and complication rate were similar between the knees with an oxidized zirconium and cobalt-chrome femoral component. Conclusions The weight, size, and shape of polyethylene wear particles were similar in the knees with an oxidized zirconium and a cobalt-chrome femoral component. We found the theoretical advantages of this surface did not provide the actual advantage. Level of Evidence Level I, therapeutic study. See the guidelines for Authors for a complete description of levels of evidence. PMID:19949906

Interfacial surfactant competition and its impact on poly(ethylene oxide)/Au and poly(ethylene oxide)/Ag nanocomposite properties

PubMed Central

Seyhan, Merve; Kucharczyk, William; Yarar, U Ecem; Rickard, Katherine; Rende, Deniz; Baysal, Nihat; Bucak, Seyda; Ozisik, Rahmi

2017-01-01

The structure and properties of nanocomposites of poly(ethylene oxide), with Ag and Au nanoparticles, surface modified with a 1:1 (by volume) oleylamine/oleic acid mixture, were investigated via transmission electron microscopy, scanning electron microscopy, thermogravimetric analysis, differential scanning calorimetry (DSC), infrared spectroscopy, dynamic mechanical analysis, and static mechanical testing. Results indicated that there was more oleylamine on Ag nanoparticles but more oleic acid on Au nanoparticles. This difference in surfactant populations on each nanoparticle led to different interfacial interactions with poly(ethylene oxide) and drastically influenced the glass transition temperature of these two nanocomposite systems. Almost all other properties were found to correlate strongly with dispersion and distribution state of Au and Ag nanoparticles, such that the property in question changed direction at the onset of agglomeration. PMID:28461744

Electrode-Impregnable and Cross-Linkable Poly(ethylene oxide)-Poly(propylene oxide)-Poly(ethylene oxide) Triblock Polymer Electrolytes with High Ionic Conductivity and a Large Voltage Window for Flexible Solid-State Supercapacitors.

PubMed

Han, Jae Hee; Lee, Jang Yong; Suh, Dong Hack; Hong, Young Taik; Kim, Tae-Ho

2017-10-04

We present cross-linkable precursor-type gel polymer electrolytes (GPEs) that have large ionic liquid uptake capability, can easily penetrate electrodes, have high ion conductivity, and are mechanically strong as high-performance, flexible all-solid-state supercapacitors (SC). Our polymer precursors feature a hydrophilic-hydrophobic poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock main-chain structure and trifunctional silane end groups that can be multi-cross-linked with each other through a sol-gel process. The cross-linked solid-state electrolyte film with moderate IL content (200 wt %) shows a well-balanced combination of excellent ionic conductivity (5.0 × 10 -3 S cm -1 ) and good mechanical stability (maximum strain = 194%). Moreover, our polymer electrolytes have various advantages including high thermal stability (decomposition temperature > 330 °C) and the capability to impregnate electrodes to form an excellent electrode-electrolyte interface due to the very low viscosity of the precursors. By assembling our GPE-impregnated electrodes and solid-state GPE film, we demonstrate an all-solid-state SC that can operate at 3 V and provides an improved specific capacitance (112.3 F g -1 at 0.1 A g -1 ), better rate capability (64% capacity retention until 20 A g -1 ), and excellent cycle stability (95% capacitance decay over 10 000 charge/discharge cycles) compared with those of a reference SC using a conventional PEO electrolyte. Finally, flexible SCs with a high energy density (22.6 W h kg -1 at 1 A g -1 ) and an excellent flexibility (>93% capacitance retention after 5000 bending cycles) can successfully be obtained.

Synthesis and Characterization of Hydrophilic-Hydrophobic Poly(Arylene Ether Sulfone) Random and Segmented Copolymers for Membrane Applications

NASA Astrophysics Data System (ADS)

Nebipasagil, Ali

Poly(arylene ether sulfone)s are high-performance engineering thermoplastics that have been investigated extensively over the past several decades due to their outstanding mechanical properties, high glass transition temperatures (Tg), solvent resistance and exceptional thermal, oxidative and hydrolytic stability. Their thermal and mechanical properties are highly suited to a variety of applications including membrane applications such as reverse osmosis, ultrafiltration, and gas separation. This dissertation covers structure-property-performance relationships of poly(arylene ether sulfone) and poly(ethylene oxide)-containing random and segmented copolymers for reverse osmosis and gas separation membranes. The second chapter of this dissertation describes synthesis of disulfonated poly(arylene ether sulfone) random copolymers with oligomeric molecular weights that contain hydrophilic and hydrophobic segments for thin film composite (TFC) reverse osmosis membranes. These copolymers were synthesized and chemically modified to obtain novel crosslinkable poly(arylene ether sulfone) oligomers with acrylamide groups on both ends. The acrylamideterminated oligomers were crosslinked with UV radiation in the presence of a multifunctional acrylate and a UV initiator. Transparent, dense films were obtained with high gel fractions. Mechanically robust TFC membranes were prepared from either aqueous or water-methanol solutions cast onto a commercial UDELRTM foam support. This was the first example that utilized a water or alcohol solvent system and UV radiation to obtain reverse osmosis TFC membranes. The membranes were characterized with regard to composition, surface properties, and water uptake. Water and salt transport properties were elucidated at the department of chemical engineering at the University of Texas at Austin. The gas separation membranes presented in chapter three were poly(arylene ether sulfone) and poly(ethylene oxide) (PEO)-containing polyurethanes. Poly(arylene ether sulfone) copolymers with controlled molecular weights were synthesized and chemically modified to obtain poly(arylene ether sulfone) polyols with aliphatic hydroxyethyl terminal functionality. The hydroxyethyl-terminated oligomers and a,u-hydroxy-terminated PEO were chain extended with a diisocyanate to obtain polyurethanes. Compositions with high poly(arylene ether sulfone) content relative to the hydrophilic PEO blocks were of interest due to their mechanical integrity. The membranes were characterized to analyze their compositions, thermal and mechanical properties, water uptake, and molecular weights. These membranes were also evaluated by collaborators at the University of Texas at Austin to explore single gas transport properties. The results showed that both polymer and transport properties closely related to PEO-content. The CO2/CH4 gas selectivity of our membranes were improved from 25 to 34 and the CO2/N2 gas selectivity nearly doubled from 25 to 46 by increasing PEO-content from 0 to 30 wt.% in polyurethanes. Chapter four also focuses on polymers for gas separation membranes. Disulfonated poly(arylene ether sulfone) and poly(ethylene oxide)-containing polyurethanes were synthesized for potential applications as gas separation membranes. Disulfonated polyols containing 20 and 40 mole percent of disulfonated repeat units with controlled molecular weights were synthesized. Poly(arylene ether sulfone) polyols and alpha,o-hydroxy-terminated poly(ethylene oxide) were subsequently chain extended with a diisocyanate to obtain polyurethanes. Thermal and mechanical characterization revealed that the polyurethanes had a phase-mixed complex morphology.

Polyplex formation between four-arm poly(ethylene oxide)-b-poly(2-(diethylamino)ethyl methacrylate) and plasmid DNA in gene delivery.

PubMed

He, E; Yue, C Y; Simeon, F; Zhou, L H; Too, H P; Tam, K C

2009-12-01

Amphiphilic polyelectrolytes comprising cationic and uncharged hydrophilic segments condensed negatively charged DNA to form a core-shell structure stabilized by a layer of hydrophilic corona chains. At physiological pH, four-arm star-shaped poly(ethylene oxide)-b-poly(2-(diethylamino)ethyl methacrylate) (four-arm PEO-b-PDEAEMA) block copolymer possessed positively charged amine groups that interacted with negatively charged plasmid DNA to form polymer/DNA complexes. The mechanism and physicochemical properties of the complex formation were investigated at varying molar ratio of amine groups on polymer chains and phosphate group on plasmid DNA segments (N/P ratio). The capability of the star block copolymer to condense DNA was demonstrated through gel electrophoresis and ethidium bromide exclusion assay. In the absence of salt, the hydrodynamic radius of polyplexes was about 94 nm at low polymer/DNA ratio, and it decreased to about 34 nm at large N/P ratios, forming a compact spherical structure with a weighted average molecular weight of 4.39 +/- 0.22 x 10(6) g/mol. Approximately 15 polymeric chains were required to condense a plasmid DNA. The addition of monovalent salt to the polyplexes significantly altered the size of the complexes, which would have an impact on cell transfection. Because of the electrostatic interaction induced by the diffusion of small ions, the polyplex increased in size to about 53 nm with a less compact structure. In vitro cytotoxicty of polymer and polymer/pDNA complexes were evaluated, and the polyplexes exhibited low toxicity at low N/P ratios. At N/P ratio of 4.5, the four-arm PEO-b-PDEAEMA showed the highest level of transfection in Neuro-2A cells. These observations showed that the star-shaped multi-arm polymers offers interesting properties in self-association and condensation ability for plasmid DNA and can serve as a nonviral DNA delivery system. Copyright 2008 Wiley Periodicals, Inc.

Investigation of the adsorption of polymer chains on amine-functionalized double-walled carbon nanotubes.

PubMed

Ansari, R; Ajori, S; Rouhi, S

2015-12-01

Molecular dynamics (MD) simulations were used to study the adsorption of different polymer chains on functionalized double-walled carbon nanotubes (DWCNTs). The nanotubes were functionalized with two different amines: NH2 (a small amine) and CH2-NH2 (a large amine). Considering three different polymer chains, all with the same number of atoms, the effect of polymer type on the polymer-nanotube interaction was studied. In general, it was found that covalent functionalization considerably improved the polymer-DWCNT interaction. By comparing the results obtained with different polymer chains, it was observed that, unlike polyethylene and polyketone, poly(styrene sulfonate) only weakly interacts with the functionalized DWCNTs. Accordingly, the smallest radius of gyration was obtained with adsorbed poly(styrene sulfonate). It was also observed that the DWCNTs functionalized with the large amine presented more stable interactions with polyketone and poly(styrene sulfonate) than with polyethylene, whereas the DWCNTs functionalized with the small amine showed better interfacial noncovalent bonding with polyethylene.

Effect of chain length on binding of fatty acids to Pluronics in microemulsions.

PubMed

James-Smith, Monica A; Shekhawat, Dushyant; Cheung, Sally; Moudgil, Brij M; Shah, Dinesh O

2008-03-15

We investigated the effect of fatty acid chain length on the binding capacity of drug and fatty acid to Pluronic F127-based microemulsions. This was accomplished by using turbidity experiments. Pluronic-based oil-in-water microemulsions of various compositions were synthesized and titrated to turbidity with concentrated Amitriptyline, an antidepressant drug. Sodium salts of C(8), C(10), or C(12) fatty acid were used in preparation of the microemulsion and the corresponding binding capacities were observed. It has been previously determined that, for microemulsions prepared with sodium caprylate (C(8) fatty acid soap), a maximum of 11 fatty acid molecules bind to the microemulsion per 1 molecule of Pluronic F127 and a maximum of 12 molecules of Amitriptyline bind per molecule of F127. We have found that with increasing the chain length of the fatty acid salt component of the microemulsion, the binding capacity of both the fatty acid and the Amitriptyline to the microemulsion decreases. For sodium salts of C(8), C(10) and C(12) fatty acids, respectively, a maximum of approximately 11, 8.4 and 8.3 molecules of fatty acid molecules bind to 1 Pluronic F127 molecule. We propose that this is due to the decreasing number of free monomers with increasing chain length. As chain length increases, the critical micelle concentration (cmc) decreases, thus leading to fewer monomers. Pluronics are symmetric tri-block copolymers consisting of propylene oxide (PO) and ethylene oxide (EO). The polypropylene oxide block, PPO is sandwiched between two polyethylene oxide (PEO) blocks. The PEO blocks are hydrophilic while PPO is hydrophobic portion in the Pluronic molecule. Due to this structure, we propose that the fatty acid molecules that are in monomeric form most effectively diffuse between the PEO "tails" and bind to the hydrophobic PPO groups.

Iron catalyst for preparation of polymethylene from synthesis gas and method for producing the catalyst

DOEpatents

Sapienza, R.S.; Slegeir, W.A.

1990-05-15

This invention relates to a process for synthesizing hydrocarbons; more particularly, the invention relates to a process for synthesizing long-chain hydrocarbons known as polymethylene from carbon monoxide and hydrogen or from carbon monoxide and water or mixtures thereof in the presence of a catalyst comprising iron and platinum or palladium or mixtures thereof which may be supported on a solid material, preferably an inorganic refractory oxide. This process may be used to convert a carbon monoxide containing gas to a product which could substitute for high density polyethylene.

Iron catalyst for preparation of polymethylene from synthesis gas and method for producing the catalyst

DOEpatents

Sapienza, Richard S.; Slegeir, William A.

1990-01-01

This invention relates to a process for synthesizing hydrocarbons; more particularly, the invention relates to a process for synthesizing long-chain hydrocarbons known as polymethylene from carbon monoxide and hydrogen or from carbon monoxide and water or mixtures thereof in the presence of a catalyst comprising iron and platinum or palladium or mixtures thereof which may be supported on a solid material, preferably an inorganic refractory oxide. This process may be used to convert a carbon monoxide containing gas to a product which could substitute for high density polyethylene.

Synthesis and morphology of hydroxyapatite/polyethylene oxide nanocomposites with block copolymer compatibilized interfaces

NASA Astrophysics Data System (ADS)

Lee, Ji Hoon; Shofner, Meisha

2012-02-01

In order to exploit the promise of polymer nanocomposites, special consideration should be given to component interfaces during synthesis and processing. Previous results from this group have shown that nanoparticles clustered into larger structures consistent with their native shape when the polymer matrix crystallinity was high. Therefore in this research, the nanoparticles are disguised from a highly-crystalline polymer matrix by cloaking them with a matrix-compatible block copolymer. Specifically, spherical and needle-shaped hydroxyapatite nanoparticles were synthesized using a block copolymer templating method. The block copolymer used, polyethylene oxide-b-polymethacrylic acid, remained on the nanoparticle surface following synthesis with the polyethylene oxide block exposed. These nanoparticles were subsequently added to a polyethylene oxide matrix using solution processing. Characterization of the nanocomposites indicated that the copolymer coating prevented the nanoparticles from assembling into ordered clusters and that the matrix crystallinity was decreased at a nanoparticle spacing of approximately 100 nm.

Solid-state rechargeable magnesium battery

DOEpatents

Shao, Yuyan; Liu, Jun; Liu, Tianbiao; Li, Guosheng

2016-09-06

Embodiments of a solid-state electrolyte comprising magnesium borohydride, polyethylene oxide, and optionally a Group IIA or transition metal oxide are disclosed. The solid-state electrolyte may be a thin film comprising a dispersion of magnesium borohydride and magnesium oxide nanoparticles in polyethylene oxide. Rechargeable magnesium batteries including the disclosed solid-state electrolyte may have a coulombic efficiency .gtoreq.95% and exhibit cycling stability for at least 50 cycles.

On the Wrapping of Polyglycolide, Poly(Ethylene Oxide), and Polyketone Polymer Chains Around Single-Walled Carbon Nanotubes Using Molecular Dynamics Simulations

NASA Astrophysics Data System (ADS)

Rouhi, S.; Alizadeh, Y.; Ansari, R.

2015-02-01

By using molecular dynamics simulations, the interaction between a single-walled carbon nanotube and three different polymers has been studied in this work. The effects of various parameters such as the nanotube geometry and temperature on the interaction energy and radius of gyration of polymers have been explored. By studying the snapshots of polymers along the single-walled carbon nanotube, it has been shown that 50 ps can be considered as a suitable time after which the shape of polymer chains around the nanotube remains almost unchanged. It is revealed that the effect of temperature on the interaction energy and radius of gyration of polymers in the range of 250 to 500 K is not significant Also, it is shown that the interaction energy depends on the nanotube diameter.

Atomistic Simulations of Hydrodynamic and Interaction Forces on Functionalized Silica Nanoparticles

NASA Astrophysics Data System (ADS)

Lane, J. Matthew D.; Ismail, Ahmed E.; Chandross, Michael; Lorenz, Christian D.; Grest, Gary S.

2009-03-01

It is often desired to prevent the flocculation and phase separation of nanoparticles in solution. This can be accomplished either by manipulating the solvent or by tailoring the surface chemistry of the nanoparticles through functionalization with a monolayer of oligomer chains. Since it is not known how these functionalized coatings affect the interactions between nanoparticles and with the surrounding solvent, we present results from a series of molecular dynamics simulations of polyethylene oxide (PEO) coated silica nanoparticles of varying size (5 to 20 nm diameter) in water. For a single nanoparticle we determined the Stokes drag on the nanoparticle as it moves through the solvent and as it approaches a wall. Due to hydrodynamic interactions there are large finite size effects which we estimate by varying the size of the simulation cell. We also determined both solvent-mediated (velocity-independent) and lubrication (velocity-dependent) forces between two nanoparticles as a function of the coverage and chain length of the PEO chains.

Response to ``Comment on `Unified explanation of the anomalous dynamic properties of highly asymmetric polymer blends' '' [J. Chem. Phys. 138, 197101 (2013)

NASA Astrophysics Data System (ADS)

Ngai, K. L.; Capaccioli, S.

2013-05-01

The Comment of Colmenero asserts no change in Fs(Q,t) of the poly(ethylene oxide) (PEO) chains in blends with poly(methyl methacrylate) on crossing times of about 1-2 ns in data obtained by neutron scattering experiments and simulations. The assertion is opposite to that reported in the original papers where the neutron data and simulations were published. To make this point clear, we cite the data and the very statements made in the original papers concluding that indeed in the time interval from 60 ps to 1-2 ns the dynamics of PEO chain follows approximately the Rouse model, but becomes slower and departs from the Rouse model in the dependencies on time, momentum transfer, and temperature at longer times past tc = 1-2 ns. It is noteworthy that similar crossover of chain dynamics in entangled homopolymers at the ns time scale was found by neutron scattering.

Temperature dependent dielectric properties and ion transportation in solid polymer electrolyte for lithium ion batteries

NASA Astrophysics Data System (ADS)

Sengwa, R. J.; Dhatarwal, Priyanka; Choudhary, Shobhna

2016-05-01

Solid polymer electrolyte (SPE) film consisted of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) blend matrix with lithium tetrafluroborate (LiBF4) as dopant ionic salt and poly(ethylene glycol) (PEG) as plasticizer has been prepared by solution casting method followed by melt pressing. Dielectric properties and ionic conductivity of the SPE film at different temperatures have been determined by dielectric relaxation spectroscopy. It has been observed that the dc ionic conductivity of the SPE film increases with increase of temperature and also the decrease of relaxation time. The temperature dependent relaxation time and ionic conductivity values of the electrolyte are governed by the Arrhenius relation. Correlation observed between dc conductivity and relaxation time confirms that ion transportation occurs with polymer chain segmental dynamics through hopping mechanism. The room temperature ionic conductivity is found to be 4 × 10-6 S cm-1 which suggests the suitability of the SPE film for rechargeable lithium batteries.

Temperature dependent dielectric properties and ion transportation in solid polymer electrolyte for lithium ion batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sengwa, R. J., E-mail: rjsengwa@rediffmail.com; Dhatarwal, Priyanka, E-mail: dhatarwalpriyanka@gmail.com; Choudhary, Shobhna, E-mail: shobhnachoudhary@rediffmail.com

2016-05-06

Solid polymer electrolyte (SPE) film consisted of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) blend matrix with lithium tetrafluroborate (LiBF{sub 4}) as dopant ionic salt and poly(ethylene glycol) (PEG) as plasticizer has been prepared by solution casting method followed by melt pressing. Dielectric properties and ionic conductivity of the SPE film at different temperatures have been determined by dielectric relaxation spectroscopy. It has been observed that the dc ionic conductivity of the SPE film increases with increase of temperature and also the decrease of relaxation time. The temperature dependent relaxation time and ionic conductivity values of the electrolyte are governedmore » by the Arrhenius relation. Correlation observed between dc conductivity and relaxation time confirms that ion transportation occurs with polymer chain segmental dynamics through hopping mechanism. The room temperature ionic conductivity is found to be 4 × 10{sup −6} S cm{sup −1} which suggests the suitability of the SPE film for rechargeable lithium batteries.« less

Polyethylene Glycol Based Graphene Aerogel Confined Phase Change Materials with High Thermal Stability.

PubMed

Fu, Yang; Xiong, Weilai; Wang, Jianying; Li, Jinghua; Mei, Tao; Wang, Xianbao

2018-05-01

Polyethylene glycol (PEG) based graphene aerogel (GA) confined shaped-stabilized phase change materials (PCMs) are simply prepared by a one-step hydrothermal method. Three-dimensional GA inserted by PEG molecule chains, as a supporting material, obtained by reducing graphene oxide sheets, is used to keep their stabilized shape during a phase change process. The volume of GA is obviously expended after adding PEG, and only 9.8 wt% of GA make the composite achieve high energy efficiency without leakage during their phase change because of hydrogen bonding widely existing in the GA/PEG composites (GA-PCMs). The heat storage energy of GA-PCMs is 164.9 J/g, which is 90.2% of the phase change enthalpy of pure PEG. In addition, this composite inherits the natural thermal properties of graphene and thus shows enhanced thermal conductivity compared with pure PEG. This novel study provides an efficient way to fabricate shape-stabilized PCMs with a high content of PEG for thermal energy storage.

Temperature-Dependent Implicit-Solvent Model of Polyethylene Glycol in Aqueous Solution.

PubMed

Chudoba, Richard; Heyda, Jan; Dzubiella, Joachim

2017-12-12

A temperature (T)-dependent coarse-grained (CG) Hamiltonian of polyethylene glycol/oxide (PEG/PEO) in aqueous solution is reported to be used in implicit-solvent material models in a wide temperature (i.e., solvent quality) range. The T-dependent nonbonded CG interactions are derived from a combined "bottom-up" and "top-down" approach. The pair potentials calculated from atomistic replica-exchange molecular dynamics simulations in combination with the iterative Boltzmann inversion are postrefined by benchmarking to experimental data of the radius of gyration. For better handling and a fully continuous transferability in T-space, the pair potentials are conveniently truncated and mapped to an analytic formula with three structural parameters expressed as explicit continuous functions of T. It is then demonstrated that this model without further adjustments successfully reproduces other experimentally known key thermodynamic properties of semidilute PEG solutions such as the full equation of state (i.e., T-dependent osmotic pressure) for various chain lengths as well as their cloud point (or collapse) temperature.

Thermal conductivity of cross-linked polyethylene from molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Xiong, Xue; Yang, Ming; Liu, Changlin; Li, Xiaobo; Tang, Dawei

2017-07-01

The thermal conductivity of cross-linked bulk polyethylene is studied using molecular dynamics simulation. The atomic structure of the cross-linked polyethylene (PEX) is generated through simulated bond formation using LAMMPS. The thermal conductivity of PEX is studied with different degrees of crosslinking, chain length, and tensile strain. Generally, the thermal conductivity increases with the increasing degree of crosslinking. When the length of the primitive chain increases, the thermal conductivity increases linearly. When the polymer is stretched along one direction, the thermal conductivity increases in the stretched direction and decreases in the direction perpendicular to it. However, the thermal conductivity varies slightly when the polymer is stretched in three directions simultaneously.

Effect of PEO molecular weight on the miscibility and dynamics in epoxy/PEO blends.

PubMed

Lu, Shoudong; Zhang, Rongchun; Wang, Xiaoliang; Sun, Pingchuan; Lv, Weifeng; Liu, Qingjie; Jia, Ninghong

2015-11-01

In this work, the effect of poly(ethylene oxide) (PEO) molecular weight in blends of epoxy (ER) and PEO on the miscibility, inter-chain weak interactions and local dynamics were systematically investigated by multi-frequency temperature modulation DSC and solid-state NMR techniques. We found that the molecular weight (M(w)) of PEO was a crucial factor in controlling the miscibility, chain dynamics and hydrogen bonding interactions between PEO and ER. A critical PEO molecular weight (M(crit)) around 4.5k was found. PEO was well miscible with ER when the molecular weight was below M(crit), where the chain motion of PEO was restricted due to strong inter-chain hydrogen bonding interactions. However, for the blends with high molecular weight PEO (M(w) > M(crit)), the miscibility between PEO and ER was poor, and most of PEO chains were considerably mobile. Finally, polarization inversion spin exchange at magic angle (PISEMA) solid-state NMR experiment further revealed the different mobility of the PEO in ER/PEO blends with different molecular weight of PEO at molecular level. Based on the DSC and NMR results, a tentative model was proposed to illustrate the miscibility in ER/PEO blends.

Nanoscale confinement effects on the relaxation dynamics in networks of diglycidyl ether of bisphenol-A and low-molecular-weight poly(ethylene oxide).

PubMed

Kalogeras, Ioannis M; Stathopoulos, Andreas; Vassilikou-Dova, Aglaia; Brostow, Witold

2007-03-22

Thermoplastic poly(ethylene oxide) (PEO) (Mw(PEO) approximately 4000) has been used to prepare thermosetting nanocomposites incorporating diglycidyl ether of bisphenol A (DGEBA) epoxy oligomer. Blends with various PEO/DGEBA weight ratios were cured using stoichiometric portions of 4,4'-diaminodiphenylmethane. The resulting semi-interpenetrating polymer networks were studied by several techniques. Nanoscale confinement effects, thermal (glass transition, melting and crystallization temperatures) and structural features of our materials are similar to those for networks with much higher Mw(PEO) and different curing agents; however, the polyether crystallization onset occurs in our case at a lower PEO concentration; shorter PEO chains organize themselves more easily into crystalline domains. Very low estimates of the k parameter of the Gordon-Taylor equation, used to fit the compositional dependences of the dielectric and calorimetric glass transition temperatures, and a strong plasticization of the motion of the glyceryl segments (beta-relaxation) in the epoxy resin were observed. These illustrate an intensified weakening in the strength of the intermolecular interactions in the modified networks, as compared to the high strength of the self-association of hydroxyls in the neat resin. The significance of hydrogen-bonding interactions between the components for obtaining structurally homogeneous thermoset-i-thermoplastic networks is discussed.

Adhesion mapping of chemically modified and poly(ethylene oxide)-grafted glass surfaces.

PubMed

Jogikalmath, G; Stuart, J K; Pungor, A; Hlady, V

1999-08-01

Two-dimensional mapping of the adhesion pull-off forces was used to study the origin of surface heterogeneity in the grafted poly(ethylene oxide) (PEO) layer. The variance of the pull-off forces measured over the μm-sized regions after each chemical step of modifying glass surfaces was taken to be a measure of the surface chemical heterogeneity. The attachment of γ-glycidoxypropyltrimethoxy silane (GPS) to glass decreased the pull-off forces relative to the clean glass and made the surface more uniform. The subsequent hydrolysis of the terminal epoxide groups resulted in a larger surface heterogeneity which was modeled by two populations of the terminal hydroxyl groups, each with its own distribution of adhesion forces and force variance. The activation of the hydroxyls with carbonyldiimmidazole (CDI) healed the surface and lowered its adhesion, however, the force variance remained rather large. Finally, the grafting of the α,ω-diamino poly(ethyleneoxide) chains to the CDI-activated glass largely eliminated adhesion except at a few discrete regions. The adhesion on the PEO grafted layer followed the Poisson distribution of the pull-off forces. With the exception of the glass surface, a correlation between the water contact angles and the mean pull-off forces measured with the Si(3)N(4) tip surfaces was found for all modified glass surfaces.

Nonfouling Characteristics of Dextran-Containing Surfaces

PubMed Central

Martwiset, Surangkhana; Koh, Anna E.; Chen, Wei

2008-01-01

Hydroxyl groups in dextrans have been selectively oxidized to aldehyde groups by sodium periodate in a controlled fashion with percentage of conversion ranging from 6% to 100%. Dextrans (10 k, 70 k, 148 k, 500 k, and 2 000 kDa) and oxidized 10 k dextrans have been successfully grafted to functionalized silicon surfaces. The effect of molecular weight on protein adsorption is not nearly as striking as that of the extent of oxidation. When ∼ 25% of the hydroxyl groups have been converted to aldehyde groups, there is negligible protein adsorption on surfaces containing the oxidized polysaccharides. Conformations of grafted polymers depend strongly on their chemical structures, i.e. the relative amounts of –OH and –CHO groups. That the dependence of the chain conformation as well as the protein resistance on the balance of the hydrogen bond donors (-OH) and the acceptors (-OH and –CHO) implies the importance of chemical structure of surface molecules, specifically the interactions between surface and surrounding water molecules on protein adsorption. Oxidized dextrans are potential poly(ethylene glycol)-alternatives for nonfouling applications. PMID:16952261

Effect of poly(ethylene oxide) homopolymer and two different poly(ethylene oxide-b-poly(propylene oxide)-b-poly(ethylene oxide) triblock copolymers on morphological, optical, and mechanical properties of nanostructured unsaturated polyester.

PubMed

Builes, Daniel H; Hernández-Ortiz, Juan P; Corcuera, Ma Angeles; Mondragon, Iñaki; Tercjak, Agnieszka

2014-01-22

Novel nanostructured unsaturated polyester resin-based thermosets, modified with poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), and two poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) block copolymers (BCP), were developed and analyzed. The effects of molecular weights, blocks ratio, and curing temperatures on the final morphological, optical, and mechanical properties were reported. The block influence on the BCP miscibility was studied through uncured and cured mixtures of unsaturated polyester (UP) resins with PEO and PPO homopolymers having molecular weights similar to molecular weights of the blocks of BCP. The final morphology of the nanostructured thermosetting systems, containing BCP or homopolymers, was investigated, and multiple mechanisms of nanostructuration were listed and explained. By considering the miscibility of each block before and after curing, it was determined that the formation of the nanostructured matrices followed a self-assembly mechanism or a polymerization-induced phase separation mechanism. The miscibility between PEO or PPO blocks with one of two phases of UP matrix was highlighted due to its importance in the final thermoset properties. Relationships between the final morphology and thermoset optical and mechanical properties were examined. The mechanisms and physics behind the morphologies lead toward the design of highly transparent, nanostructured, and toughened thermosetting UP systems.

Gamma inert sterilization: a solution to polyethylene oxidation?

PubMed

Medel, Francisco J; Kurtz, Steven M; Hozack, William J; Parvizi, Javad; Purtill, James J; Sharkey, Peter F; MacDonald, Daniel; Kraay, Matthew J; Goldberg, Victor; Rimnac, Clare M

2009-04-01

In the 1990s, oxidation was found to occur in ultra-high molecular weight polyethylene total joint replacement components following gamma irradiation and prolonged shelf aging in air. Orthopaedic manufacturers developed barrier packaging to reduce oxidation during and after radiation sterilization. The present study explores the hypothesis that polyethylene components sterilized in a low-oxygen environment undergo similar in vivo oxidative mechanisms as inserts sterilized in air. In addition, the potential influence of the different sterilization processes on the wear performance of the polyethylene components was examined. An analysis of oxidation, wear, and surface damage was performed for forty-eight acetabular liners and 123 tibial inserts. The mean implantation time was 12.3+/-3.7 years for thirty-one acetabular liners that had been gamma sterilized in air and 4.0+/-2.5 years for the seventeen acetabular liners that had been gamma sterilized in inert gas. The mean implantation time was 11.0+/-3.2 years for the twenty-six tibial inserts that had been sterilized in air and 2.8+/-2.2 years for the ninety-seven tibial inserts that had been gamma sterilized in inert gas. Oxidation and hydroperoxide levels were characterized in loaded and unloaded regions of the inserts. Measurable oxidation and oxidation potential were observed in all cohorts. The oxidation and hydroperoxide levels were regional. Surfaces with access to body fluids were more heavily oxidized than protected bearing surfaces were. This variation appeared to be greater in historical (gamma-in-air-sterilized) components. Regarding wear performance, historical and conventional acetabular liners showed similar wear penetration rates, whereas a low incidence of delamination was confirmed for the conventional tibial inserts in the first decade of implantation. The present study explores the impact of industry-wide changes in sterilization practices for polyethylene. We found lower oxidation and oxidation potential in the conventional acetabular liners and tibial inserts that had been gamma sterilized in inert gas as compared with the historical components that had been gamma sterilized in air. However, we also found strong evidence that conventional components undergo mechanisms of in vivo oxidation similar to those observed following gamma irradiation in air. In addition, gamma sterilization in inert gas did not provide polyethylene with a significant improvement in terms of wear resistance as compared with gamma sterilization in air, except for a lower incidence of delamination in the first decade of implantation for tibial inserts.

Structure-induced switching of interpolymer adhesion at a solid-polymer melt interface.

PubMed

Jiang, Naisheng; Sen, Mani; Zeng, Wenduo; Chen, Zhizhao; Cheung, Justin M; Morimitsu, Yuma; Endoh, Maya K; Koga, Tadanori; Fukuto, Masafumi; Yuan, Guangcui; Satija, Sushil K; Carrillo, Jan-Michael Y; Sumpter, Bobby G

2018-02-14

Here we report a link between the interfacial structure and adhesive property of homopolymer chains physically adsorbed (i.e., via physisorption) onto solids. Polyethylene oxide (PEO) was used as a model and two different chain conformations of the adsorbed polymer were created on silicon substrates via the well-established Guiselin's approach: "flattened chains" which lie flat on the solid and are densely packed, and "loosely adsorbed polymer chains" which form bridges jointing up nearby empty sites on the solid surface and cover the flattened chains. We investigated the adhesion properties of the two different adsorbed chains using a custom-built adhesion testing device. Bilayers of a thick PEO overlayer on top of the flattened chains or loosely adsorbed chains were subjected to the adhesion test. The results revealed that the flattened chains do not show any adhesion even with the chemically identical free polymer on top, while the loosely adsorbed chains exhibit adhesion. Neutron reflectivity experiments corroborated that the difference in the interfacial adhesion is not attributed to the interfacial brodening at the free polymer-adsorbed polymer interface. Instead, coarse-grained molecular dynamics simulation results suggest that the tail parts of the loosely adsorbed chains act as "connector molecules", bridging the free chains and substrate surface and improving the interfacial adhesion. These findings not only shed light on the structure-property relationship at the interface, but also provide a novel approach for developing sticking/anti-sticking technologies through precise control of the interfacial polymer nanostructures.

Degradation mechanisms of cable insulation materials during radiation-thermal ageing in radiation environment

NASA Astrophysics Data System (ADS)

Seguchi, Tadao; Tamura, Kiyotoshi; Ohshima, Takeshi; Shimada, Akihiko; Kudoh, Hisaaki

2011-02-01

Radiation and thermal degradation of ethylene-propylene rubber (EPR) and crosslinked polyethylene (XLPE) as cable insulation materials were investigated by evaluating tensile properties, gel-fraction, and swelling ratio, as well as by the infrared (FTIR) analysis. The activation energy of thermal oxidative degradation changed over the range 100-120 °C for both EPR and XLPE. This may be attributed to the fact that the content of an antioxidant used as the stabilizer for polymers decreases by evaporation during thermal ageing at high temperatures. The analysis of antioxidant content and oxidative products in XLPE as a model sample showed that a small amount of antioxidant significantly reduced the extent of thermal oxidation, but was not effective for radiation induced oxidation. The changes in mechanical properties were well reflected by the degree of oxidation. A new model of polymer degradation mechanisms was proposed where the degradation does not take place by chain reaction via peroxy radical and hydro-peroxide. The role of the antioxidant in the polymer is the reduction of free radical formation in the initiation step in thermal oxidation, and it could not stop radical reactions for either radiation or thermal oxidation.

Field Effect Transistor Behavior in Electrospun Polyaniline/Polyethylene Oxide Demonstrated

NASA Technical Reports Server (NTRS)

Mueller, Carl H.; Theofylaktos, Onoufrios; Robinson, Daryl C.; Miranda, Felix A.

2004-01-01

Novel transistors and logic devices based on nanotechnology concepts are under intense development. The potential for ultra-low-power circuitry makes nanotechnology attractive for applications such as digital electronics and sensors. For NASA applications, nanotechnology offers tremendous opportunities for increased onboard data processing, and thus autonomous decisionmaking ability, and novel sensors that detect and respond to environmental stimuli with little oversight requirements. Polyaniline/polyethylene oxide (PANi/PEO) nanofibers are of interest because they have electrical conductivities that can be changed from insulating to metallic by varying the doping levels and conformations of the polymer chain. At the NASA Glenn Research Center, we have observed field effect transistor (FET) behavior in electrospun PANi/PEO nanofibers doped with camphorsulfonic acid. The nanofibers were deposited onto Au electrodes, which had been prepatterned onto oxidized silicon substrates. The preceding scanning electron image shows the device used in the transistor measurements. Saturation channel currents are observed at surprisingly low source/drain voltages (see the following graph). The hole mobility in the depletion regime is 1.4x10(exp -4)sq cm/V sec, whereas the one-dimensional charge density (at zero gate bias) is calculated to be approximately 1 hole per 50 two-ring repeat units of polyaniline, consistent with the rather high channel conductivity (approx.10(exp -3) S/cm). Reducing or eliminating the PEO content in the fiber is expected to enhance device parameters. Electrospinning is thus proposed as a simple method of fabricating one-dimensional polymer FET's.

Polyethylene glycol modified, cross-linked starch-coated iron oxide nanoparticles for enhanced magnetic tumor targeting.

PubMed

Cole, Adam J; David, Allan E; Wang, Jianxin; Galbán, Craig J; Hill, Hannah L; Yang, Victor C

2011-03-01

While successful magnetic tumor targeting of iron oxide nanoparticles has been achieved in a number of models, the rapid blood clearance of magnetically suitable particles by the reticuloendothelial system (RES) limits their availability for targeting. This work aimed to develop a long-circulating magnetic iron oxide nanoparticle (MNP) platform capable of sustained tumor exposure via the circulation and, thus, potentially enhanced magnetic tumor targeting. Aminated, cross-linked starch (DN) and aminosilane (A) coated MNPs were successfully modified with 5 kDa (A5, D5) or 20 kDa (A20, D20) polyethylene glycol (PEG) chains using simple N-Hydroxysuccinimide (NHS) chemistry and characterized. Identical PEG-weight analogues between platforms (A5 & D5, A20 & D20) were similar in size (140-190 nm) and relative PEG labeling (1.5% of surface amines - A5/D5, 0.4% - A20/D20), with all PEG-MNPs possessing magnetization properties suitable for magnetic targeting. Candidate PEG-MNPs were studied in RES simulations in vitro to predict long-circulating character. D5 and D20 performed best showing sustained size stability in cell culture medium at 37 °C and 7 (D20) to 10 (D5) fold less uptake in RAW264.7 macrophages when compared to previously targeted, unmodified starch MNPs (D). Observations in vitro were validated in vivo, with D5 (7.29 h) and D20 (11.75 h) showing much longer half-lives than D (0.12 h). Improved plasma stability enhanced tumor MNP exposure 100 (D5) to 150 (D20) fold as measured by plasma AUC(0-∞). Sustained tumor exposure over 24 h was visually confirmed in a 9L-glioma rat model (12 mg Fe/kg) using magnetic resonance imaging (MRI). Findings indicate that a polyethylene glycol modified, cross-linked starch-coated MNP is a promising platform for enhanced magnetic tumor targeting, warranting further study in tumor models. Copyright © 2010 Elsevier Ltd. All rights reserved.

Molecular Mechanisms of ZnO Nanoparticle Dispersion in Solution: Modeling of Surfactant Association, Electrostatic Shielding and Counter Ion Dynamics.

PubMed

Duchstein, Patrick; Milek, Theodor; Zahn, Dirk

2015-01-01

Molecular models of 5 nm sized ZnO/Zn(OH)2 core-shell nanoparticles in ethanolic solution were derived as scale-up models (based on an earlier model created from ion-by-ion aggregation and self-organization) and subjected to mechanistic analyses of surface stabilization by block-copolymers. The latter comprise a poly-methacrylate chain accounting for strong surfactant association to the nanoparticle by hydrogen bonding and salt-bridges. While dangling poly-ethylene oxide chains provide only a limited degree of sterical hindering to nanoparticle agglomeration, the key mechanism of surface stabilization is electrostatic shielding arising from the acrylates and a halo of Na+ counter ions associated to the nanoparticle. Molecular dynamics simulations reveal different solvent shells and distance-dependent mobility of ions and solvent molecules. From this, we provide a molecular rationale of effective particle size, net charge and polarizability of the nanoparticles in solution.

Molecular Mechanisms of ZnO Nanoparticle Dispersion in Solution: Modeling of Surfactant Association, Electrostatic Shielding and Counter Ion Dynamics

PubMed Central

Duchstein, Patrick; Milek, Theodor; Zahn, Dirk

2015-01-01

Molecular models of 5 nm sized ZnO/Zn(OH)2 core-shell nanoparticles in ethanolic solution were derived as scale-up models (based on an earlier model created from ion-by-ion aggregation and self-organization) and subjected to mechanistic analyses of surface stabilization by block-copolymers. The latter comprise a poly-methacrylate chain accounting for strong surfactant association to the nanoparticle by hydrogen bonding and salt-bridges. While dangling poly-ethylene oxide chains provide only a limited degree of sterical hindering to nanoparticle agglomeration, the key mechanism of surface stabilization is electrostatic shielding arising from the acrylates and a halo of Na+ counter ions associated to the nanoparticle. Molecular dynamics simulations reveal different solvent shells and distance-dependent mobility of ions and solvent molecules. From this, we provide a molecular rationale of effective particle size, net charge and polarizability of the nanoparticles in solution. PMID:25962096

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang, Naisheng; Sen, Mani; Zeng, Wenduo

In this paper, we report a link between the interfacial structure and adhesive property of homopolymer chains physically adsorbed (i.e., via physisorption) onto solids. Polyethylene oxide (PEO) was used as a model and two different chain conformations of the adsorbed polymer were created on silicon substrates via the well-established Guiselin's approach: “flattened chains” which lie flat on the solid and are densely packed, and “loosely adsorbed polymer chains” which form bridges jointing up nearby empty sites on the solid surface and cover the flattened chains. We investigated the adhesion properties of the two different adsorbed chains using a custom-built adhesionmore » testing device. Bilayers of a thick PEO overlayer on top of the flattened chains or loosely adsorbed chains were subjected to the adhesion test. The results revealed that the flattened chains do not show any adhesion even with the chemically identical free polymer on top, while the loosely adsorbed chains exhibit adhesion. Neutron reflectivity experiments corroborated that the difference in the interfacial adhesion is not attributed to the interfacial brodening at the free polymer–adsorbed polymer interface. Instead, coarse-grained molecular dynamics simulation results suggest that the tail parts of the loosely adsorbed chains act as “connector molecules”, bridging the free chains and substrate surface and improving the interfacial adhesion. Finally, these findings not only shed light on the structure–property relationship at the interface, but also provide a novel approach for developing sticking/anti-sticking technologies through precise control of the interfacial polymer nanostructures.« less

Molecular arrangement of symmetric and non-symmetric triblock copolymers of poly(ethylene oxide) and poly(isobutylene) at the air/water interface.

PubMed

Fuchs, Christian; Hussain, Hazrat; Schwieger, Christian; Schulz, Matthias; Binder, Wolfgang H; Kressler, Jörg

2015-01-01

The behavior of a series of amphiphilic triblock copolymers of poly(ethylene oxide) (PEO) and poly(isobutylene) (PIB); including both symmetric (same degree of polymerization (DP) of the terminal PEO blocks) PEOm-b-PIBn-b-PEOm and non-symmetric (different DP of the terminal PEO blocks) PEOm-b-PIBn-b-PEOz, is investigated at the air/water interface by measuring surface pressure vs mean molecular area isotherms (π vs mmA), Langmuir-Blodgett (LB) technique, and infrared reflection-absorption spectroscopy (IRRAS). The block copolymer (PEO32-b-PIB160-b-PEO32) with longer PEO segments forms a stable monolayer and the isotherm reveals a pseudo-plateau starting at π∼5.7 mN/m, also observed in the IRRAS, which is assigned to the pancake-to-brush transition related to the PEO dissolution into the subphase and subsequent PEO brush dehydration. Another plateau is observed at π∼40 mN/m, which is attributed to the film collapse due to multilayer formation. The pancake-to-brush transition could not be observed for samples with smaller PEO chains. The isotherms for block copolymers, with short PEO chains, both symmetric (PEO3-b-PIBn-b-PEO3) and non-symmetric (PEO12-b-PIBn-b-PEO3), reveal another transition at π∼20-25 mN/m. This is interpreted to be due to the conformational transition from a folded state where the middle PIB block is anchored to the water surface at both ends by the terminal hydrophilic segments to an unfolded state with PIB anchored to the water surface at one end. It is assumed that this transition involves the removal of PEO3 chains from the water surface in case of non-symmetric PEO12-b-PIB85-b-PEO3 and in case of symmetric, probably one PEO3 of each PEO3-b-PIB85-b-PEO3 chain. Because of the weaker interaction of the short PEO3 chains with the water surface as compared with the relatively longer PEO12 chains, the film of PEO3-b-PIB85-b-PEO3 collapses at much lower surface pressure after the transition as compared with the PEO12-b-PIB85-b-PEO3. The AFM images reveal the formation of microdomains of almost uniform height (6-7 nm) in LB films of PEO3-b-PIB85-b-PEO3 and PEO12-b-PIB85-b-PEO3 after transferring onto silicon surfaces. These domains are assumed to be the mesomorphic domains of ordered and folded PIB chains. Copyright © 2014 Elsevier Inc. All rights reserved.

A directional entrapment modification on the polyethylene surface by the amphiphilic modifier of stearyl-alcohol poly(ethylene oxide) ether

NASA Astrophysics Data System (ADS)

Lu, Qiang; Chen, Yi; Huang, Juexin; Huang, Jian; Wang, Xiaolin; Yao, Jiaying

2018-05-01

A novel entrapment modification method involving directional implantation of the amphiphilic modifier of stearyl-alcohol poly(ethylene oxide) ether (AEO) into the high-density polyethylene (HDPE) surface is proposed. This modification technique allows the AEO modifier to be able to spontaneously attain and subsequently penetrate into the swollen HDPE surface with its hydrophobic stearyl segment, while its hydrophilic poly(ethylene oxide) (PEO) segment spontaneously points to water. The AEO modifier with a HLB number below 8.7 was proved appropriate for the directional entrapment, Nevertheless, AEOs with larger HLB numbers were also effective modifiers in the presence of salt additives. In addition, a larger and hydrophobic micelle, induced respectively by the AEO concentration above 1.3 × 10-2 mol/L and the entrapping temperature above the cloud point of AEO, could lead to a sharp contact angle decline of the modified surface. Finally, a hydrophilic HDPE surface with the modifier coverage of 38.9% was reached by the directional entrapment method, which is far larger than that of 19.2% by the traditional entrapment method.

ONR Far East Scientific Information Bulletin

DTIC Science & Technology

1990-09-01

In bone, grafting onto a polymer chain, inter- continuous processes, such as reactive extru- chain reactions, formation of interpenetrat- sion and...reaction kinetics, rheology, and side- and end-chain grafting , homopolymer transport phenomena occurring during REX. chain coupling, polymer...the Grafting reactions yield block or graft coupling species becomes a part of the chain, copolymers. Polyethylene, polypropylene, or by

Polymer Energy Rechargeable System Battery Being Developed

NASA Technical Reports Server (NTRS)

Manzo, Michelle A.

2003-01-01

Long description. Illustrations of discotic liquid crystals, rod-coil polymers, lithium-ion conducting channel dilithium phthalocyanine (Li2Pc) from top and side, novel star polyethylene oxide structures, composite polyethylene oxide materials (showing polyethylene oxide + lithium salt, carbon atoms and oxygen atoms), homopolyrotaxanes, and diblock copolymers In fiscal year 2000, NASA established a program to develop the next generation, lithium-based, polymer electrolyte batteries for aerospace applications. The goal of this program, known as Polymer Energy Rechargeable Systems (PERS), is to develop a space-qualified, advanced battery system embodying polymer electrolyte and lithium-based electrode technologies and to establish world-class domestic manufacturing capabilities for advanced batteries with improved performance characteristics that address NASA s future aerospace battery requirements.

Increase of Long-chain Branching by Thermo-oxidative Treatment of LDPE

NASA Astrophysics Data System (ADS)

Rolón-Garrido, Víctor H.; Luo, Jinji; Wagner, Manfred H.

2011-07-01

Low-density polyethylene (LDPE) was exposed to thermal and thermo-oxidative treatment at 170 °C, and subsequently characterized by linear-viscoelastic measurements and in uniaxial extension. The Molecular Stress Function (MSF) model was used to quantify the elongational viscosities measured. For the thermally treated samples, exposure times between 2 and 6 hours were applied. Formation of long-chain branching (LCB) was found to occur only during the first two hours of thermal treatment. At longer exposure times, no difference in the level of strain hardening was observed. This was quantified by use of the MSF model: the nonlinear parameter fmax2 increased from fmax2 = 14 for the virgin sample to fmax2 = 22 for the samples thermally treated between 2 and 6 hours. For the thermo-oxidatively treated samples, which were exposed to air during thermal treatment between 30 and 90 minutes, the level of strain hardening increases drastically up to fmax2 = 55 with increasing exposure times from 30 up to 75 min due to LCB formation, and then decreases for an exposure time of 90 minutes due to chain scission dominating LCB formation. The nonlinear parameter β of the MSF model was found to be β = 2 for all samples, indicating that the general type of the random branching structure remains the same under all thermal conditions. Consequently only the parameter fmax2 of the MSF model and the linear-viscoelastic spectra were required to describe quantitatively the experimental observations. The strain hardening index, which is sometimes used to quantify strain hardening, follows accurately the trend of the MSF model parameter fmax2.

Design of Hybrid Solid Polymer Electrolytes: Structure and Properties

NASA Technical Reports Server (NTRS)

Bronstein, Lyudmila M.; Karlinsey, Robert L.; Ritter, Kyle; Joo, Chan Gyu; Stein, Barry; Zwanziger, Josef W.

2003-01-01

This paper reports synthesis, structure, and properties of novel hybrid solid polymer electrolytes (SPE's) consisting of organically modified aluminosilica (OM-ALSi), formed within a poly(ethylene oxide)-in-salt (Li triflate) phase. To alter the structure and properties we fused functionalized silanes containing poly(ethylene oxide) (PEO) tails or CN groups.

Iridescent cellulose nanocrystal/polyethylene oxide composite films with low coefficient of thermal expansion

Treesearch

Jairo A. Diaz; Julia L. Braun; Robert J. Moon; Jeffrey P. Youngblood

2015-01-01

Simultaneous control over optical and thermal properties is particularly challenging and highly desired in fields like organic electronics. Here we incorporated cellulose nanocrystals (CNCs) into polyethylene oxide (PEO) in an attempt to preserve the iridescent CNC optical reflection given by their chiral nematic organisation, while reducing the composite thermal...

A new approach to the immobilisation of poly(ethylene oxide) for the reduction of non-specific protein adsorption on conductive substrates

NASA Astrophysics Data System (ADS)

Cole, Martin A.; Thissen, Helmut; Losic, Dusan; Voelcker, Nicolas H.

2007-04-01

Biomedical and biotechnological devices often require surface modifications to improve their performance. In most cases, uniform coatings are desired which provide a specific property or lead to a specific biological response. In the present work, we have generated pinhole-free coatings providing amine functional groups achieved by electropolymerisation of tyramine on highly doped silicon substrates. Furthermore, amine groups were used for the subsequent grafting of poly(ethylene oxide) aldehyde via reductive amination. All surface modification steps were characterized by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The results indicate that the stability and the density of amine functional groups introduced at the surface via electropolymerisation compare favourably with alternative coatings frequently used in biomedical and biotechnological devices such as plasma polymer films. Furthermore, protein adsorption on amine and poly(ethylene oxide) coatings was studied by XPS and a colorimetric assay to test enzymatic activity. The grafting of poly(ethylene oxide) under cloud point conditions on electropolymerised tyramine layers resulted in surfaces with extremely low protein fouling character.

Amperometric Biosensor Based on Zirconium Oxide/Polyethylene Glycol/Tyrosinase Composite Film for the Detection of Phenolic Compounds.

PubMed

Ahmad, Nor Monica; Abdullah, Jaafar; Yusof, Nor Azah; Ab Rashid, Ahmad Hazri; Abd Rahman, Samsulida; Hasan, Md Rakibul

2016-06-29

A phenolic biosensor based on a zirconium oxide/polyethylene glycol/tyrosinase composite film for the detection of phenolic compounds has been explored. The formation of the composite film was expected via electrostatic interaction between hexacetyltrimethylammonium bromide (CTAB), polyethylene glycol (PEG), and zirconium oxide nanoparticles casted on screen printed carbon electrode (SPCE). Herein, the electrode was treated by casting hexacetyltrimethylammonium bromide on SPCE to promote a positively charged surface. Later, zirconium oxide was mixed with polyethylene glycol and the mixture was dropped cast onto the positively charged SPCE/CTAB. Tyrosinase was further immobilized onto the modified SPCE. Characterization of the prepared nanocomposite film and the modified SPCE surface was investigated by scanning electron microscopy (SEM), Electrochemical Impedance Spectroscopy (EIS), and Cyclic voltamogram (CV). The developed biosensor exhibits rapid response for less than 10 s. Two linear calibration curves towards phenol in the concentrations ranges of 0.075-10 µM and 10-55 µM with the detection limit of 0.034 µM were obtained. The biosensor shows high sensitivity and good storage stability for at least 30 days.

Structure and property relations of macromolecular self-assemblies at interfaces

NASA Astrophysics Data System (ADS)

Yang, Zhihao

Hydrophilic polymer chains, poly(ethylene glycol) (PEG), are attached to glass surfaces by silylation of the silanol groups on glass surfaces with the omega-(methoxyl terminated PEG) trimethoxysilanes. These tethered polymer chains resemble the self-assembled monolayers (SAMs) of PEG, which exhibit excellent biocompatibility and provide a model system for studying the interactions of proteins with polymer surfaces. The low molecular weight PEGs tend to extend, forming a brush-like monolayer, whereas the longer polymer chains tend to interpenetrate each other, forming a mushroom-like PEG monolayer at the interface. Interactions between a plasma protein, bovine serum albumin, and the PEG-SAMs are investigated in terms of protein adsorption and diffusion on the surfaces by the technique of fluorescence recovery after photobleaching (FRAP). The diffusion and aggregation behaviors of the protein on the two monolayers are found to be quite different despite the similarities in adsorption and desorption behaviors. The results are analyzed with a hypothesis of the hydrated surface dynamics. A method of covalently bonding phospholipid molecules to silica substrates followed by loading with free phospholipids is demonstrated to form well organized and stable phospholipid self-assembled monolayers. Surfaces of such SAMs structurally mimic the aqueous sides of phospholipid bilayer membranes. The dynamics of phospholipids and an adsorbed protein, lipase, in the SAMs are probed with FRAP, in terms of lateral diffusion of both phospholipids and protein molecules. The esterase activity of lipase on the SAM surfaces is confirmed by the hydrolysis reaction of a substrate, umbelliferone stearate, showing such lipid SAMs posess biomembrane functionality in terms of interfacial activation of the membranous enzymes. Dynamics of polyethylene oxide and polypropylene oxide tri-block copolymers, PEO-PPO-PEO and PPO-PEO-PPO, at the air/water interface upon thermal stimulation is studied by surface light scattering, in terms of the dynamic surface tension changes in response to a temperature jump. The characteristic of the surface tension relaxation is found to be highly related to the molecular structure and concentration of the copolymers at the interface.

Extremely High Thermal Conductivity of Aligned Carbon Nanotube-Polyethylene Composites.

PubMed

Liao, Quanwen; Liu, Zhichun; Liu, Wei; Deng, Chengcheng; Yang, Nuo

2015-11-10

The ultra-low thermal conductivity of bulk polymers may be enhanced by combining them with high thermal conductivity materials such as carbon nanotubes. Different from random doping, we find that the aligned carbon nanotube-polyethylene composites has a high thermal conductivity by non-equilibrium molecular dynamics simulations. The analyses indicate that the aligned composite not only take advantage of the high thermal conduction of carbon nanotubes, but enhance thermal conduction of polyethylene chains.

Efficient protein-repelling thin films regulated by chain mobility of low-Tg polymers with increased stability via crosslinking

NASA Astrophysics Data System (ADS)

Zhang, Jinghui; Huang, Zhiwei; Liu, Dan

2017-12-01

Polymer thin films are generally employed as coatings on implants to prevent protein adsorption. Polymer chain mobility and surface softness have been found to contribute to the protein resistance, but also bring film instability in a liquid protein medium. We investigated the protein resistance ability of three low-Tg polymers, including hydrophobic polymers polyisoprene (PI), poly(n-butyl methacrylate) (PnBMA) and hydrophilic polyethylene oxide (PEO), by overcoming the instability issue with crosslinking. We found that the Tgs of PI and PEO can be increased to around 0 °C after crosslinking. The remained strong chain mobility of both films can still resist protein adsorption regardless the hydrophobicity, yet greatly increases the film stability under an aqueous circumstance. The PnBMA film increased its Tg to around room temperature after crosslinking, which deteriorated the protein-resistance ability having the surface covered by BSA molecules. Our results support that the chain mobility of a polymer film plays an important role in resisting protein adsorption due to the increased entropy associated with more mobile polymer chains. By tune the degree of crosslinking, the stability of polymer in aqueous environment can be increased while the protein resistant ability can be remained. Our results provide a new strategy to design polymer materials for effective antifouling.

Molecular Simulation Evaluation of Macromolecular Transport through Nanofiltration Membranes

NASA Astrophysics Data System (ADS)

Almodovar Arbelo, Noelia; Boudouris, Bryan; Corti, David

A hybrid Monte Carlo and Molecular Dynamics simulation technique was implemented to elucidate the equilibrium behavior and transport properties of a model macromolecule as it navigated across a nanoporous polymer thin film (i.e., a nanofiltration membrane). The model linear homopolymer chosen was one that had interactions that were representative of poly(ethylene oxide) (PEO) due to the known interactions of PEO with solution molecules when a PEO chain is dissolved in an aqueous environment. The structural rearrangements of the PEO chain as it passes through the nanopore under an imposed chemical potential gradient was quantified as a function of solvent quality, polymer chain length, nanopore diameter and shape, and PEO-nanopore wall interactions. Thus, these computational studies provide a more detailed picture of the underlying physical mechanisms that drive macromolecular transport through nanopores, and, in particular, how dimensionally-large macromolecules (i.e., with large radii of gyration) enter and move through dimensionally-small pores (i.e., small radii nanopores). The insights gained from these studies will aid in the development of more cost-effective water purification systems in separation technologies for myriad industrial applications.

Dynamics and conformations of PEO chains chemically bonded on silica: comparison between 1H and 2H NMR.

PubMed

Tajouri, T; Hommel, H

2007-06-01

1H NMR was used to study the motion of monomer units in a layer of poly(ethylene oxide) chains grafted on silica. First, the dependence of the relaxation times on the grafting ratios is discussed qualitatively from a phenomenological point of view. Next, the NMR line narrowing effect by high-speed rotation is observed in the same samples with different grafting ratios. The magic angle spinning technique permits determination of two correlation times for each grafting ratio: tau(c) characteristic of an environment with a fast motion and tau(l) characteristic of an environment with a slow motion. In addition, the dynamics of these grafted chains are investigated by deuterium NMR (2H NMR), which is sensitive to the anisotropy of molecular motion. The evolution has been studied for two extreme grafting ratios and each time as a function of temperature. The anisotropy is more marked at low temperatures and for a low grafting ratio. The results are consistent with the 1H NMR relaxation times measured as a function of temperature. Copyright 2007 John Wiley & Sons, Ltd.

Adsorption energies of poly(ethylene oxide)-based surfactants and nanoparticles on an air-water surface.

PubMed

Zell, Zachary A; Isa, Lucio; Ilg, Patrick; Leal, L Gary; Squires, Todd M

2014-01-14

The self-assembly of polymer-based surfactants and nanoparticles on fluid-fluid interfaces is central to many applications, including dispersion stabilization, creation of novel 2D materials, and surface patterning. Very often these processes involve compressing interfacial monolayers of particles or polymers to obtain a desired material microstructure. At high surface pressures, however, even highly interfacially active objects can desorb from the interface. Methods of directly measuring the energy which keeps the polymer or particles bound to the interface (adsorption/desorption energies) are therefore of high interest for these processes. Moreover, though a geometric description linking adsorption energy and wetting properties through the definition of a contact angle can be established for rigid nano- or microparticles, such a description breaks down for deformable or aggregating objects. Here, we demonstrate a technique to quantify desorption energies directly, by comparing surface pressure-density compression measurements using a Wilhelmy plate and a custom-microfabricated deflection tensiometer. We focus on poly(ethylene oxide)-based polymers and nanoparticles. For PEO-based homo- and copolymers, the adsorption energy of PEO chains scales linearly with molecular weight and can be tuned by changing the subphase composition. Moreover, the desorption surface pressure of PEO-stabilized nanoparticles corresponds to the saturation surface pressure for spontaneously adsorbed monolayers, yielding trapping energies of ∼10(3) k(B)T.

Enhanced Thermal Conductivity and Dielectric Properties of Iron Oxide/Polyethylene Nanocomposites Induced by a Magnetic Field.

PubMed

Chi, Qingguo; Ma, Tao; Dong, Jiufeng; Cui, Yang; Zhang, Yue; Zhang, Changhai; Xu, Shichong; Wang, Xuan; Lei, Qingquan

2017-06-08

Iron Oxide (Fe 3 O 4 ) nanoparticles were deposited on the surface of low density polyethylene (LDPE) particles by solvothermal method. A magnetic field was introduced to the preparation of Fe 3 O 4 /LDPE composites, and the influences of the magnetic field on thermal conductivity and dielectric properties of composites were investigated systematically. The Fe 3 O 4 /LDPE composites treated by a vertical direction magnetic field exhibited a high thermal conductivity and a large dielectric constant at low filler loading. The enhancement of thermal conductivity and dielectric constant is attributed to the formation of the conductive chains of Fe 3 O 4 in LDPE matrix under the action of the magnetic field, which can effectively enhance the heat flux and interfacial polarization of the Fe 3 O 4 /LDPE composites. Moreover, the relatively low dielectric loss and low conductivity achieved are attributed to the low volume fraction of fillers and excellent compatibility between Fe 3 O 4 and LDPE. Of particular note is the dielectric properties of Fe 3 O 4 /LDPE composites induced by the magnetic field also retain good stability across a wide temperature range, and this contributes to the stability and lifespan of polymer capacitors. All the above-mentioned properties along with the simplicity and scalability of the preparation for the polymer nanocomposites make them promising for the electronics industry.

High Ionic Conductivity of Composite Solid Polymer Electrolyte via In Situ Synthesis of Monodispersed SiO2 Nanospheres in Poly(ethylene oxide).

PubMed

Lin, Dingchang; Liu, Wei; Liu, Yayuan; Lee, Hye Ryoung; Hsu, Po-Chun; Liu, Kai; Cui, Yi

2016-01-13

High ionic conductivity solid polymer electrolyte (SPE) has long been desired for the next generation high energy and safe rechargeable lithium batteries. Among all of the SPEs, composite polymer electrolyte (CPE) with ceramic fillers has garnered great interest due to the enhancement of ionic conductivity. However, the high degree of polymer crystallinity, agglomeration of ceramic fillers, and weak polymer-ceramic interaction limit the further improvement of ionic conductivity. Different from the existing methods of blending preformed ceramic particles with polymers, here we introduce an in situ synthesis of ceramic filler particles in polymer electrolyte. Much stronger chemical/mechanical interactions between monodispersed 12 nm diameter SiO2 nanospheres and poly(ethylene oxide) (PEO) chains were produced by in situ hydrolysis, which significantly suppresses the crystallization of PEO and thus facilitates polymer segmental motion for ionic conduction. In addition, an improved degree of LiClO4 dissociation can also be achieved. All of these lead to good ionic conductivity (1.2 × 10(-3) S cm(-1) at 60 °C, 4.4 × 10(-5) S cm(-1) at 30 °C). At the same time, largely extended electrochemical stability window up to 5.5 V can be observed. We further demonstrated all-solid-state lithium batteries showing excellent rate capability as well as good cycling performance.

Using solvent-free sample preparation to promote protonation of poly(ethylene oxide)s with labile end-groups in matrix-assisted laser desorption/ionisation.

PubMed

Mazarin, Michael; Phan, Trang N T; Charles, Laurence

2008-12-01

Protonation is usually required to observe intact ions during matrix-assisted laser desorption/ionization (MALDI) of polymers containing fragile end-groups while cation adduction induces chain-end degradation. These polymers, generally obtained via living free radical polymerization techniques, are terminated with a functionality in which a bond is prone to homolytic cleavage, as required by the polymerization process. A solvent-free sample preparation method was used here to avoid salt contaminant from the solvent traditionally used in the dried-droplet MALDI procedure. Solvent-based and solvent-free sample preparations were compared for a series of three poly(ethylene oxide) polymers functionalized with a labile end-group in a nitroxide-mediated polymerization reaction, using 2,4,6-trihydroxyacetophenone (THAP) as the matrix without any added salt. Intact oligomer ions could only be produced as protonated molecules in solvent-free MALDI while sodium adducts of degraded polymers were formed from the dried-droplet samples. Although MALDI analysis was performed at the laser threshold, fragmentation of protonated macromolecules was still observed to occur. However, in contrast to sodiated molecules, dissociation of protonated oligomers does not involve the labile C--ON bond of the end-group. As the macromolecule size increased, protonation appeared to be less efficient and sodium adduction became the dominant ionization process, although no sodium salt was added in the preparation. Formation of sodiated degraded macromolecules would be dictated by increasing cation affinity as the size of the oligomers increases and would reveal the presence of salts at trace levels in the MALDI samples.

In vivo degradation of polyethylene liners after gamma sterilization in air.

PubMed

Kurtz, Steven M; Rimnac, Clare M; Hozack, William J; Turner, Joseph; Marcolongo, Michele; Goldberg, Victor M; Kraay, Matthew J; Edidin, Avram A

2005-04-01

Ultra-high molecular weight polyethylene degrades during storage in air following gamma sterilization, but the extent of in vivo degradation remains unclear. The purpose of this study was to quantify the extent to which the mechanical properties and oxidation of conventional polyethylene acetabular liners treated with gamma sterilization in air change in vivo. Fourteen modular cementless acetabular liners were revised at an average of 10.3 years (range, 5.9 to 13.5 years) after implantation. All liners, which had been machined from GUR 415 resin, had been gamma-sterilized in air; the average shelf life was 0.3 year (range, 0.0 to 0.8 year). After removal, the components were expeditiously frozen to minimize ex vivo changes to the polyethylene prior to characterization. The average duration between freezing and testing was 0.6 year. Mechanical properties and oxidation were measured with use of the small-punch test and Fourier transform infrared spectroscopy, respectively, in the loaded and unloaded regions of the liners. There was substantial regional variation in the mechanical properties and oxidation of the retrieved liners. The ultimate load was observed to vary by >90% near the surface. On the average, the rim and the unloaded bearing showed evidence of severe oxidation near the surface after long-term in vivo aging, but these trends were not typically observed on the loaded bearing surface or near the backside of the liners. The mechanical properties of polyethylene that has been gamma-sterilized in air may decrease substantially in vivo, depending on the location in the liner. The most severe oxidation was observed at the rim, suggesting that the femoral head inhibits access of oxygen-containing body fluids to the bearing surface. This is perhaps why in vivo oxidation has not been associated with clinical performance to date.

DFT Modeling of Cross-Linked Polyethylene: Role of Gold Atoms and Dispersion Interactions.

PubMed

Blaško, Martin; Mach, Pavel; Antušek, Andrej; Urban, Miroslav

2018-02-08

Using DFT modeling, we analyze the concerted action of gold atoms and dispersion interactions in cross-linked polyethylene. Our model consists of two oligomer chains (PEn) with 7, 11, 15, 19, or 23 carbon atoms in each oligomer cross-linked with one to three Au atoms through C-Au-C bonds. In structures with a single gold atom the C-Au-C bond is located in the central position of the oligomer. Binding energies (BEs) with respect to two oligomer radical fragments and Au are as high as 362-489 kJ/mol depending on the length of the oligomer chain. When the dispersion contribution in PEn-Au-PEn oligomers is omitted, BE is almost independent of the number of carbon atoms, lying between 293 and 296 kJ/mol. The dispersion energy contributions to BEs in PEn-Au-PEn rise nearly linearly with the number of carbon atoms in the PEn chain. The carbon-carbon distance in the C-Au-C moiety is around 4.1 Å, similar to the bond distance between saturated closed shell chains in the polyethylene crystal. BEs of pure saturated closed shell PEn-PEn oligomers are 51-187 kJ/mol. Both Au atoms and dispersion interactions contribute considerably to the creation of nearly parallel chains of oligomers with reasonably high binding energies.

Characterization of the organic ligand shell of semiconductor quantum dots by fluorescence quenching experiments.

PubMed

Boldt, Klaus; Jander, Sebastian; Hoppe, Kathrin; Weller, Horst

2011-10-25

We present the characterization of the organic ligand shell of CdSe/Cd(x)Zn(1-x)S/ZnS nanoparticles by means of fluorescence quenching experiments. Both electron scavengers and acceptors for resonance energy transfer were employed as probes. Different quenching behavior for short and long chain thiol ligands in water was found. It could be shown that poly(ethylene oxide) (PEO)-capping of the particles comprises a densely packed inner shell and a loosely packed outer shell in which ions and small molecules diffuse unhindered. A quantitative uptake of quencher molecules into the PEO shell was observed, through which the particle volume including the ligand sphere could be determined.

Theoretical Insight into Dispersion of Silica Nanoparticles in Polymer Melts.

PubMed

Wei, Zhaoyang; Hou, Yaqi; Ning, Nanying; Zhang, Liqun; Tian, Ming; Mi, Jianguo

2015-07-30

Silica nanoparticles dispersed in polystyrene, poly(methyl methacrylate), and poly(ethylene oxide) melts have been investigated using a density functional approach. The polymers are regarded as coarse-grained semiflexible chains, and the segment sizes are represented by their Kuhn lengths. The particle-particle and particle-polymer interactions are calculated with the Hamaker theory to reflect the relationship between particles and polymer melts. The effects of particle volume fraction and size on the particle dispersion have been quantitatively determined to evaluate their dispersion/aggregation behavior in these polymer melts. It is shown that theoretical predictions are generally in good agreement with the corresponding experimental results, providing the reasonable verification of particle dispersion/agglomeration and polymer depletion.

Dependence on sphere size of the phase behavior of mixtures of rods and spheres

NASA Astrophysics Data System (ADS)

Urakami, Naohito; Imai, Masayuki

2003-07-01

By the addition of chondroitin sulfate (Chs) to the aqueous suspension of tobacco mosaic virus (TMV), the aggregation of TMV occurs at very dilute TMV concentration compared with the addition of polyethylene oxide (PEO). The difference of physical behavior between Chs and PEO is the chain conformation in solution. The Chs chain has a semirigid nature, whereas the PEO chain has a flexible nature. In this study, the Chs and PEO chains are simplified to spherical particles having different size, and we use the spherocylinder model for TMV particle. The effect of the sphere size on the phase behaviors in the mixtures of rods and spheres is investigated by Monte Carlo simulations. By the addition of small spheres, the system transforms from the miscible isotropic phase to the miscible nematic phase. On the other hand, by the addition of large spheres, the system changes from the miscible isotropic phase to the immiscible nematic phase through the immiscible isotropic phase. The different phase behaviors between the small and the large spheres originate from the difference of overlapping volume of the depletion zone. In addition, we perform the Monte Carlo simulations in the case that semirigid chains are used as the Chs chain models. The same phase behaviors are observed as the mixtures of rods and large spheres. Thus the sphere model captures the phase behaviors of rod and polymer mixture systems.

Effect of support size on the catalytic activity of metal-oxide-doped silica particles in the glycolysis of polyethylene terephthalate.

PubMed

Wi, Rinbok; Imran, Muhammad; Lee, Kyoung G; Yoon, Sun Hong; Cho, Bong Gyoo; Kim, Do Hyun

2011-07-01

Zinc oxide (ZnO) and cerium oxide (CeO2) nanoparticles were deposited on the surface of preformed silica spheres with diameters ranging from 60 to 750 nm. Ultrasonic irradiation was employed to promote the deposition of the metal oxide nanoparticles on the surface of silica. Silica-supported zinc oxide or cerium oxide was used as a catalyst in the glycolysis of polyethylene terephthalate, one of the key processes in the depolymerization of polyethylene terephthalate. The effect of the support size on the catalytic activity was studied in terms of monomer yield, and the monomer concentration was analyzed via high-performance liquid chromatography (HPLC). The morphologies and surface properties of the catalysts were characterized using a scanning electron microscope, a transmission electron microscope, and a BET surface area analyzer, while the monomer was characterized via HPLC and nuclear-magnetic-resonance spectroscopy. Both the zinc oxide and cerium oxide deposited on a smaller support showed better distribution and less aggregation. The high specific surface area of the smaller support catalysts provided a large number of active sites. The highest monomer yield was obtained with a catalyst of 60-nm silica support.

Acoustic, Thermal and Molecular Interactions of Polyethylene Glycol (2000, 3000, 6000)

NASA Astrophysics Data System (ADS)

Venkatramanan, K.; Padmanaban, R.; Arumugam, V.

Polyethylene Glycol (PEG) is a condensation polymer of ethylene oxide and water. PEG find its application as emulsifying agents, detergents, soaps, plasticizers, ointments, etc. Though the chemical and physical properties of PEG are known, still because of their uses in day to day life, it becomes necessary to study few physical properties like ultrasonic velocity, viscosity and hence adiabatic compressibility, free length, etc. In the present study, an attempt has been made to compute the activation energy and hence to analyse the molecular interactions of aqueous solutions of Polyethylene Glycol of molar mass 2000, 3000 and 6000 at different concentrations (2%, 4%, 6%, 8% and 10%) at different temperatures (303K, 308K, 313K, 318K) by determining relative viscosity, ultrasonic velocity and density. Various parameters like adiabatic compressibility, viscous relaxation time, inter molecular free length, free volume, internal pressure, etc are calculated at 303K and the results are discussed in the light of polymer-solvent interaction. This study helps to understand the behavior of macro-molecules with respect to changing concentration and temperature. Furthermore, viscosity and activation energy results are correlated to understand the increased entanglement of the polymer chains due to the increase in the concentration of a polymer solution that leads to an increase in viscosity and an increase in the activation energy of viscous flow.

Structure-induced switching of interpolymer adhesion at a solid–polymer melt interface

DOE PAGES

Jiang, Naisheng; Sen, Mani; Zeng, Wenduo; ...

2018-01-11

In this paper, we report a link between the interfacial structure and adhesive property of homopolymer chains physically adsorbed (i.e., via physisorption) onto solids. Polyethylene oxide (PEO) was used as a model and two different chain conformations of the adsorbed polymer were created on silicon substrates via the well-established Guiselin's approach: “flattened chains” which lie flat on the solid and are densely packed, and “loosely adsorbed polymer chains” which form bridges jointing up nearby empty sites on the solid surface and cover the flattened chains. We investigated the adhesion properties of the two different adsorbed chains using a custom-built adhesionmore » testing device. Bilayers of a thick PEO overlayer on top of the flattened chains or loosely adsorbed chains were subjected to the adhesion test. The results revealed that the flattened chains do not show any adhesion even with the chemically identical free polymer on top, while the loosely adsorbed chains exhibit adhesion. Neutron reflectivity experiments corroborated that the difference in the interfacial adhesion is not attributed to the interfacial brodening at the free polymer–adsorbed polymer interface. Instead, coarse-grained molecular dynamics simulation results suggest that the tail parts of the loosely adsorbed chains act as “connector molecules”, bridging the free chains and substrate surface and improving the interfacial adhesion. Finally, these findings not only shed light on the structure–property relationship at the interface, but also provide a novel approach for developing sticking/anti-sticking technologies through precise control of the interfacial polymer nanostructures.« less

Miscibility of poly(lactic acid) and poly(ethylene oxide) solvent polymer blends and nanofibers made by solution blow spinning

USDA-ARS?s Scientific Manuscript database

The miscibility of blends of poly(lactic acid) (PLA) and poly(ethylene oxide) (PEO) was studied in polymer solutions by dilute solution viscometry and in solution blow spun nanofibers by microscopy (SEM, TEM) and by thermal and spectral analysis. Three blends of PLA and PEO were solution blended in...

Biological resistance of polyethylene composites made with chemically modified fiber or flour

Treesearch

Rebecca E. Ibach; Craig M. Clemons

2002-01-01

The role of moisture in the biological decay of wood-plastic composites was investigated. Southern pine wood fiber and ponderosa pine wood flour were chemically modified using either acetic anhydride (AA), butylene oxide (BO), or propylene oxide (PO). A 50:50 mixture of high density polyethylene and either chemically modified fiber or flour, or untreated fiber or flour...

Comparison between Cellulose Nanocrystal and Cellulose Nanofibril Reinforced Poly(ethylene oxide) Nanofibers and Their Novel Shish-Kebab-Like Crystalline Structures

Treesearch

Xuezhu Xu; Haoran Wang; Long Jiang; Xinnan Wang; Scott A. Payne; J.Y. Zhu; Ruipeng Li

2014-01-01

Poly(ethylene oxide) (PEO) nanofiber mats were produced by electrospinning. Biobased cellulose nanocrystals (CNCs) and cellulose nanofibrils (CNFs) as reinforcement nanofillers were also added to the polymer to produce composite nanofiber mats. The effects of the two cellulose nanofillers on the rheological properties of the PEO solutions and the microstructure,...

[Effect of sterilisation with formaldehyde, gamma irradiation and ethylene oxide on the properties of polyethylene joint replacement components].

PubMed

Fulín, P; Pokorný, D; Slouf, M; Vacková, T; Dybal, J; Sosna, A

2014-01-01

Each method of sterilisation has some effect on the structure and properties of UHMWPE and thus also on joint replacement longevity. This study was designed to compare, using objective methods of measurement, several kinds of sterilisation and to recommend the one which has the best prospect for making joint replacements last longer. Two groups of UHMWPE samples were tested. Group 1 included virgin GUR 1020 polyethylene, non-modified and non-sterilised (Meditech, Germany). Group 2 comprised of three sets of samples sterilised with formaldehyde, gamma irradiation and ethylene oxide, respectively. In both groups, physicochemical properties were assessed by infrared spectroscopy (IR), and the oxidation (OI) and trans-vinyl (VI) indices, which show the degree of oxidation of a material, were determined. Free-radical concentrations were measured by the method of electron spin resonance (ESR). The mechanical properties of each sample were studied using small punch tests (SPT) and testing microhardness (MH). Any change in mechanical properties can affect, to various degrees, the quality and longevity of a prosthetic joint. The samples sterilised by gamma irradiation showed higher values of both the OI (0.37) and the VI index (0.038) than the other samples (OI, 0.02 to 0.05 and VI, 0). Also, the free-radical concentration was detectable only in the gamma-sterilised sample. Values obtained for mechanical properties were as follows: peak load in the range of 58.48 N (gamma irradiation) to 59.60 N (ethylene oxide); ultimate load in the range of 46.69 N (gamma irradiation) to 57.50 N (ethylene oxide); ultimate displacement in the range of 4.29 mm (gamma irradiation) to 4.58 mm (virgin polyethylene and formaldehyde); and work to failure in the range of 185.18 mJ (gamma irradiation) to 205.89 mJ (virgin polyethylene). Microhardness values were obtained in the following ranges: 41.2 to 44.6 MPa (virgin polyethylene); 40.2 to 44.1 MPa (formaldehyde); 46.1 to 49.3 MPa (gamma irradiation); and 40.3 to 44.2 MPa (ethylene oxide). The samples sterilised with formaldehyde and ethylene oxide have mechanical properties very similar to virgin polyethylene, they are not damaged by oxidation and do not contain free radicals. Owing to these characteristics, the immediate and long-term oxidation stability of the three samples is higher. The sample sterilised by gamma irradiation showed the presence of free radicals and immediate and long-term oxidative degradation. This results in the deterioration of mechanical properties and the growth of crystallinity due to enhanced oxidation and leads to higher polyethylene microhardness. Sterilisation with gamma irradiation results in oxidative degradation and mechanical property deterioration, which is one of the potential risks of a shorter life span of joint replacements. The use of ethylene oxide or formaldehyde does not change polymer properties nor has any effect on oxidation of materials. Therefore, a longer life expectancy of the joint replacements sterilised with ethylene oxide can be expected. The life span of their joint replacements is a key issue for the patients. Prosthetic joint loosening is painful and the patient often requires re-implantation. A higher number of re-implantations is associated with higher costs for the institution involved and, consequently, for the whole health care system. Although this study basically deals with chemical issues, it informs the surgeon of the latest developments leading to the improvement of implanted materials, which can increase the life expectancy of joint replacements and patients' satisfaction.

Amperometric Biosensor Based on Zirconium Oxide/Polyethylene Glycol/Tyrosinase Composite Film for the Detection of Phenolic Compounds

PubMed Central

Ahmad, Nor Monica; Abdullah, Jaafar; Yusof, Nor Azah; Ab Rashid, Ahmad Hazri; Abd Rahman, Samsulida; Hasan, Md. Rakibul

2016-01-01

A phenolic biosensor based on a zirconium oxide/polyethylene glycol/tyrosinase composite film for the detection of phenolic compounds has been explored. The formation of the composite film was expected via electrostatic interaction between hexacetyltrimethylammonium bromide (CTAB), polyethylene glycol (PEG), and zirconium oxide nanoparticles casted on screen printed carbon electrode (SPCE). Herein, the electrode was treated by casting hexacetyltrimethylammonium bromide on SPCE to promote a positively charged surface. Later, zirconium oxide was mixed with polyethylene glycol and the mixture was dropped cast onto the positively charged SPCE/CTAB. Tyrosinase was further immobilized onto the modified SPCE. Characterization of the prepared nanocomposite film and the modified SPCE surface was investigated by scanning electron microscopy (SEM), Electrochemical Impedance Spectroscopy (EIS), and Cyclic voltamogram (CV). The developed biosensor exhibits rapid response for less than 10 s. Two linear calibration curves towards phenol in the concentrations ranges of 0.075–10 µM and 10–55 µM with the detection limit of 0.034 µM were obtained. The biosensor shows high sensitivity and good storage stability for at least 30 days. PMID:27367738

Injectible bodily prosthetics employing methacrylic copolymer gels

DOEpatents

Mallapragada, Surya K.; Anderson, Brian C.

2007-02-27

The present invention provides novel block copolymers as structural supplements for injectible bodily prosthetics employed in medical or cosmetic procedures. The invention also includes the use of such block copolymers as nucleus pulposus replacement materials for the treatment of degenerative disc disorders and spinal injuries. The copolymers are constructed by polymerization of a tertiary amine methacrylate with either a (poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) polymer, such as the commercially available Pluronic.RTM. polymers, or a poly(ethylene glycol) methyl ether polymer.

pH-sensitive methacrylic copolymer gels and the production thereof

DOEpatents

Mallapragada, Surya K [Ames, IA; Anderson, Brian C [Lake Bluff, IA

2007-05-15

The present invention provides novel gel forming methacrylic blocking copolymers that exhibit cationic pH-sensitive behavior as well as good water solubility. The copolymers are constructed by polymerization of a tertiary amine methacrylate with either a (poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) polymer, such as the commercially available Pluronic.RTM. polymers, or a poly(ethylene glycol)methyl ether polymer. The polymers may be used for drug and gene delivery, protein separation, as structural supplements, and more.

Molecular Dynamics Studies of Polyethylene Oxide and Polyethylene Glycol: Hydrodynamic Radius and Shape Anisotropy

PubMed Central

Lee, Hwankyu; Venable, Richard M.; MacKerell, Alexander D.; Pastor, Richard W.

2008-01-01

A revision (C35r) to the CHARMM ether force field is shown to reproduce experimentally observed conformational populations of dimethoxyethane. Molecular dynamics simulations of 9, 18, 27, and 36-mers of polyethylene oxide (PEO) and 27-mers of polyethylene glycol (PEG) in water based on C35r yield a persistence length λ = 3.7 Å, in quantitative agreement with experimentally obtained values of 3.7 Å for PEO and 3.8 Å for PEG; agreement with experimental values for hydrodynamic radii of comparably sized PEG is also excellent. The exponent υ relating the radius of gyration and molecular weight (\\documentclass[10pt]{article} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{pmc} \\usepackage[Euler]{upgreek} \\pagestyle{empty} \\oddsidemargin -1.0in \\begin{document} \\begin{equation*}R_{{\\mathrm{g}}}{\\propto}M_{{\\mathrm{w}}}^{{\\upsilon}}\\end{equation*}\\end{document}) of PEO from the simulations equals 0.515 ± 0.023, consistent with experimental observations that low molecular weight PEG behaves as an ideal chain. The shape anisotropy of hydrated PEO is 2.59:1.44:1.00. The dimension of the middle length for each of the polymers nearly equals the hydrodynamic radius \\documentclass[10pt]{article} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{pmc} \\usepackage[Euler]{upgreek} \\pagestyle{empty} \\oddsidemargin -1.0in \\begin{document} \\begin{equation*}R_{{\\mathrm{h}}}\\end{equation*}\\end{document}obtained from diffusion measurements in solution. This explains the correspondence of \\documentclass[10pt]{article} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{pmc} \\usepackage[Euler]{upgreek} \\pagestyle{empty} \\oddsidemargin -1.0in \\begin{document} \\begin{equation*}R_{{\\mathrm{h}}}\\end{equation*}\\end{document} and \\documentclass[10pt]{article} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{pmc} \\usepackage[Euler]{upgreek} \\pagestyle{empty} \\oddsidemargin -1.0in \\begin{document} \\begin{equation*}R_{{\\mathrm{p}}},\\end{equation*}\\end{document} the pore radius of membrane channels: a polymer such as PEG diffuses with its long axis parallel to the membrane channel, and passes through the channel without substantial distortion. PMID:18456821

Surface grafting of poly(ethylene glycol) onto poly(acrylamide-co-vinyl amine) cross-linked films under mild conditions.

PubMed

Yamamoto, Y; Sefton, M V

1998-01-01

Poly(ethylene glycol) (PEG) was grafted onto poly(acrylamide-co-vinyl amine) (poly(AM-co-VA)) film using tresylated PEG (TPEG) at 37 degrees C in aqueous buffers (pH 7.4) with a view to surface-modifying microencapsulated mammalian cells. Poly(AM-co-VA) film was synthesized by Hofmann degradation of a cross-linked poly(acrylamide) film. Conversion to vinyl amine on the surface of the film was approximately 50%, but bulk conversion was not observed; surface specificity was thought to be the result of cleavage of aminated polymer chains at the surface due to chain scission. Reaction between primary amine and TPEG gave a graft yield of 2 mol% (based on XPS) with respect to available surface amine groups, equivalent to 54 mol% ethylene oxide based on monomer units. Physical adsorption of non-activated polymer was done under identical conditions as a control and the difference in oxygen content was significant compared to TPEG. The type of buffer agent and buffer concentration did not influence graft yields. This graft reaction, which was completed in as little as 2 h was considered to be mild enough to be used for a surface modification of microcapsules containing cells without affecting their viability. Such a surface modification technique may prove to be a useful means of enhancing the biocompatibility of microcapsules (or any tissue engineering construct) even after cell encapsulation or seeding.

Relationship between morphological change and crystalline phase transitions of polyethylene-poly(ethylene oxide) diblock copolymers, revealed by the temperature-dependent synchrotron WAXD/SAXS and infrared/Raman spectral measurements.

PubMed

Weiyu, Cao; Tashiro, Kohji; Hanesaka, Makoto; Takeda, Shinichi; Masunaga, Hiroyasu; Sasaki, Sono; Takata, Masaki

2009-02-26

The phase transition behaviors of low-molecular-weight polyethylene-poly(ethylene oxide) (PE-b-PEO) diblock copolymers with the monomeric units of PE/PEO = 17/40 and 39/86 have been successfully investigated through the temperature-dependent measurements of wide-angle X-ray diffraction (WAXD), small-angle X-ray scattering (SAXS), infrared and Raman spectra, as well as thermal analysis. These diblock copolymers had been believed to show only order-to-disorder transition of lamellar morphology in a wide temperature region, but it has been found here for the first time that this copolymer clearly exhibits the three stages of transitions among lamella, gyroid, cylinder, and spherical phases in the heating and cooling processes. The WAXD and IR/Raman spectral measurements allowed us to relate these morphological changes to the microscopic changes in the aggregation states of PEO and PE segments. In the low-temperature region the PEO segments form the monoclinic crystal of (7/2) helical chain conformation and the PE segments of planar-zigzag form take the orthorhombic crystalline phase. These crystalline lamellae of PEO and PE segments are alternately stacked with the long period of 165 Angstroms. In a higher temperature region, where the PEO crystalline parts are on the way of melting but the PE parts are still in the orthorhombic phase, the gyroid morphology is detected in the SAXS data. By heating further, the gyroid morphology changes to the hexagonally packed cylindrical morphology, where the orthorhombic phase of PE segments is gradually disordered because of thermally activated molecular motion and finally transforms to the pseudohexagonal or rotator phase. Once the PE segments are perfectly melted, the higher-order structure changes from the cylinder to the spherical morphology. These morphological transitions might relate to the thermally activated motions of two short chain segments of the diblock copolymer, although the details of the transition mechanism are unclear at the present stage.

1.55 Micrometer Sub-Micron Finger, Interdigitated MSM Photodetector Arrays with Low Dark Current

DTIC Science & Technology

2010-02-02

pf a- IGZO TFTs. IV. RF Characteristics of Room Temperature Deposited Indium Zinc Oxide Thin - Film Transistors Depletion-mode indium zinc...III. High Performance Indium Gallium Zinc Oxide Thin Film Transistors Fabricated On Polyethylene Terephthalate Substrates High-performance...amorphous (a-) InGaZnO-based thin film transistors (TFTs) were fabricated on flexible polyethylene terephthalate (PET) substrates coated with indium

Molecular dynamics simulations of polyamidoamine dendrimers and their complexes with linear poly(ethylene oxide) at different pH conditions: static properties and hydrogen bonding.

PubMed

Tanis, I; Karatasos, K

2009-11-21

Models consisting of an amine-terminated poly(amidoamine) (PAMAM) dendrimer with and without the presence of a linear poly(ethylene oxide) (PEO) chain were studied in aqueous solutions by means of fully atomistic molecular dynamics simulations. Dendrimers of two generations, 3rd and 4th and at different pH conditions were examined, in order to address issues associated with characteristics pertinent to the shape of the dendrimers in the presence or absence of PEO as well as to the volume fraction of the penetrating solvent molecules and counterions as compared to recent experimental studies. In addition, hydrogen-bonding characteristics such as the intensity and the longevity of intra- and intermolecular hydrogen-bonded pairs are examined for the first time in these systems. It was found that the volume fraction of the penetrating solvent molecules increased upon decrease of pH, but no dependence on the size of the molecules was observed. The density of the solvent within the dendritic interior did not exceed that of the bulk, while the corresponding number of counterions entering the dendrimer boundaries exhibited a marked increase between the 3rd and the 4th generation of the dendrimers. Intramolecular hydrogen bonding was favored at high pH conditions, while intermolecular hydrogen bonding between PAMAM and the solvent or the PEO was significantly enhanced upon protonation of the dendrimer's amines. The presence of PEO imparted appreciable changes in the dendrimer's shape particularly in the physiological pH conditions. In addition, it incurred a decrease in intramolecular hydrogen bonding and acted antagonistically to the formation of water/dendrimer hydrogen bonds. The higher degree of hydrogen bonding between PAMAM and PEO was observed at low pH levels, indicating that under these conditions the formed complexes are expected to be more stable. The findings of the present study were found to be in good agreement with the relevant experimental findings where available, thus assessing the role of several structural and conformational details in the manifested behavior and providing further insight of the effects of non-covalent complexation of PAMAM dendrimers with linear poly(ethylene oxide).

Effect of chain topology on crystallization within nanoporous alumina

NASA Astrophysics Data System (ADS)

Yao, Yang; Suzuki, Yasuhito; Sakai, Takamasa; Seiwert, Jan; Frey, Holger; Steinhart, Martin; Butt, Hans-Juergen; Floudas, George

Polymer topology has inevitable influence on the structure, packing, and dynamic of chains. Herein, we investigate for the first time the impact of polymer architecture on crystallization under 2D confinement, the latter provided by nanoporous alumina (AAO). We employ two poly(ethylene oxide) (PEO) star polymers to study the effect of (i) end groups and (ii) molecular weight on polymer crystallization in the bulk and under confinement. Bulk end groups reduce the crystallization/melting temperatures and the corresponding equilibrium melting point. Under confinement, in the absence of catalyst, homogeneous nucleation prevails as with linear PEOs. The homogeneous nucleation temperatures for the star polymers agree with that of linear ones provided that the arm molecular weight is used instead. Long-range dynamics pertinent to star relaxation are affecting the homogeneous nucleation temperature. On the other hand, the segmental dynamics speed up on confinement. In addition to star PEO, we study the effect of another topology, i.e. hyperbranched PEO, on the nucleation mechanism.

Chain architecture and micellization: A mean-field coarse-grained model for poly(ethylene oxide) alkyl ether surfactants

DOE Office of Scientific and Technical Information (OSTI.GOV)

García Daza, Fabián A.; Mackie, Allan D., E-mail: allan.mackie@urv.cat; Colville, Alexander J.

2015-03-21

Microscopic modeling of surfactant systems is expected to be an important tool to describe, understand, and take full advantage of the micellization process for different molecular architectures. Here, we implement a single chain mean field theory to study the relevant equilibrium properties such as the critical micelle concentration (CMC) and aggregation number for three sets of surfactants with different geometries maintaining constant the number of hydrophobic and hydrophilic monomers. The results demonstrate the direct effect of the block organization for the surfactants under study by means of an analysis of the excess energy and entropy which can be accurately determinedmore » from the mean-field scheme. Our analysis reveals that the CMC values are sensitive to branching in the hydrophilic head part of the surfactant and can be observed in the entropy-enthalpy balance, while aggregation numbers are also affected by splitting the hydrophobic tail of the surfactant and are manifested by slight changes in the packing entropy.« less

Degradation of homogeneous polymer solutions in high shear turbulent pipe flow

NASA Astrophysics Data System (ADS)

Elbing, B. R.; Winkel, E. S.; Solomon, M. J.; Ceccio, S. L.

2009-12-01

This study quantifies degradation of polyethylene oxide (PEO) and polyacrylamide (PAM) polymer solutions in large diameter (2.72 cm) turbulent pipe flow at Reynolds numbers to 3 × 105 and shear rates greater than 105 1/s. The present results support a universal scaling law for polymer chain scission reported by Vanapalli et al. (2006) that predicts the maximum chain drag force to be proportional to Re 3/2, validating this scaling law at higher Reynolds numbers than prior studies. Use of this scaling gives estimated backbone bond strengths from PEO and PAM of 3.2 and 3.8 nN, respectively. Additionally, with the use of synthetic seawater as a solvent the onset of drag reduction occurred at higher shear rates relative to the pure water solvent solutions, but had little influence on the extent of degradation at higher shear rates. These results are significant for large diameter pipe flow applications that use polymers to reduce drag.

NMR study on the network structure of a mixed gel of kappa and iota carrageenans.

PubMed

Hu, Bingjie; Du, Lei; Matsukawa, Shingo

2016-10-05

The temperature dependencies of the (1)H T2 and diffusion coefficient (D) of a mixed solution of kappa-carrageenan and iota-carrageenan were measured by NMR. Rheological and NMR measurements suggested an exponential formation of rigid aggregates of kappa-carrageenan and a gradual formation of fine aggregates of iota-carrageenan during two step increases of G'. The results also suggested that longer carrageenan chains are preferentially involved in aggregation, thus resulting in a decrease in the average Mw of solute carrageenans. The results of diffusion measurements for poly(ethylene oxide) (PEO) suggested that kappa-carrageenan formed thick aggregates that decreased hindrance to PEO diffusion by decreasing the solute kappa-carrageenan concentration in the voids of the aggregated chains, and that iota-carrageenan formed fine aggregates that decreased the solute iota-carrageenan concentration less. DPEO in a mixed solution of kappa-carrageenan and iota-carrageenan suggested two possibilities for the microscopic network structure: an interpenetrating network structure, or micro-phase separation. Copyright © 2016. Published by Elsevier Ltd.

Block copolymer micelles with a dual-stimuli-responsive core for fast or slow degradation.

PubMed

Han, Dehui; Tong, Xia; Zhao, Yue

2012-02-07

We report the design and demonstration of a dual-stimuli-responsive block copolymer (BCP) micelle with increased complexity and control. We have synthesized and studied a new amphiphilic ABA-type triblock copolymer whose hydrophobic middle block contains two types of stimuli-sensitive functionalities regularly and repeatedly positioned in the main chain. Using a two-step click chemistry approach, disulfide and o-nitrobenzyle methyl ester groups are inserted into the main chain, which react to reducing agents and light, respectively. With the end blocks being poly(ethylene oxide), micelles formed by this BCP possess a core that can be disintegrated either rapidly via photocleavage of o-nitrobenzyl methyl esters or slowly through cleavage of disulfide groups by a reducing agent in the micellar solution. This feature makes possible either burst release of an encapsulated hydrophobic species from disintegrated micelles by UV light, or slow release by the action of a reducing agent, or release with combined fast-slow rate profiles using the two stimuli.

Chain architecture and micellization: A mean-field coarse-grained model for poly(ethylene oxide) alkyl ether surfactants

NASA Astrophysics Data System (ADS)

García Daza, Fabián A.; Colville, Alexander J.; Mackie, Allan D.

2015-03-01

Microscopic modeling of surfactant systems is expected to be an important tool to describe, understand, and take full advantage of the micellization process for different molecular architectures. Here, we implement a single chain mean field theory to study the relevant equilibrium properties such as the critical micelle concentration (CMC) and aggregation number for three sets of surfactants with different geometries maintaining constant the number of hydrophobic and hydrophilic monomers. The results demonstrate the direct effect of the block organization for the surfactants under study by means of an analysis of the excess energy and entropy which can be accurately determined from the mean-field scheme. Our analysis reveals that the CMC values are sensitive to branching in the hydrophilic head part of the surfactant and can be observed in the entropy-enthalpy balance, while aggregation numbers are also affected by splitting the hydrophobic tail of the surfactant and are manifested by slight changes in the packing entropy.

Polyethylene Oxide (PEO) and Polyethylene Glycol (PEG) Polymer Sieving Matrix for RNA Capillary Electrophoresis

PubMed Central

Yamaguchi, Yoshinori; Li, Zhenqing; Zhu, Xifang; Liu, Chenchen; Zhang, Dawei; Dou, Xiaoming

2015-01-01

The selection of sieving polymer for RNA fragments separation by capillary electrophoresis is imperative. We investigated the separation of RNA fragments ranged from 100 to 10,000 nt in polyethylene glycol (PEG) and polyethylene oxide (PEO) solutions with different molecular weight and different concentration. We found that the separation performance of the small RNA fragments (<1000 nt) was improved with the increase of polymer concentration, whereas the separation performance for the large ones (>4000 nt) deteriorated in PEG/PEO solutions when the concentration was above 1.0%/0.6%, respectively. By double logarithmic plot of mobility and RNA fragment size, we revealed three migration regimes for RNA in PEG (300-500k) and PEO (4,000k). Moreover, we calculated the smallest resolvable nucleotide length (N min) from the resolution length analysis. PMID:25933347

Adsorption of poly(ethylene succinate) chain onto graphene nanosheets: A molecular simulation.

PubMed

Kelich, Payam; Asadinezhad, Ahmad

2016-09-01

Understanding the interaction between single polymer chain and graphene nanosheets at local and global length scales is essential for it underlies the mesoscopic properties of polymer nanocomposites. A computational attempt was then performed using atomistic molecular dynamics simulation to gain physical insights into behavior of a model aliphatic polyester, poly(ethylene succinate), single chain near graphene nanosheets, where the effects of the polymer chain length, graphene functionalization, and temperature on conformational properties of the polymer were studied comparatively. Graphene functionalization was carried out through extending the parameters set of an all-atom force field. The results showed a significant conformational transition of the polymer chain from three-dimensional statistical coil, in initial state, to two-dimensional fold, in final state, during adsorption on graphene. The conformational order, overall shape, end-to-end separation statistics, and mobility of the polymer chain were found to be influenced by the graphene functionalization, temperature, and polymer chain length. Furthermore, the polymer chain dynamics mode during adsorption on graphene was observed to transit from normal diffusive to slow subdiffusive mode. The findings from this computational study could shed light on the physics of the early stages of aliphatic polyester chain organization induced by graphene. Copyright © 2016 Elsevier Inc. All rights reserved.

Processable conductive graphene/polyethylene nanocomposites: Effects of graphene dispersion and polyethylene blending with oxidized polyethylene on rheology and microstructure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Iqbal, Muhammad Z.; Abdala, Ahmed A.; Mittal, Vikas

Poor dispersion of graphene in non-polar polymer matrices creates composites with limited applications. A method to improve the dispersion of graphene in polyethylene (PE) via blending PE with oxidized PE (OPE) is examined. Graphene was produced by simultaneous thermal exfoliation and reduction of graphite oxide. Nanocomposites of graphene with PE as well as graphene with PE/OPE-blends were prepared by solvent blending. Improved dispersion of graphene in PE/OPE blends substantially decreases percolation from both rheological (0.3 vol%) and electrical (0.13 vol%) measurements compared to neat PE nanocomposites (1 and 0.29 vol%), respectively. A universal Brownian dispersion of graphene in polymers wasmore » concluded similar to that of nanotubes, following the Doi-Edwards theory. Micromechanical models, such as Mori-Tanaka and Halpin-Tsai models, modeled the mechanical properties of the nanocomposites. The nanocomposites microstructure, studied by small angle x-ray scattering, confirmed better dispersion of graphene at lower loadings and the formation of surface fractals in the blend/graphene nanocomposites; whereas only mass fractals were observed in neat PE/graphene nanocomposites.« less

Wear Analysis in THA Utilizing Oxidized Zirconium and Crosslinked Polyethylene

PubMed Central

Garvin, Kevin L.; Mangla, Jimmi; Murdoch, Nathan; Martell, John M.

2008-01-01

Oxidized zirconium, a material with a ceramic surface on a metal substrate, and highly cross-linked polyethylene are two materials developed to reduce wear. We measured in vivo femoral head penetration in patients with these advanced bearings. We hypothesized the linear wear rates would be lower than those published for cobalt-chrome and standard polyethylene. We retrospectively reviewed a select series of 56 THAs in a relatively young, active patient population utilizing oxidized zirconium femoral heads and highly cross-linked polyethylene acetabular liners. Femoral head penetration was determined using the Martell computerized edge-detection method. All patients were available for 2-year clinical and radiographic followup. True linear wear was 4 μm/year (95% confidence intervals, ± 59 μm/year). The early wear rates in this cohort of relatively young, active patients were low and we believe justify the continued study of these alternative bearing surfaces. Level of Evidence: Level IV, therapeutic study. See the Guidelines for Authors for a complete description of levels of evidence. PMID:18946711

Surface modification of amorphous substrates by disulfide derivatives: A photo-assisted route to direct functionalization of chalcogenide glasses

NASA Astrophysics Data System (ADS)

Amalric, Julien; Marchand-Brynaert, Jacqueline

2011-12-01

A novel route for chalcogenide glass surface modification is disclosed. The formation of an organic monolayer from disulfide derivatives is studied on two different glasses of formula GexAsySez by water contact angle measurement, X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy in attenuated total reflection mode (FTIR-ATR). The potential anchoring group is the disulfide functionality. Since thioctic acid derivatives absorb around 335 nm, an irradiation step is included, in order to favor S-S disruption. Three types of disulfide compounds are grafted onto small glass breaks for contact angle and XPS analyses. The results show effective changes of surface state. According to contact angle measurement, the deposited organic layer functionalized by a small polyethylene glycol chain leads to a more hydrophilic surface, long alkyl chain or a perfluorinated carbon chain leads to a more hydrophobic surface. XPS shows the presence at the surface of an organic layer with sulfur and ethylene oxide chains, or augmentation of organic carbons or fluorine and Csbnd F bonds. The photo-assisted grafting of the disulfides onto an ATR prism made of chalcogenide glass shows that this surface modification process does not affect infrared transparency, despite UV treatment, and accurate structural analysis can be performed.

Importance of poly(ethylene glycol) conformation for the synthesis of silver nanoparticles in aqueous solution

USDA-ARS?s Scientific Manuscript database

In the formation of silver nanoparticles (NPs) using silver nitrate in a poly(ethylene glycol) (PEG) aqueous solution, which acts as both a reducing and stabilizing agent, the PEG chain structure was found to play a significant role. Even though PEG 100 (100 kg/mol) has limited reducing sites of hyd...

Enhancing the specificity of polymerase chain reaction by graphene oxide through surface modification: zwitterionic polymer is superior to other polymers with different charges.

PubMed

Zhong, Yong; Huang, Lihong; Zhang, Zhisen; Xiong, Yunjing; Sun, Liping; Weng, Jian

Graphene oxides (GOs) with different surface characteristics, such as size, reduction degree and charge, are prepared, and their effects on the specificity of polymerase chain reaction (PCR) are investigated. In this study, we demonstrate that GO with a large size and high reduction degree is superior to small and nonreduced GO in enhancing the specificity of PCR. Negatively charged polyacrylic acid (PAA), positively charged polyacrylamide (PAM), neutral polyethylene glycol (PEG) and zwitterionic polymer poly(sulfobetaine) (pSB) are used to modify GO. The PCR specificity-enhancing ability increases in the following order: GO-PAA < GO-PAM < GO-PEG < GO-pSB. Thus, zwitterionic polymer-modified GO is superior to other GO derivatives with different charges in enhancing the specificity of PCR. GO derivatives are also successfully used to enhance the specificity of PCR for the amplification of human mitochondrial DNA using blood genomic DNA as template. Molecular dynamics simulations and molecular docking are performed to elucidate the interaction between the polymers and Pfu DNA polymerase. Our data demonstrate that the size, reduction degree and surface charge of GO affect the specificity of PCR. Based on our results, zwitterionic polymer-modified GO may be used as an efficient additive for enhancing the specificity of PCR.

Block ionomer complexes as prospective nanocontainers for drug delivery.

PubMed

Oh, Kyung T; Bronich, Tatiana K; Bromberg, Lev; Hatton, T Alan; Kabanov, Alexander V

2006-09-28

Nanosized environmentally responsive materials are of special interest for various applications, including drug delivery. Block ionomer complexes (BIC) composed of graft-comb copolymers of Pluronic and poly(acrylic acid) (Pluronic-PAA) and a model cationic surfactant, hexadecyltrimethylammonium bromide (HTAB), were synthesized by mixing the polymer and surfactant in aqueous media. According to TEM, the resulting BIC represented spherical particles of nanoscale size (50 to 100 nm). The stability of the BIC in the aqueous dispersion depended on the lengths of the hydrophilic poly(ethylene oxide) and hydrophobic poly(propylene oxide) chains in Pluronic molecules as well as on the surface charge of the resulting complexes. The latter was controlled by changing the ratio of the Pluronic-PAA and HTAB in the BIC and by changing the pH due to reversible ionization of the PAA chains. The acidification of the media below pH 6.0 resulted in the appearance of a strong positive charge on the BIC, which in the intracellular environment can trigger interaction of such BIC with the cell membranes. An efficient solubilization of a model hydrophobic molecule, Sudan III, and a drug, Etoposide, in such BIC was demonstrated with the loading capacities of about 6 to 15% by weight of the dispersed complex. Overall, these BIC wield a promise as environmentally responsive nanocarriers for pharmaceuticals.

Fluorescence probe studies of the interactions between poly(oxyethylene) and surfactant micelles and microemulsion droplets in aqueous solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zana, R.; Lianos, P.; Lang, J.

1985-01-03

The interaction between poly(ethylene oxide) (POE) and the aggregates present in micellar solutions of sodium dodecyl sulfate (SDS), mixed micellar solutions of SDS + 1-pentanol, and oil in water microemulsions made of SDS + 1-pentanol + oil (dodecane or toluene) has been investigated by means of fluorescence probing methods. It is shown that the addition of POE results in a decrease of the aggregation number of SDS in the aggregates present in all the systems investigated. Most likely this decrease is due to the adsorption of the POE chain in the micelle palisade layer and the ensuing increase of micellemore » ionization. 22 references, 5 figures, 2 tables.« less

Crystallization in diblock copolymer thin films at different degrees of supercooling

NASA Astrophysics Data System (ADS)

Darko, C.; Botiz, I.; Reiter, G.; Breiby, D. W.; Andreasen, J. W.; Roth, S. V.; Smilgies, D.-M.; Metwalli, E.; Papadakis, C. M.

2009-04-01

The crystalline structures in thin films of polystyrene- b -poly(ethylene oxide) (PS- b -PEO) diblock copolymers were studied in dependence on the degree of supercooling. Atomic force microscopy showed that the crystalline domains (lamellae) consist of grains, which are macroscopic at low and intermediate degrees of supercooling, but of submicrometer size for strong supercooling. Using grazing-incidence wide-angle x-ray scattering, we could determine the grain orientation distribution function which shows that the chain stems are perpendicular to the lamellae at low supercooling, but tilted at intermediate and strong supercooling. These results suggest that, at intermediate and strong supercooling, the crystalline PEO lamellae do not grow homogeneously, but by the formation of small crystallites at the growth front.

Modeling and simulation of Li-ion conduction in poly(ethylene oxide)

NASA Astrophysics Data System (ADS)

Gitelman, L.; Israeli, M.; Averbuch, A.; Nathan, M.; Schuss, Z.; Golodnitsky, D.

2007-12-01

Polyethylene oxide (PEO) containing a lithium salt (e.g., LiI) serves as a solid polymer electrolyte (SPE) in thin-film batteries and its ionic conductivity is a key parameter of their performance. We model and simulate Li + ion conduction in a single PEO molecule. Our simplified stochastic model of ionic motion is based on an analogy between protein channels of biological membranes that conduct Na +, K +, and other ions, and the PEO helical chain that conducts Li + ions. In contrast with protein channels and salt solutions, the PEO is both the channel and the solvent for the lithium salt (e.g., LiI). The mobile ions are treated as charged spherical Brownian particles. We simulate Smoluchowski dynamics in channels with a radius of ca. 0.1 nm and study the effect of stretching and temperature on ion conductivity. We assume that each helix (molecule) forms a random angle with the axis between these electrodes and the polymeric film is composed of many uniformly distributed oriented boxes that include molecules with the same direction. We further assume that mechanical stretching aligns the molecular structures in each box along the axis of stretching (intra-box alignment). Our model thus predicts the PEO conductivity as a function of the stretching, the salt concentration and the temperature. The computed enhancement of the ionic conductivity in the stretch direction is in good agreement with experimental results. The simulation results are also in qualitative agreement with recent theoretical and experimental results.

Biodegradable thermoresponsive polymeric magnetic nanoparticles: a new drug delivery platform for doxorubicin

NASA Astrophysics Data System (ADS)

Andhariya, Nidhi; Chudasama, Bhupendra; Mehta, R. V.; Upadhyay, R. V.

2011-04-01

The use of nanoparticles as drug delivery systems for anticancer therapeutics has great potential to revolutionize the future of cancer therapy. The aim of this study is to construct a novel drug delivery platform comprising a magnetic core and biodegradable thermoresponsive shell of tri-block-copolymer. Oleic acid-coated Fe3O4 nanoparticles and hydrophilic anticancer drug "doxorubicin" are encapsulated with PEO-PLGA-PEO (polyethylene oxide-poly d, l lactide-co-glycolide-polyethylene oxide) tri-block-copolymer. Structural, magnetic, and physical properties of Fe3O4 core are determined by X-ray diffraction, vibrating sample magnetometer, and transmission electron microscopy techniques, respectively. The hydrodynamic size of composite nanoparticles is determined by dynamic light scattering and is found to be 36.4 nm at 25 °C. The functionalization of magnetic core with various polymeric chain molecules and their weight proportions are determined by Fourier transform infrared spectroscopy and thermogravimetric analysis, respectively. Encapsulation of doxorubicin into the polymeric magnetic nanoparticles, its loading efficiency, and kinetics of drug release are investigated by UV-vis spectroscopy. The loading efficiency of drug is 89% with a rapid release for the initial 7 h followed by the sustained release over a period of 36 h. The release of drug is envisaged to occur in response to the physiological temperature by deswelling of thermoresponsive PEO-PLGA-PEO block-copolymer. This study demonstrates that temperature can be exploited successfully as an external parameter to control the release of drug.

The influence of polymer architecture on the assembly of poly(ethylene oxide) grafted C60 fullerene clusters in aqueous solution: a molecular dynamics simulation study.

PubMed

Hooper, Justin B; Bedrov, Dmitry; Smith, Grant D

2009-03-28

The effect of polymer architecture on the aggregation behavior of C60 fullerenes tethered with a single chain of poly(ethylene oxide) (PEO) in aqueous solution has been investigated using coarse-grained, implicit solvent molecular dynamics simulations. The PEO-grafted fullerenes were comprised of a single tether of 60 repeat units represented as a linear polymer, a three-arm star (20 repeat units/arm) or a six-arm star (10 repeat units/arm). Additionally, the influence of arm length on self-assembly of the PEO-fullerene conjugates was investigated for the three-arm stars. Self-assembly is driven by favorable fullerene-fullerene and fullerene-PEO interactions. Our simulations reveal that it should be possible to control the size and geometry of the self-assembled fullerene aggregates in water through variation of PEO architecture and PEO molecular weight. We found that aggregate size and shape could be understood qualitatively in terms of the packing parameter concept that has been employed for diblock polymer and surfactant self-assembly. Higher molecular weight PEO (longer arms) and more compact PEO (more arms for the same molecular weight) resulted in greater steric repulsion between fullerenes, engendering greater aggregate surface curvature and hence the formation of smaller, more spherically shaped aggregates. Finally, weak attractive interactions between PEO and the fullerenes were found to play an important role in determining aggregate shape, size and the dynamics of self-assembly.

Molecular dynamics simulation study of the structure of poly(ethylene oxide) brushes on nonpolar surfaces in aqueous solution.

PubMed

Bedrov, Dmitry; Smith, Grant D

2006-07-04

The structure of poly(ethylene oxide) (PEO, M(w) = 526) brushes of various grafting density (sigma) on nonpolar graphite and hydrophobic (oily) surfaces in aqueous solution has been studied using atomistic molecular dynamics simulations. Additionally, the influence of PEO-surface interactions on the brush structure was investigated by systematically reducing the strength of the (dispersion) attraction between PEO and the surfaces. PEO chains were found to adsorb strongly to the graphite surface due primarily to the relative strength of dispersion interactions between PEO and the atomically dense graphite compared to those between water and graphite. For the oily surface, PEO-surface and water-surface dispersion interactions are much weaker, greatly reducing the energetic driving force for PEO adsorption. This reduction is mediated to some extent by a hydrophobic driving force for PEO adsorption on the oily surface. Reduction in the strength of PEO-surface attraction results in reduced adsorption of PEO for both surfaces, with the effect being much greater for the graphite surface where the strong PEO-surface dispersion interactions dominate. At high grafting density (sigma approximately 1/R(g)(2)), the PEO density profiles exhibited classical brush behavior and were largely independent of the strength of the PEO-surface interaction. With decreasing grafting density (sigma < 1/R(g)(2)), coverage of the surface by PEO requires an increasingly large fraction of PEO segments resulting in a strong dependence of the PEO density profile on the nature of the PEO-surface interaction.

Jeffamine® based polymers as highly conductive polymer electrolytes and cathode binder materials for battery application

NASA Astrophysics Data System (ADS)

Aldalur, Itziar; Zhang, Heng; Piszcz, Michał; Oteo, Uxue; Rodriguez-Martinez, Lide M.; Shanmukaraj, Devaraj; Rojo, Teofilo; Armand, Michel

2017-04-01

We report a simple synthesis route towards a new type of comb polymer material based on polyether amines oligomer side chains (i.e., Jeffamine® compounds) and a poly(ethylene-alt-maleic anhydride) backbone. Reaction proceeds by imide ring formation through the NH2 group allowing for attachment of side chains. By taking advantage of the high configurational freedoms and flexibility of propylene oxide/ethylene oxide units (PO/EO) in Jeffamine® compounds, novel polymer matrices were obtained with good elastomeric properties. Fully amorphous solid polymer electrolytes (SPEs) based on lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and Jeffamine®-based polymer matrices show low glass transition temperatures around -40 °C, high ionic conductivities and good electrochemical stabilities. The ionic conductivities of Jeffamine-based SPEs (5.3 × 10-4 S cm-1 at 70 °C and 4.5 × 10-5 S cm-1 at room temperature) are higher than those of the conventional SPEs comprising of LiTFSI and linear poly(ethylene oxide) (PEO), due to the amorphous nature and the high concentration of mobile end-groups of the Jeffamine-based polymer matrices rather than the semi-crystalline PEO The feasibility of Jeffamine-based compounds in lithium metal batteries is further demonstrated by the implementation of Jeffamine®-based polymer as a binder for cathode materials, and the stable cycling of Li|SPE|LiFePO4 and Li|SPE|S cells using Jeffamine-based SPEs.

Biodegradability of degradable plastic waste.

PubMed

Agamuthu, P; Faizura, Putri Nadzrul

2005-04-01

Plastic waste constitutes the third largest waste volume in Malaysian municipal solid waste (MSW), next to putrescible waste and paper. The plastic component in MSW from Kuala Lumpur averages 24% (by weight), whereas the national mean is about 15%. The 144 waste dumps in the country receive about 95% of the MSW, including plastic waste. The useful life of the landfills is fast diminishing as the plastic waste stays un-degraded for more than 50 years. In this study the compostability of polyethylene and pro-oxidant additive-based environmentally degradable plastics (EDP) was investigated. Linear low-density polyethylene (LLDPE) samples exposed hydrolytically or oxidatively at 60 degrees C showed that the abiotic degradation path was oxidative rather than hydrolytic. There was a weight loss of 8% and the plastic has been oxidized as shown by the additional carbonyl group exhibited in the Fourier transform infra red (FTIR) Spectrum. Oxidation rate seemed to be influenced by the amount of pro-oxidant additive, the chemical structure and morphology of the plastic samples, and the surface area. Composting studies during a 45-day experiment showed that the percentage elongation (reduction) was 20% for McD samples [high-density polyethylene, (HDPE) with 3% additive] and LL samples (LLDPE with 7% additive) and 18% reduction for totally degradable plastic (TDP) samples (HDPE with 3% additive). Lastly, microbial experiments using Pseudomonas aeroginosa on carbon-free media with degradable plastic samples as the sole carbon source, showed confirmatory results. A positive bacterial growth and a weight loss of 2.2% for degraded polyethylene samples were evident to show that the degradable plastic is biodegradable.

Release mechanisms of acetaminophen from polyethylene oxide/polyethylene glycol matrix tablets utilizing magnetic resonance imaging.

PubMed

Tajiri, Tomokazu; Morita, Shigeaki; Sakamoto, Ryosaku; Suzuki, Masazumi; Yamanashi, Shigeyuki; Ozaki, Yukihiro; Kitamura, Satoshi

2010-08-16

Release mechanism of acetaminophen (AAP) from extended-release tablets of hydrogel polymer matrices containing polyethylene oxide (PEO) and polyethylene glycol (PEG) were achieved using flow-through cell with magnetic resonance imaging (MRI). The hydrogel forming abilities are observed characteristically and the layer thickness which is corresponding to the diffusion length of AAP has a good correlation with the drug release profiles. In addition, polymeric erosion contribution to AAP releasing from hydrogel matrix tablets was directly quantified using size-exclusion chromatography (SEC). The matrix erosion profile indicates that the PEG erosion kinetic depends primarily on the composition ratio of PEG to PEO. The present study has confirmed that the combination of in situ MRI and SEC should be well suited to investigate the drug release mechanisms of hydrogel matrix such as PEO/PEG. Copyright (c) 2010 Elsevier B.V. All rights reserved.

Dynamic mechanical properties of hydroxyapatite/polyethylene oxide nanocomposites: characterizing isotropic and post-processing microstructures

NASA Astrophysics Data System (ADS)

Shofner, Meisha; Lee, Ji Hoon

2012-02-01

Compatible component interfaces in polymer nanocomposites can be used to facilitate a dispersed morphology and improved physical properties as has been shown extensively in experimental results concerning amorphous matrix nanocomposites. In this research, a block copolymer compatibilized interface is employed in a semi-crystalline matrix to prevent large scale nanoparticle clustering and enable microstructure construction with post-processing drawing. The specific materials used are hydroxyapatite nanoparticles coated with a polyethylene oxide-b-polymethacrylic acid block copolymer and a polyethylene oxide matrix. Two particle shapes are used: spherical and needle-shaped. Characterization of the dynamic mechanical properties indicated that the two nanoparticle systems provided similar levels of reinforcement to the matrix. For the needle-shaped nanoparticles, the post-processing step increased matrix crystallinity and changed the thermomechanical reinforcement trends. These results will be used to further refine the post-processing parameters to achieve a nanocomposite microstructure with triangulated arrays of nanoparticles.

Surface grafting of cellulose nanocrystals with poly(ethylene oxide) in aqueous media.

PubMed

Kloser, Elisabeth; Gray, Derek G

2010-08-17

Aqueous suspensions of poly(ethylene oxide)-grafted nanocrystalline cellulose (PEO-grafted NCC) were prepared in order to achieve steric instead of electrostatic stabilization. A two-step process was employed: in the first step NCC suspensions prepared by sulfuric acid hydrolysis were desulfated with sodium hydroxide, and in the second step the surfaces of the crystals were functionalized with epoxy-terminated poly(ethylene oxide) (PEO epoxide) under alkaline conditions. The PEO-grafted samples were analyzed by conductometric titration, ATR-IR, solid-state NMR, MALDI-TOF MS, SEC MALLS, and AFM. The covalent nature of the linkage was confirmed by weight increase and MALDI-TOF analysis. The PEO-grafted cellulose nanocrystals (CNCs) formed a stable colloidal suspension that remained well dispersed, while the desulfated nanoparticles aggregated and precipitated. Upon concentration of the PEO-grafted aqueous NCC suspension, a chiral nematic phase was observed.

Immobilization of isolated FI catalyst on polyhedral oligomeric silsesquioxane-functionalized silica for the synthesis of weakly entangled polyethylene.

PubMed

Li, Wei; Yang, Huaqin; Zhang, Jingjing; Mu, Jingshan; Gong, Dirong; Wang, Xiaodong

2016-09-25

Polyhedral oligomeric silsesquioxanes (POSSs) were adsorbed on methylaluminoxane-activated silica for the immobilization of fluorinated bis(phenoxyimine)Ti complexes (FI catalyst). These POSSs have been characterized as horizontal spacers isolating the active sites and hindering the chain overlap in polymerization. The heterogeneous catalyst exhibits considerable activity in the synthesis of weakly entangled polyethylene.

Supramolecular recognition control of polyethylene glycol modified N-doped graphene quantum dots: tunable selectivity for alkali and alkaline-earth metal ions.

PubMed

Yang, Siwei; Sun, Jing; Zhu, Chong; He, Peng; Peng, Zheng; Ding, Guqiao

2016-02-07

The graphene quantum dot based fluorescent probe community needs unambiguous evidence about the control on the ion selectivity. In this paper, polyethylene glycol modified N-doped graphene quantum dots (PN-GQDs) were synthesized by alkylation reaction between graphene quantum dots and organic halides. We demonstrate the tunable selectivity and sensitivity by controlling the supramolecular recognition through the length and the end group size of the polyether chain on PN-GQDs. The relationship formulae between the selectivity/detection limit and polyether chains are experimentally deduced. The polyether chain length determines the interaction between the PN-GQDs and ions with different ratios of charge to radius, which in turn leads to a good selectivity control. Meanwhile the detection limit shows an exponential growth with the size of end groups of the polyether chain. The PN-GQDs can be used as ultrasensitive and selective fluorescent probes for Li(+), Na(+), K(+), Mg(2+), Ca(2+) and Sr(2+), respectively.

Selective laser sintering of ultra high molecular weight polyethylene for clinical applications.

PubMed

Rimell, J T; Marquis, P M

2000-01-01

Rapid prototyping is a relatively new technology, which although prominent in the engineering industry is only just starting to make an impact in the medical field. Its current medical uses are mainly confined to surgical planning and teaching, but the technology also has the potential to allow for patient-tailored prostheses. The work reported here describes the application of a simplified selective laser sintering apparatus with ultra high molecular weight polyethylene (UHMWPE). The morphology and chemistry of the starting powders and lased material have been characterized using Fourier Transform Infra Red spectroscopy and a combination of light and scanning electron microscopy. It was found that solid linear continuous bodies could be formed, but material shrinkage caused problems when trying to form sheet-like structures. The porosity of the formed material was also a concern. The material exposed to the laser beam was shown to have undergone degradation in terms of chain scission, cross-linking, and oxidation. It has been concluded that to apply this technology to the fabrication of UHMWPE devices requires the development of improved starting powders, in particular with increased density. Copyright 2000 John Wiley & Sons, Inc.

Super Soft All-Ethylene Oxide Polymer Electrolyte for Safe All-Solid Lithium Batteries

PubMed Central

Porcarelli, Luca; Gerbaldi, Claudio; Bella, Federico; Nair, Jijeesh Ravi

2016-01-01

Here we demonstrate that by regulating the mobility of classic −EO− based backbones, an innovative polymer electrolyte system can be architectured. This polymer electrolyte allows the construction of all solid lithium-based polymer cells having outstanding cycling behaviour in terms of rate capability and stability over a wide range of operating temperatures. Polymer electrolytes are obtained by UV-induced (co)polymerization, which promotes an effective interlinking between the polyethylene oxide (PEO) chains plasticized by tetraglyme at various lithium salt concentrations. The polymer networks exhibit sterling mechanical robustness, high flexibility, homogeneous and highly amorphous characteristics. Ambient temperature ionic conductivity values exceeding 0.1 mS cm−1 are obtained, along with a wide electrochemical stability window (>5 V vs. Li/Li+), excellent lithium ion transference number (>0.6) as well as interfacial stability. Moreover, the efficacious resistance to lithium dendrite nucleation and growth postulates the implementation of these polymer electrolytes in next generation of all-solid Li-metal batteries working at ambient conditions. PMID:26791572

Role of oxygen functional groups in reduced graphene oxide for lubrication

PubMed Central

Gupta, Bhavana; Kumar, Niranjan; Panda, Kalpataru; Kanan, Vigneshwaran; Joshi, Shailesh; Visoly-Fisher, Iris

2017-01-01

Functionalized and fully characterized graphene-based lubricant additives are potential 2D materials for energy-efficient tribological applications in machine elements, especially at macroscopic contacts. Two different reduced graphene oxide (rGO) derivatives, terminated by hydroxyl and epoxy-hydroxyl groups, were prepared and blended with two different molecular weights of polyethylene glycol (PEG) for tribological investigation. Epoxy-hydroxyl-terminated rGO dispersed in PEG showed significantly smaller values of the friction coefficient. In this condition, PEG chains intercalate between the functionalized graphene sheets, and shear can take place between the PEG and rGO sheets. However, the friction coefficient was unaffected when hydroxyl-terminated rGO was coupled with PEG. This can be explained by the strong coupling between graphene sheets through hydroxyl units, causing the interaction of PEG with the rGO to be non- effective for lubrication. On the other hand, antiwear properties of hydroxyl-terminated rGO were significantly enhanced compared to epoxy-hydroxyl functionalized rGO due to the integrity of graphene sheet clusters. PMID:28344337

Super Soft All-Ethylene Oxide Polymer Electrolyte for Safe All-Solid Lithium Batteries

NASA Astrophysics Data System (ADS)

Porcarelli, Luca; Gerbaldi, Claudio; Bella, Federico; Nair, Jijeesh Ravi

2016-01-01

Here we demonstrate that by regulating the mobility of classic -EO- based backbones, an innovative polymer electrolyte system can be architectured. This polymer electrolyte allows the construction of all solid lithium-based polymer cells having outstanding cycling behaviour in terms of rate capability and stability over a wide range of operating temperatures. Polymer electrolytes are obtained by UV-induced (co)polymerization, which promotes an effective interlinking between the polyethylene oxide (PEO) chains plasticized by tetraglyme at various lithium salt concentrations. The polymer networks exhibit sterling mechanical robustness, high flexibility, homogeneous and highly amorphous characteristics. Ambient temperature ionic conductivity values exceeding 0.1 mS cm-1 are obtained, along with a wide electrochemical stability window (>5 V vs. Li/Li+), excellent lithium ion transference number (>0.6) as well as interfacial stability. Moreover, the efficacious resistance to lithium dendrite nucleation and growth postulates the implementation of these polymer electrolytes in next generation of all-solid Li-metal batteries working at ambient conditions.

Macroscopic lateral heterogeneity observed in a laterally mobile immiscible mixed polyelectrolyte-neutral polymer brush

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Hoyoung; Tsouris, Vasilios; Lim, Yunho

We studied mixed poly(ethylene oxide) (PEO) and poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) brushes. The question we attempted to answer was: when the chain grafting points are laterally mobile, how will this lateral mobility influence the structure and phase behavior of the mixed brush? Three different model mixed PEO/PDMAEMA brush systems were prepared: (1) a laterally mobile mixed brush by spreading onto the air–water interface a mixture of poly(ethylene oxide)–poly(n-butyl acrylate) (PEO–PnBA) and poly(2-(dimethylamino)ethyl methacrylate)–poly(n-butyl acrylate) (PDMAEMA–PnBA) diblock copolymers (the specific diblock copolymers used will be denoted as PEO 113–PnBA 100 and PDMAEMA 118–PnBA 100, where the subscripts refer to the number-average degreesmore » of polymerization of the individual blocks), (2) a mobility-restricted (inseparable) version of the above mixed brush prepared using a PEO–PnBA–PDMAEMA triblock copolymer (denoted as PEO 113–PnBA 89–PDMAEMA 120) having respective brush molecular weights matched with those of the diblock copolymers, and (3) a different laterally mobile mixed PEO and PDMAEMA brush prepared from a PEO 113–PnBA 100 and PDMAEMA 200–PnBA 103 diblock copolymer combination, which represents a further more height-mismatched mixed brush situation than described in (1). These three mixed brush systems were investigated by surface pressure–area isotherm and X-ray (XR) reflectivity measurements. These experimental data were analyzed within the theoretical framework of a continuum self-consistent field (SCF) polymer brush model. The combined experimental and theoretical results suggest that the mobile mixed brush derived using the PEO 113–PnBA 100 and PDMAEMA 118–PnBA 100 combination (i.e., mixed brush System #1) undergoes a lateral macroscopic phase separation at high chain grafting densities, whereas the more height-mismatched system (System #3) is only microscopically phase separated under comparable brush density conditions even though the lateral mobility of the grafted chains is unrestricted. The macroscopic phase separation observed in the laterally mobile mixed brush system is in contrast with the microphase separation behavior commonly observed in two-dimensional laterally mobile charged small molecule mixtures. Further study is needed to determine the detailed morphologies of the macro- and microphase-separated mixed PEO/PDMAEMA brushes.« less

Molecular dynamics simulations of steady-state crystal growth and homogeneous nucleation in polyethylene-like polymer

NASA Astrophysics Data System (ADS)

Yamamoto, Takashi

2008-11-01

Molecular mechanisms of crystal growth and homogeneous nucleation from the melt of polyethylene-like linear polymer are investigated by molecular dynamics simulations. The present paper is aimed at extending our previous work with respect to the system size and the boundary condition, thereby enabling detailed studies on the structures of sufficiently large lamellae and fully equilibrated melt. Lamellae of uniform thickness but with marked tapered edges are found to grow at constant velocity from the substrate. Three-dimensional shape of the growing lamellae exhibits peculiar undulation at the growth front, the origin of which is suggested to be the inhomogeneous thickness distribution within the lamellae. Trajectories of chains crystallizing onto the growth front reveal an unexpected pathway for chain folding, where a partially attached chain stem forms a new fold by plunging its head back into a neighboring stem position through slithering snake motions of the chain. Detailed statistics of folds and cilia show that the folds are rather neat and mostly make re-entries into the nearest or the second or third nearest neighboring stem positions, whereas the cilia are generally short but with a small number of longer cilia forming thick amorphous layers. Structure of supercooled melt investigated versus temperature reveals that, at moderate degree of supercooling, the overall chain conformation remains Gaussian random coil but the persistent length of chains increases monotonically with increasing supercooling. Exceptions are at the largest supercooling where homogeneous nucleation takes place; usual melt structure becomes rapidly unstable and emerges many crystallites of random orientations. During early 10-20ns after the quench, density of melt, radius of gyration of chains, and fraction of kinked bonds show marked alterations. These structural changes are highly cooperative and are considered simply due to the emergence of many embryonic crystals in the melt. Conformations of the chains forming nuclei are also traced to reveal that the homogeneous nuclei are fringed micelle like aggregates of chains, but the chains as a whole have folded conformations, which are similar to those reported in previous simulations on a single polyethylene in a vacuum.

Heterogeneous chain dynamics and aggregate lifetimes in precise acid-containing polyethylenes: Experiments and simulations

DOE PAGES

Middleton, L. Robert; Tarver, Jacob D.; Cordaro, Joseph; ...

2016-11-10

Melt state dynamics for a series of strictly linear polyethylenes with precisely spaced associating functional groups were investigated. The periodic pendant acrylic acid groups form hydrogen-bonded acid aggregates within the polyethylene (PE) matrix. The dynamics of these nanoscale heterogeneous morphologies were investigated from picosecond to nanosecond timescales by both quasi-elastic neutron scattering (QENS) measurements and fully atomistic molecular dynamics (MD) simulations. Two dynamic processes were observed. The faster dynamic processes which occur at the picosecond timescales are compositionally insensitive and indicative of spatially restricted local motions. The slower dynamic processes are highly composition dependent and indicate the structural relaxation ofmore » the polymer backbone. Higher acid contents, or shorter PE spacers between pendant acid groups, slow the structural relaxation timescale and increase the stretching parameter (β) of the structural relaxation. Additionally, the dynamics of specific hydrogen atom positions along the backbone correlate structural heterogeneity imposed by the associating acid groups with a mobility gradient along the polymer backbone. At time intervals (<2 ns), the mean-squared displacements for the four methylene groups closest to the acid groups are up to 10 times smaller than those of methylene groups further from the acid groups. At longer timescales acid aggregates rearrange and the chain dynamics of the slow, near-aggregate regions and the faster bridge regions converge, implying a characteristic timescale for the passage of chains between aggregates. As a result, the characterization of the nanoscale chain dynamics in these associating polymer systems both provides validation of simulation force fields and provides understanding of heterogeneous chain dynamics in associating polymers.« less

Preservation of Mercury in Polyethylene Containers.

ERIC Educational Resources Information Center

Piccolino, Samuel Paul

1983-01-01

Reports results of experiments favoring use of 0.5 percent nitric acid with an oxidant (potassium dichromate or potassium permanganate) to preserve samples in polyethylene containers for mercury analysis. Includes procedures used and statistical data obtained from the experiments. (JN)

Sequential pyrolysis of plastic to recover polystyrene HCL and terephthalic acid

DOEpatents

Evans, Robert J.; Chum, Helena L.

1995-01-01

A process of pyrolyzing plastic waste feed streams containing polyvinyl chloride, polyethylene terephthalate, polystyrene and polyethylene to recover polystyrene HCl and terephthalic acid comprising: heating the plastic waste feed stream to a first temperature; adding an acid or base catalyst on an oxide or carbonate support; heating the plastic waste feed stream to pyrolyze polyethylene terephthalate and polyvinyl chloride; separating terephthalic acid or HCl; heating to a second temperature to pyrolyze polystyrene; separating styrene; heating the waste feed stream to a third temperature to pyrolyze polyethylene; and separating hydrocarbons.

Inhibition of bacterial and leukocyte adhesion under shear stress conditions by material surface chemistry.

PubMed

Patel, Jasmine D; Ebert, Michael; Stokes, Ken; Ward, Robert; Anderson, James M

2003-01-01

Biomaterial-centered infections, initiated by bacterial adhesion, persist due to a compromised host immune response. Altering implant materials with surface modifying endgroups (SMEs) may enhance their biocompatibility by reducing bacterial and inflammatory cell adhesion. A rotating disc model, which generates shear stress within physiological ranges, was used to characterize adhesion of leukocytes and Staphylococcus epidermidis on polycarbonate-urethanes and polyetherurethanes modified with SMEs (polyethylene oxide, fluorocarbon and dimethylsiloxane) under dynamic flow conditions. Bacterial adhesion in the absence of serum was found to be mediated by shear stress and surface chemistry, with reduced adhesion exhibited on materials modified with polydimethylsiloxane and polyethylene oxide SMEs. In contrast, bacterial adhesion was enhanced on materials modified with fluorocarbon SMEs. In the presence of serum, bacterial adhesion was primarily neither material nor shear dependent. However, bacterial adhesion in serum was significantly reduced to < or = 10% compared to adhesion in serum-free media. Leukocyte adhesion in serum exhibited a shear dependency with increased adhesion occurring in regions exposed to lower shear-stress levels of < or = 7 dyne/cm2. Additionally, polydimethylsiloxane and polyethylene oxide SMEs reduced leukocyte adhesion on polyether-urethanes. In conclusion, these results suggest that surface chemistry and shear stress can mediate bacterial and cellular adhesion. Furthermore, materials modified with polyethylene oxide SMEs are capable of inhibiting bacterial adhesion, consequently minimizing the probability of biomaterial-centered infections.

Comparative toxicity of pristine graphene oxide and its carboxyl, imidazole or polyethylene glycol functionalized products to Daphnia magna: A two generation study.

PubMed

Liu, Yingying; Han, Wenli; Xu, Zhizhen; Fan, Wenhong; Peng, Weihua; Luo, Shenglian

2018-06-01

To investigate the chronic toxicity of graphene oxide (GO) and its functionalized products (GO-carboxyl, GO-imidazole and GO-polyethylene glycol), a two-generation study was conducted using the aquatic model species Daphnia magna. Each generation of daphnids were exposed for 21 days to 1.0 mg L -1 graphene material, with body length, neonate number, time of first brood and the intrinsic rate of natural increase (r) assessed as endpoints. Chronic exposure to GO, GO-carboxyl, and GO-imidazole had no adverse effect on body length or offspring number in the daphnid F0 generation, however, this exposure paradigm led to significant growth or reproduction inhibition in the following generation. Meanwhile, GO was found to show the strongest inhibitory effect, sequentially followed by GO-carboxyl and GO-imidazole. With exposure to GO-polyethylene glycol, no significant effects on growth or reproduction were observed for both F0 and F1 generation daphnids. These results reveal that carboxyl, imidazole and polyethylene glycol functional attachments alleviate the bio-toxicity of GO, especially polyethylene glycol. The increased C/O atomic ratio present in GO-carboxyl, GO-imidazole and GO-polyethylene glycol due to functionalization may mainly explain the reduced toxicity. Copyright © 2018 Elsevier Ltd. All rights reserved.

Theoretical study of binding and permeation of ether-based polymers through interfaces.

PubMed

Samanta, Susruta; Hezaveh, Samira; Roccatano, Danilo

2013-11-27

We present a molecular dynamics simulation study on the interactions of poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), and their ABA-type block copolymer, poloxamers, at water/n-heptane and 1,2-dimyristoyl-sn-glycero-3-phospatidycholine (DMPC) lipid bilayer/water interfaces. The partition coefficients in water/1-octanol of the linear polyethers up to three monomers were calculated. The partition coefficients evidenced a higher hydrophobicity of the PPO in comparison to PEO. At the water/n-heptane interface, the polymers tend to adopt elongated conformations in agreement with similar experimental ellipsometry studies of different poloxamers. In the case of the poloxamers at the n-heptane/water interface, the stronger preference of the PPO block for the hydrophobic phase resulted in bottle-brush-type polymer conformations. At lipid bilayer/water interface, the PEO polymers, as expected from their hydrophilic nature, are weakly adsorbed on the surface of the lipid bilayer and locate in the water phase close to the headgroups. The free energy barriers of permeation calculated for short polymer chains suggest a thermodynamics propensity for the water phase that increase with the chain length. The lower affinity of PEO for the hydrophobic interior of the lipid bilayer resulted in the spontaneous expulsion within the simulation time. On the contrary, PPO chains and poloxamers have a longer residence time inside the bilayer, and they tend to concentrate in the tail region of the bilayer near the polar headgroups. In addition, polymers with PPO unit length comparable to the thickness of the hydrophobic region of the bilayer tend to span across the bilayer.

Synthesis of silver nanoparticles in melts of amphiphilic polyesters

NASA Astrophysics Data System (ADS)

Vasylyev, S.; Damm, C.; Segets, D.; Hanisch, M.; Taccardi, N.; Wasserscheid, P.; Peukert, W.

2013-03-01

The current work presents a one-step procedure for the synthesis of amphiphilic silver nanoparticles suitable for production of silver-filled polymeric materials. This solvent free synthesis via reduction of Tollens’ reagent as silver precursor in melts of amphiphilic polyesters consisting of hydrophilic poly(ethylene glycol) blocks and hydrophobic alkyl chains allows the production of silver nanoparticles without any by-product formation. This makes them especially interesting for the production of medical devices with antimicrobial properties. In this article the influences of the chain length of the hydrophobic block in the amphiphilic polyesters and the process temperature on the particle size distribution (PSD) and the stability of the particles against agglomeration are discussed. According to the results of spectroscopic and viscosimetric investigations the silver precursor is reduced to elemental silver nanoparticles by a single electron transfer process from the poly(ethylene glycol) chain to the silver ion.

Statistical mechanics of addition polymerisation. Calculations of the expectation and variance of the average atmosphere in growing self avoiding walks

NASA Astrophysics Data System (ADS)

Taniya, Abraham; Deepthi, Murali; Padmanabhan, Alapat

2018-06-01

Recent calculations on the change in radial dimensions of reacting (growing) polyethylene in the gas phase experiencing Lennard Jones and Kihara type potentials revealed that a single reacting polyethylene molecule does not experience polymer collapse. This implies that a transition that is the converse of what happens when molten polyethylene crystallizes, i.e. it transforms from random coil like structure to folded rigid rod type structure, occurs. The predicted behaviour of growing polyethylene was explained by treating the head of the growing polymer chain as myopic whereas as the whole chain (i.e. when under equilibrium conditions) being treated as having normal vision, i.e. the growing chain does not see the attractive part of the LJ or Kihara Potentials. In this paper we provide further proof for this argument in two ways. Firstly we carry forward the exact enumeration calculations on growing self avoiding walks reported in that paper to larger values of number of steps by using Monte Carlo type calculations. We thereby assign physical significance to the connective constant of self avoiding walks, which until now was treated as a purely abstract mathematical entity. Secondly since a reacting polymer molecule that grows by addition polymerisation sees only one step ahead at a time, we extend this calculation by estimating the average atmosphere for molecules, with repulsive potential only (growing self avoiding walks in two dimensions), that look at two, three, four, five ...steps ahead. Our calculation shows that the arguments used in the previous work are correct.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Riande, E.; Guzman, J.; Roman, J.S.

The dipole moments of poly (thiodiethylene glycol terephthalate) chains were determined as a function of temperature by means of dielectric constant measurements in dioxane. The experimental results were found to be in fair agreement with theoretical results based on a rotational isomeric state model in which the required conformational energies were obtained from previous configurational analysis on poly(ethylene terephthalate), poly(diethylene glycol terephthalate) and poly(thiodiethylene glycol). Since poly(thiodiethylene glycol terephthalate) can be considered an alternating copolymer of ethylene terephthalate and thioethylene units, its configuration-dependent properties were compared with those of poly(ethylene terephthalate) and poly(ethylene sulfide). It was found the flexibility ofmore » the copolymer, as expressed by the partition function, intermediate to that of its parent homopolymers. The theoretical results also indicate that the dimensions of poly(thiodiethylene glycol) are similar to those of poly(ethylene terephthalate) while its dipole moment ratio resembles that of poly(ethylene sulfide).« less

Wear Behaviours and Oxidation Effects on Different UHMWPE Acetabular Cups Using a Hip Joint Simulator

PubMed Central

Jaber, Sami Abdel; Merola, Massimiliano

2018-01-01

Given the long-term problem of polyethylene wear, medical interest in the new improved cross-linked polyethylene (XLPE), with or without the adding of vitamin E, has risen. The main aim of this study is to gain further insights into the mutual effects of radiation cross-linking and addition of vitamin E on the wear performance of ultra-high-molecular-weight polyethylene (UHMWPE). We tested four different batches of polyethylene (namely, a standard one, a vitamin E-stabilized, and two cross-linked) in a hip joint simulator for five million cycles where bovine calf serum was used as lubricant. The acetabular cups were then analyzed using a confocal profilometer to characterize the surface topography. Moreover; the cups were analyzed by using Fourier Transformed Infrared Spectroscopy and Differential Scanning Calorimetry in order to assess the chemical characteristics of the pristine materials. Comparing the different cups’ configuration, mass loss was found to be higher for standard polyethylene than for the other combinations. Mass loss negatively correlated to the cross-link density of the polyethylenes. None of the tested formulations showed evidence of oxidative degradation. We found no correlation between roughness parameters and wear. Furthermore, we found significantly differences in the wear behavior of all the acetabular cups. XLPEs exhibited lower weight loss, which has potential for reduced wear and decreased osteolysis. However, surface topography revealed smoother surfaces of the standard and vitamin E stabilized polyethylene than on the cross-linked samples. This observation suggests incipient crack generations on the rough and scratched surfaces of the cross-linked polyethylene liners. PMID:29547536

Fabrication and study of properties of magnetite nanoparticles in hybrid micelles of polystyrene-block-polyethylene oxide and sodium dodecyl sulfate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Loginova, T. P., E-mail: tlg@ineos.ac.ru; Timofeeva, G. I.; Lependina, O. L.

2016-01-15

Magnetite nanoparticles have been formed for the first time in hybrid micelles of polystyrene-block-polyethylene oxide and sodium dodecyl sulfate in water by ultrasonic treatment at room temperature. An analysis by small-angle X-ray scattering and transmission electron microscopy (TEM) showed that magnetite nanoparticles in hybrid micelles of block copolymer and sodium dodecyl sulfate are polydesperse (have sizes from 0.5 to 20 nm). The specific magnetization of solid samples has been measured.

Polyethylene glycol assisted growth of Sn-doped ZnO nanorod arrays prepared via sol-gel immersion method

NASA Astrophysics Data System (ADS)

Ismail, A. S.; Mamat, M. H.; Malek, M. F.; Saidi, S. A.; Yusoff, M. M.; Mohamed, R.; Sin, N. D. Md; Suriani, A. B.; Rusop, M.

2018-05-01

Tin-doped zinc oxide (SZO) nanorod films at different concentrations of polyethylene glycol (PEG) were successfully deposited on zinc oxide (ZnO) seeded layer catalyst using sol-gel immersion method. The morphology of the samples were characterized using field emission scanning electron microscopy (FESEM), optical properties using UV-Vis spectrophotometer and electrical properties using I-V measurement system. The current-voltage (I-V) characteristics displayed that 5 wt % sample produced the highest conductivity.

Hydrolytic degradation of poly(ethylene oxide)-block-polycaprolactone worm micelles.

PubMed

Geng, Yan; Discher, Dennis E

2005-09-21

Spherical micelles and nanoparticles made with degradable polymers have been of great interest for therapeutic application, but degradation-induced changes in a spherical morphology can be subtle and mechanism/kinetics appears poorly understood. Here, we report the first preparation of giant and flexible worm micelles self-assembled from degradable copolymer poly(ethylene oxide)-block-polycaprolactone. Such worm micelles spontaneously shorten to generate spherical micelles, triggered by polycaprolactone hydrolysis, with distinct mechanism and kinetics from that which occurs in bulk material.

Oxidized zirconium on ceramic; Catastrophic coupling.

PubMed

Ozden, V E; Saglam, N; Dikmen, G; Tozun, I R

2017-02-01

Oxidized zirconium (Oxinium™; Smith & Nephew, Memphis, TN, USA) articulated with polyethylene in total hip arthroplasty (THA) appeared to have the potential to reduce wear dramatically. The thermally oxidized metal zirconium surface is transformed into ceramic-like hard surface that is resistant to abrasion. The exposure of soft zirconium metal under hard coverage surface after the damage of oxidized zirconium femoral head has been described. It occurred following joint dislocation or in situ succeeding disengagement of polyethylene liner. We reported three cases of misuse of Oxinium™ (Smith & Nephew, Memphis, TN, USA) heads. These three cases resulted in catastrophic in situ wear and inevitable failure although there was no advice, indication or recommendation for this use from the manufacturer. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

Electrical Characterization of Polyaniline/polyethylene Oxide Nanofibers for Field Effect Transistors

NASA Technical Reports Server (NTRS)

Mueller, Carl H.; Theofylaktos, Noulie; Pinto, Nicholas J.; Robinson, Daryl C.; Miranda, Felix A.

2002-01-01

Nanofibers comprised of polyaniline/polyethylene oxide (PANI/PEO) are being developed for novel logic devices. We report the electrical conductivity of PANI/PEO nanofibers with diameters in the 100 to 200 nm range. We measured conductivity values of approx. 0.3 to 1.0 S/cm, which is higher than the values reported for thicker nanofibers, but less than the bulk value of PANI. The electrical measurements were performed by depositing the fibers on pre-electroded, oxidized silicon (Si) substrates. The excellent adherence of the nanofibers to the SiO2 as well as the gold (Au) electrodes may be useful in the design of future devices.

Comparison study of PE epitaxy on carbon nanotubes and graphene oxide and PE/graphene oxide as amphiphilic molecular structure for solvent separation

NASA Astrophysics Data System (ADS)

He, Linghao; Zheng, Xiaoli; Xu, Qun; Chen, Zhimin; Fu, Jianwei

2012-03-01

Carbon nanotubes (CNTs) and graphene nanosheets, as one-dimensional and two-dimensional carbon-based nanomaterials respectively, have different abilities to induce the polymer crystallization. In this study, hybrid materials, polyethylene (PE) decorating on CNTs and graphene oxide (GO), were prepared by a facile and efficient method using supercritical carbon dioxide (SC CO2) as anti-solvent. And the morphology and crystallization behavior of PE on CNTs and GO were investigated by transmission electron microscopy, Fourier transform infrared spectroscopy, Raman spectra, wide angle X-ray diffraction, and differential scanning calorimetry. Although both CNTs and GO could act as nucleating agents to induce PE epitaxial growth, CNTs were decorated by PE lamellar crystals forming nanohybrid "shish-kebab" (NHSK) structure, whereas GO sheets were only decorated with petal-like PE crystals. The varying morphologies of the nanohybrids depend on the PE epitaxy and the interactions between polymer chains and substrates. High surface curvature and the perfect ordered crystal structure of CNTs make PE crystals periodically grow on CNTs. While PE crystals grow and form multiple orientation-lamellae on GO due to the lattice matching and complex interactions between PE chains and GO. In addition, our experimental results show an interesting and evident stratification phenomenon for the PE/GO hybrid material, implying that GO decorated by PE have a screening function for the solvents. We anticipate that this work can widen the area of functionalization of carbon-based nanomaterials with a controlled means by an environmentally benign method, which are important for the functional design in nanodevice applications.

Nanostructures and surface hydrophobicity of self-assembled thermosets involving epoxy resin and poly(2,2,2-trifluoroethyl acrylate)-block-poly(ethylene oxide) amphiphilic diblock copolymer.

PubMed

Yi, Fangping; Zheng, Sixun; Liu, Tianxi

2009-02-19

Poly(2,2,2-trifluoroethyl acrylate)-block-poly(ethylene oxide) (PTFEA-b-PEO) amphiphilic diblock copolymer was synthesized via the reversible addition-fragmentation transfer polymerization of 2,2,2-triffluroethyl acrylate with dithiobenzoyl-terminated poly(ethylene oxide) as a chain-transfer agent. The amphiphilic diblock copolymer was incorporated into epoxy resin to prepare the nanostructured epoxy thermosets. The nanostructures were investigated by means of atomic force microscopy, small-angle X-ray scattering, and dynamic mechanical analysis. In terms of the miscibility of the subchains of the block copolymer with epoxy after and before curing reaction, it is judged that the formation of the nanostructures follows the mechanism of self-assembly. The static contact angle measurements indicate that the nanostructured thermosets containing PTFEA-b-PEO diblock copolymer displayed a significant enhancement in surface hydrophobicity as well as a reduction in surface free energy. The improvement in surface properties was ascribed to the enrichment of the fluorine-containing subchain (i.e., PTFEA block) of the amphiphilic diblock copolymer on the surface of the nanostructured thermosets, which was evidenced by surface atomic force microscopy and energy-dispersive X-ray spectroscopy.

Sequential pyrolysis of plastic to recover polystyrene, HCl and terephthalic acid

DOEpatents

Evans, R.J.; Chum, H.L.

1995-11-07

A process is described for pyrolyzing plastic waste feed streams containing polyvinyl chloride, polyethylene terephthalate, polystyrene and polyethylene to recover polystyrene, HCl and terephthalic acid comprising: heating the plastic waste feed stream to a first temperature; adding an acid or base catalyst on an oxide or carbonate support; heating the plastic waste feed stream to pyrolyze polyethylene terephthalate and polyvinyl chloride; separating terephthalic acid or HCl; heating to a second temperature to pyrolyze polystyrene; separating styrene; heating the waste feed stream to a third temperature to pyrolyze polyethylene; and separating hydrocarbons. 83 figs.

Effect of ultraviolet radiation in the photo-oxidation of High Density Polyethylene and Biodegradable Polyethylene films

NASA Astrophysics Data System (ADS)

Martínez-Romo, A.; González Mota, R.; Bernal, J. J. Soto; Frausto Reyes, C.; Rosales Candelas, I.

2015-01-01

One of the most widely used plastics in the world is the High density polyethylene (HDPE), it is a stable material due to its carbon-carbon bonds, causing their slow degradation; which is why we are looking for alternative ways to accelerate the degradation process of this polymer. An alternative is the addition of oxidized groups in its molecular structure, which results in the development of polymers susceptible to biodegradation (PE-BIO). In this paper, HDPE and PE-BIO films were exposed to UV-B radiation (320-280 nm) at different exposure times, 0-60 days. The effects of UV radiation in samples of HDPE and PE-BIO were characterized using infrared spectroscopy with attenuated total reflectance (ATR). The results show that the exposed materials undergo changes in their molecular structure, due to the infrared bands formed which corresponds to the photo-oxidation of HDPE and PE films when submitted to UV-B radiation.

Poly(ethylene oxide) surfactant polymers.

PubMed

Vacheethasanee, Katanchalee; Wang, Shuwu; Qiu, Yongxing; Marchant, Roger E

2004-01-01

We report on a series of structurally well-defined surfactant polymers that undergo surface-induced self-assembly on hydrophobic biomaterial surfaces. The surfactant polymers consist of a poly(vinyl amine) backbone with poly(ethylene oxide) and hexanal pendant groups. The poly(vinyl amine) (PVAm) was synthesized by hydrolysis of poly(N-vinyl formamide) following free radical polymerization of N-vinyl formamide. Hexanal and aldehyde-terminated poly(ethylene oxide) (PEO) were simultaneously attached to PVAm via reductive amination. Surfactant polymers with different PEO:hexanal ratios and hydrophilic/hydrophobic balances were prepared, and characterized by FT-IR, 1H-NMR and XPS spectroscopies. Surface active properties at the air/water interface were determined by surface tension measurements. Surface activity at a solid surface/water interface was demonstrated by atomic force microscopy, showing epitaxially molecular alignment for surfactant polymers adsorbed on highly oriented pyrolytic graphite. The surfactant polymers described in this report can be adapted for simple non-covalent surface modification of biomaterials and hydrophobic surfaces to provide highly hydrated interfaces.

Novel self-associating poly(ethylene oxide)-b-poly(epsilon-caprolactone) based drug conjugates and nano-containers for paclitaxel delivery.

PubMed

Shahin, Mostafa; Lavasanifar, Afsaneh

2010-04-15

Poly(ethylene oxide)-block-poly(epsilon-caprolactone) (PEO-b-PCL) copolymers bearing paclitaxel (PTX) side groups on PCL (PEO-b-P(CL-PTX) were synthesized and assembled to particles of 123 nm average diameter. At 20% (w/w) PTX to polymer conjugation, PEO-b-P(CL-PTX) demonstrated only 5.0 and 6.7% PTX release after 72 h incubation at pH 7.4 and 5.0, respectively, but revealed signs of chain cleavage at pH 5.0. The cytotoxicity of PEO-b-P(CL-PTX) against MDA-MB-435 cancer cells increased as incubation time was raised from 72 to 96 h (IC(50) of 680 and 475 ng/mL, respectively), but it was still significantly lower than the cytotoxicity of free PTX (IC(50) of 3.5 ng/mL at 72 h). In further studies, micelles of PEO-b-PCL and those bearing benzyl or PTX on PCL were used for physical encapsulation of PTX, where maximum level of loading was achieved by PEO-b-P(CL-PTX) (2.22%, w/w). The release of PTX from this carrier was rapid; however. The in vitro cytotoxicity of physically loaded PTX was independent of carrier and similar to that of free PTX. This was attributed to the low concentration of polymers which fell below their critical micellar concentration in the cytotoxicity study. The results point to the potential of chemically tailored PEO-b-PCL for optimum PTX solubilization and delivery. Copyright 2010 Elsevier B.V. All rights reserved.

Systematic Experimental and Computational Investigation of Ion Transport in Novel Polyether Electrolytes

NASA Astrophysics Data System (ADS)

Pesko, Danielle; Webb, Michael; Jung, Yukyung; Zheng, Qi; Miller, Thomas, III; Coates, Geoffrey; Balsara, Nitash

Polyethers, such as poly(ethylene oxide) (PEO), are considered to be the most promising polymer electrolyte materials due to their high ionic conductivity and electrochemical stability, both essential for battery applications. To gain a fundamental understanding of the transport properties of polyether systems, we design a systematic set of linear PEO-like polymers to explore the effect of adding carbon spacers to the backbone of the chain. Ac impedance spectroscopy is employed to measure the ionic conductivity of polyether/lithium salt electrolytes; the results elucidate tradeoffs between lowering the glass transition temperature and diluting the polar groups on the polymer chain. Molecular-level insight is provided by molecular dynamics simulations of the polyether electrolytes. We define the useful and intuitive metric of ``connectivity'', a parameter calculated from simulations which describes the physical arrangements of solvation sites in a polymer melt. Direct comparison of experiment and theory allows us to determine the relationship between connectivity and conductivity. The comparison provides insight regarding the factors that control conductivity, and highlights considerations that must be taken when designing new ion-conducting polymers.

Biocellulose-based flexible magnetic paper

NASA Astrophysics Data System (ADS)

Barud, H. S.; Tercjak, A.; Gutierrez, J.; Viali, W. R.; Nunes, E. S.; Ribeiro, S. J. L.; Jafellici, M.; Nalin, M.; Marques, R. F. C.

2015-05-01

Biocellulose or bacterial cellulose (BC) is a biocompatible (nano) material produced with a three-dimensional network structure composed of microfibrils having nanometric diameters obtained by the Gluconacetobacter xylinus bacteria. BC membranes present relatively high porosity, allowing the incorporation or synthesis in situ of inorganic nanoparticles for multifunctional applications and have been used as flexible membranes for incorporation of magnetic nanocomposite. In this work, highly stable superparamagnetic iron oxide nanoparticles (SPION), functionalized with polyethylene glycol (PEG), with an average diameter of 5 nm and a saturation magnetization of 41 emu/g at 300 K were prepared. PEG-Fe2O3 hybrid was dispersed by mixing a pristine BC membrane in a stable aqueous dispersion of PEG-SPION. The PEG chains at PEG-SPION's surface provide a good permeability and strong affinity between the BC chains and SPION through hydrogen-bonding interactions. PEG-SPION also allow the incorporation of higher content of nanoparticles without compromising the mechanical properties of the nanocomposite. Structural and magnetic properties of the composite have been characterized by XRD, SEM, energy-dispersive X-ray spectroscopy (EDX), magnetization, Raman spectroscopy, and magnetic force microscopy.

Magnetic properties of Fe-doped organic-inorganic nanohybrids

NASA Astrophysics Data System (ADS)

Silva, N. J. O.; Amaral, V. S.; Carlos, L. D.; de Zea Bermudez, V.

2003-05-01

We present a magnetic study of Fe-doped diureasils (siloxane-based networks to which poly(ethylene oxide)-based chains are grafted by urea cross linkages doped with Fe(II) or Fe(III) ions. Structural studies show that the Fe(II) ions interact mainly with the organic chain, whereas the incorporation of Fe(III) leads to the formation of iron-based nanoclusters, with radius increasing from 20 to 40 Å. Fe(II)-doped samples behave as simple paramagnets, with μeff=5.32μB. Fe(III)-doped hybrids present antiferromagnetic interactions, with TN increasing with Fe(III) concentration up to 13.6 K for 6% doping. Thermal irreversibility was observed below ˜40 K and is stronger for higher concentrations. The coercive fields (HC) are of the order of 1000 Oe at 5 K. Hysteresis cycles are shifted to negative fields, revealing the presence of exchange anisotropy interactions with exchange fields (HE) of the order of 100 Oe. Both fields decrease rapidly with increasing temperature. We analyze this behavior in terms of the contribution of surface spin disorder to exchange anisotropy.

Preparation of Ultrahigh Molecular Weight Polyethylene/Graphene Nanocomposite In situ Polymerization via Spherical and Sandwich Structure Graphene/Sio2 Support

NASA Astrophysics Data System (ADS)

Su, Enqi; Gao, Wensheng; Hu, Xinjun; Zhang, Caicai; Zhu, Bochao; Jia, Junji; Huang, Anping; Bai, Yongxiao

2018-04-01

Reduced graphene oxide/SiO2 (RGO/SiO2) serving as a novel spherical support for Ziegler-Natta (Z-N) catalyst is reported. The surface and interior of the support has a porous architecture formed by RGO/SiO2 sandwich structure. The sandwich structure is like a brick wall coated with a graphene layer of concreted as skeleton which could withstand external pressures and endow the structure with higher support stabilities. After loading the Z-N catalyst, the active components anchor on the surface and internal pores of the supports. When the ethylene molecules meet the active centers, the molecular chains grow from the surface and internal catalytic sites in a regular and well-organized way. And the process of the nascent molecular chains filled in the sandwich structure polymerization could ensure the graphene disperse uniformly in the polymer matrix. Compared with traditional methods, the porous spherical graphene support of this strategy has far more advantages and could maintain an intrinsic graphene performance in the nanocomposites.

Dielectric Properties of Poly(ethylene oxide) from Molecular Dynamics Simulations

NASA Technical Reports Server (NTRS)

Smith, Grant D.

1994-01-01

The order, conformations and dynamics of poly(oxyethylene) (POE) melts have been investigated through molecular dynamics simulations. The potential energy functions were determined from detailed ab initio electronic structure calculations of the conformational energies of the model molecules 1,2-dimethoxyethane (DME) and diethylether. The x-ray structure factor for POE from simulation will be compared to experiment. In terms of conformation, simulations reveal that chains are extended in the melt relative to isolated chains due to the presence of strong intermolecular O...H interactions, which occur at the expense of intramolecular O...H interactions. Conformational dynamics about the C-C bond were found to be significantly faster than in polymethylene, while conformational dynamics about the C-O bond even faster than the C-C dynamics. The faster local dynamics in POE relative to polymethylene is consistent with C-13 NMR spin-lattice relaxation experiments. Conformational transitions showed significant second-neighbor correlation, as was found for polymethylene. This correlation of transitions with C-C neighbors was found to be reduced relative to C-O neighbors. Dielectric relaxation from simulation will also be compared with experiment.

Identification and quantification of odours from oxobiodegradable polyethylene oxidised under a free radical flow by headspace solid-phase microextraction followed by gas chromatography-olfactometry-mass spectrometry.

PubMed

Wrona, Magdalena; Vera, Paula; Pezo, Davinson; Nerín, Cristina

2017-09-01

Recently oxobiodegradable polyethylene gained popularity as food packaging material due to its potential to reduce polymer waste. However, this type of material can release after its oxidation off-odour compounds that affect the organoleptic properties of packaged food. Odour compounds released from both polyethylene and oxobiodegradable polyethylene before and after oxidation under a free radicals flow were investigated after 1 day, 2 days and 3 days of oxidation. The samples were analysed using headspace solid phase microextraction followed by gas chromatography-mass spectrometry and headspace solid phase microextraction coupled to gas chromatography-olfactometry-mass spectrometry. Sixty-two different odorous compounds were identified. 4-methylthio-2-butanone (fruit), nonanal (fat) and 3,6-nonadienal (fat) were present in different materials before oxidation. Multiple headspace-solid phase microextraction has been used to quantify all analytes. The most abundant compound was (Z)-3-hexenyl hexanoate with a concentration range between 1.5791±0.1387µg/g and 4.8181±0.3123µg/g. Compounds such as 2-dodecenal, 2-octenal, 2-pentanol, 3-nonenal, 3,6-nonadienal, ethyl 3-methylbutanoate, ethyl octenoate, hexanone, isopropyl hexanoate, octanal were below their LOD evaluated using MS detector; however, they were detected by gas chromatography-olfactometry. The minimum LOD and LOQ were 0.011µg/g and 0.036µg/g, respectively. Copyright © 2017 Elsevier B.V. All rights reserved.

Simultaneous improvement in ionic conductivity and flexibility of solid polymer electrolytes for thin film lithium ion batteries

NASA Astrophysics Data System (ADS)

Ji, Jianying

Solid polymer electrolytes (SPEs) provide advantages over liquid electrolytes in terms of safety, reliability, less temperature sensitive, and simplicity of design. With the use of a SPE in lithium batteries, high specific energy and specific power, safe operation, flexibility in packaging, and low cost of fabrication can be expected. However, after 30 years, SPEs have rarely found commercial success due to the low ionic conductivity and/or insufficient mechanical properties, both of which are related to the movement of the polymer chains. Many physical/chemical methods have been exploited to simultaneously create enhancement in ionic conductivity and mechanical properties, and some suggested ways have shown promise. However, the complex strategies have always introduced other challenge issues and incurred extra costs for manufacturing. In such a context, the development of dry solid state electrolytes is the central challenge to be faced worldwide. This thesis deals with the approaches to improving ionic conductivity and mechanical properties simultaneously. The method is to apply two kinds of controllable organic fillers: copolymer and protein. Our work revealed that the commercial available copolymer, poly (ethylene oxide)- block-polyethylene (PEO-b-PE), possesses a capability for enhancing the multiple performances of poly(ethylene oxide)(PEO)-based polymer electrolyte. And the effects of composition and molecular weight of the copolymers on performance of the resulting SPEs were examined. It was found that increasing the PE block percentage in the copolymer resulted in a significant increase in both ionic conductivity and mechanical properties, while increasing the molecular weight of the copolymer resulted in better mechanical properties, and an identical ionic conductivity. A rubber-like, soy protein-based SPE (s-SPE)was obtained by employing soy protein isolate (SPI), a soy product usually used as rigid fillers for enhancing mechanical properties of polymers, blended with poly(ethylene oxide)(PEO). The results indicated that the s-SPE with 55 wt% of SPI possesses a fully amorphous uniform structure having low Tg, in contrast with crystalline PEO-based SPE having discernable Tg and Tm. The conductivity and elasticity are both significantly improved with SPI involvement. Remarkably, this film has been elongated up to 100% without loss of ionic conductivity and 700% without mechanical damage.

Water and UV degradable lactic acid polymers

DOEpatents

Bonsignore, P.V.; Coleman, R.D.

1994-11-01

A water and UV light degradable copolymer of monomers of lactic acid and a modifying monomer were selected from the class consisting of ethylene and polyethylene glycols, propylene and polypropylene glycols, P-dioxanone, 1,5 dioxepan-2-one, 1,4 -oxathialan-2-one, 1,4-dioxide and mixtures. These copolymers are useful for waste disposal and agricultural purposes. Also disclosed is a water degradable blend of polylactic acid or modified polylactic acid and high molecular weight polyethylene oxide where the high molecular weight polyethylene oxide is present in the range of from about 2% by weight to about 50% by weight, suitable for films. A method of applying an active material selected from the class of seeds, seedlings, pesticides, herbicides, fertilizers and mixtures to an agricultural site is also disclosed.

Water and UV degradable lactic acid polymers

DOEpatents

Bonsignore, Patrick V.; Coleman, Robert D.

1994-01-01

A water and UV light degradable copolymer of monomers of lactic acid and a modifying monomer selected from the class consisting of ethylene and polyethylene glycols, propylene and polypropylene glycols, P-dioxanone, 1,5 dioxepan-2-one, 1,4 -oxathialan-2-one, 1,4-dioxide and mixtures thereof. These copolymers are useful for waste disposal and agricultural purposes. Also disclosed is a water degradable blend of polylactic acid or modified polylactic acid and high molecular weight polyethylene oxide wherein the high molecular weight polyethylene oxide is present in the range of from about 2% by weight to about 50% by weight, suitable for films. A method of applying an active material selected from the class of seeds, seedlings, pesticides, herbicides, fertilizers and mixtures thereof to an agricultural site is also disclosed.

Catalytic Mechanism of Short Ethoxy Chain Nonylphenol Dehydrogenase Belonging to a Polyethylene Glycol Dehydrogenase Group in the GMC Oxidoreductase Family

PubMed Central

Liu, Xin; Ohta, Takeshi; Kawabata, Takeshi; Kawai, Fusako

2013-01-01

Ethoxy (EO) chain nonylphenol dehydrogenase (NPEO-DH) from Ensifer sp. AS08 and EO chain octylphenol dehydrogenase from Pseudomonas putida share common molecular characteristics with polyethylene glycol (PEG) dehydrogenases (PEG-DH) and comprise a PEG-DH subgroup in the family of glucose-methanol-choline (GMC) oxidoreductases that includes glucose/alcohol oxidase and glucose/choline dehydrogenase. Three-dimensional (3D) molecular modeling suggested that differences in the size, secondary structure and hydropathy in the active site caused differences in their substrate specificities toward EO chain alkylphenols and free PEGs. Based on 3D molecular modeling, site-directed mutagenesis was utilized to introduce mutations into potential catalytic residues of NPEO-DH. From steady state and rapid kinetic characterization of wild type and mutant NPEO-DHs, we can conclude that His465 and Asn507 are directly involved in the catalysis. Asn507 mediates the transfer of proton from a substrate to FAD and His465 transfers the same proton from the reduced flavin to an electron acceptor. PMID:23306149

Catalytic mechanism of short ethoxy chain nonylphenol dehydrogenase belonging to a polyethylene glycol dehydrogenase group in the GMC oxidoreductase family.

PubMed

Liu, Xin; Ohta, Takeshi; Kawabata, Takeshi; Kawai, Fusako

2013-01-10

Ethoxy (EO) chain nonylphenol dehydrogenase (NPEO-DH) from Ensifer sp. AS08 and EO chain octylphenol dehydrogenase from Pseudomonas putida share common molecular characteristics with polyethylene glycol (PEG) dehydrogenases (PEG-DH) and comprise a PEG-DH subgroup in the family of glucose-methanol-choline (GMC) oxidoreductases that includes glucose/alcohol oxidase and glucose/choline dehydrogenase. Three-dimensional (3D) molecular modeling suggested that differences in the size, secondary structure and hydropathy in the active site caused differences in their substrate specificities toward EO chain alkylphenols and free PEGs. Based on 3D molecular modeling, site-directed mutagenesis was utilized to introduce mutations into potential catalytic residues of NPEO-DH. From steady state and rapid kinetic characterization of wild type and mutant NPEO-DHs, we can conclude that His465 and Asn507 are directly involved in the catalysis. Asn507 mediates the transfer of proton from a substrate to FAD and His465 transfers the same proton from the reduced flavin to an electron acceptor.

Chain Ends and the Ultimate Tensile Strength of Polyethylene Fibers

NASA Astrophysics Data System (ADS)

O'Connor, Thomas C.; Robbins, Mark O.

Determining the tensile yield mechanisms of oriented polymer fibers remains a challenging problem in polymer mechanics. By maximizing the alignment and crystallinity of polyethylene (PE) fibers, tensile strengths σ ~ 6 - 7 GPa have been achieved. While impressive, first-principal calculations predict carbon backbone bonds would allow strengths four times higher (σ ~ 20 GPa) before breaking. The reduction in strength is caused by crystal defects like chain ends, which allow fibers to yield by chain slip in addition to bond breaking. We use large scale molecular dynamics (MD) simulations to determine the tensile yield mechanism of orthorhombic PE crystals with finite chains spanning 102 -104 carbons in length. The yield stress σy saturates for long chains at ~ 6 . 3 GPa, agreeing well with experiments. Chains do not break but always yield by slip, after nucleation of 1D dislocations at chain ends. Dislocations are accurately described by a Frenkel-Kontorova model, parametrized by the mechanical properties of an ideal crystal. We compute a dislocation core size ξ = 25 . 24 Å and determine the high and low strain rate limits of σy. Our results suggest characterizing such 1D dislocations is an efficient method for predicting fiber strength. This research was performed within the Center for Materials in Extreme Dynamic Environments (CMEDE) under the Hopkins Extreme Materials Institute at Johns Hopkins University. Financial support was provided by Grant W911NF-12-2-0022.

Analysis of polyethylene wear debris using micro-Raman spectroscopy: a report on the presence of beta-carotene.

PubMed

Hahn, D W; Wolfarth, D L; Parks, N L

1997-04-01

This paper describes micro-Raman spectroscopy of ultra-high molecular weight polyethylene wear debris isolated from revised knee replacements. The novel application of micro-Raman spectroscopy to the analysis of in vivo-generated wear debris was used to evaluate the chemical nature of individual, retrieved polyethylene particles. The analysis revealed the presence of beta-carotene on particles from both synovial fluid and tissue samples. Raman analysis of retrieved polyethylene tibial inserts also revealed localized beta-carotene signals within the primary wear region. In this paper, a mechanism is suggested that may account for the coupling of beta-carotene and polyethylene wear debris. We also discuss the origin of beta-carotene within the implanted joint and the implications that beta-carotene, an anti-oxidant, has for the overall host response to polyethylene orthopedic components.

Effects of variation in chain length on ternary polymer electrolyte - Ionic liquid mixture - A molecular dynamics simulation study

NASA Astrophysics Data System (ADS)

Raju, S. G.; Hariharan, Krishnan S.; Park, Da-Hye; Kang, HyoRang; Kolake, Subramanya Mayya

2015-10-01

Molecular dynamics (MD) simulations of ternary polymer electrolyte - ionic liquid mixtures are conducted using an all-atom model. N-alkyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([CnMPy][TFSI], n = 1, 3, 6, 9) and polyethylene oxide (PEO) are used. Microscopic structure, energetics and dynamics of ionic liquid (IL) in these ternary mixtures are studied. Properties of these four pure IL are also calculated and compared to that in ternary mixtures. Interaction between pyrrolidinium cation and TFSI is stronger and there is larger propensity of ion-pair formation in ternary mixtures. Unlike the case in imidazolium IL, near neighbor structural correlation between TFSI reduces with increase in chain length on cation in both pure IL and ternary mixtures. Using spatial density maps, regions where PEO and TFSI interact with pyrrolidinium cation are identified. Oxygens of PEO are above and below the pyrrolidinium ring and away from the bulky alkyl groups whereas TFSI is present close to nitrogen atom of CnMPy. In pure IL, diffusion coefficient (D) of C3MPy is larger than of TFSI but D of C9MPy and C6MPy are larger than that of TFSI. The reasons for alkyl chain dependent phenomena are explored.

Molecular-Level Control of Ciclopirox Olamine Release from Poly(ethylene oxide)-Based Mucoadhesive Buccal Films: Exploration of Structure-Property Relationships with Solid-State NMR.

PubMed

Urbanova, Martina; Gajdosova, Marketa; Steinhart, Miloš; Vetchy, David; Brus, Jiri

2016-05-02

Mucoadhesive buccal films (MBFs) provide an innovative way to facilitate the efficient site-specific delivery of active compounds while simultaneously separating the lesions from the environment of the oral cavity. The structural diversity of these complex multicomponent and mostly multiphase systems as well as an experimental strategy for their structural characterization at molecular scale with atomic resolution were demonstrated using MBFs of ciclopirox olamine (CPX) in a poly(ethylene oxide) (PEO) matrix as a case study. A detailed description of each component of the CPX/PEO films was followed by an analysis of the relationships between each component and the physicochemical properties of the MBFs. Two distinct MBFs were identified by solid-state NMR spectroscopy: (i) at low API (active pharmaceutical ingredient) loading, a nanoheterogeneous solid solution of CPX molecularly dispersed in an amorphous PEO matrix was created; and (ii) at high API loading, a pseudoco-crystalline system containing CPX-2-aminoethanol nanocrystals incorporated into the interlamellar space of a crystalline PEO matrix was revealed. These structural differences were found to be closely related to the mechanical and physicochemical properties of the prepared MBFs. At low API loading, the polymer chains of PEO provided sufficient quantities of binding sites to stabilize the CPX that was molecularly dispersed in the highly amorphous semiflexible polymer matrix. Consequently, the resulting MBFs were soft, with low tensile strength, plasticity, and swelling index, supporting rapid drug release. At high CPX content, however, the active compounds and the polymer chains simultaneously cocrystallized, leaving the CPX to form nanocrystals grown directly inside the spherulites of PEO. Interfacial polymer-drug interactions were thus responsible not only for the considerably enhanced plasticity of the system but also for the exclusive crystallization of CPX in the thermodynamically most stable polymorphic form, Form I, which exhibited reduced dissolution kinetics. The bioavailability of CPX olamine formulated as PEO-based MBFs can thus be effectively controlled by inducing the complete dispersion and/or microsegregation and nanocrystallization of CPX olamine in the polymer matrix. Solid-state NMR spectroscopy is an efficient tool for exploring structure-property relationships in these complex pharmaceutical solids.

21 CFR 172.260 - Oxidized polyethylene.

Code of Federal Regulations, 2010 CFR

2010-04-01

... HUMAN CONSUMPTION (CONTINUED) FOOD ADDITIVES PERMITTED FOR DIRECT ADDITION TO FOOD FOR HUMAN CONSUMPTION... polyethylene has a minimum number average molecular weight of 1,200, as determined by high temperature vapor pressure osmometry; contains a maximum of 5 percent by weight of total oxygen; and has an acid value of 9...

Hydroxypropyl-β-CD vs. its α-homologue for a 3D modified polyrotaxane network formation and properties: the relationship between modified CD and polymer revealed through comparison.

PubMed

Li, Zhao; Zheng, Zhen; Su, Shan; Yu, Lin; Wang, Xinling

2016-09-14

The threading mechanism of the hydroxypropyl-cyclodextrin (Hy-CD)/tetrahedron-like poly(ethylene glycol) (tetra-PEG) based host-guest complex and the relationship between Hy-CD and poly(ethylene oxide) (PEO) in the three-dimensional modified polyrotaxane (PR) formed by the complex were revealed through the comparison between Hy-β-CD/tetra-PEG and Hy-α-CD/tetra-PEG based systems from the macroscopic material view to the microscopic molecular view. The complexation between Hy-CD and tetra-PEG in water experiences a threading-dethreading-rethreading process which is controlled by the intermolecular interaction intensity or molecular hindrance depending on the feed ratio of Hy-CD to tetra-PEG. In the 3D modified PR, the methyl group of the Hy part on one Hy-CD can insert into the cavity of the adjacent Hy-CD and interacts with both the interior surface of the cavity and the PEO segment within the cavity if the cavity of Hy-CD is large enough. The threaded Hy-CD in the PR straightens the chain of PEO and suppresses the segment motion of the PEO. With the decrease of the cavity size of Hy-CD, the degree of suppression on the segment motion of PEO increases. Hy-CD threaded on the PEO chain can also deform when the 3D modified PR is compressed, and the degree of deformation increases with the increase of the cavity size of Hy-CD. These results of the modified CD/PEG based complex system set it apart from the unmodified CD/PEG based one, and reveal the structure-property relationship of this new type of Hy-CD/tetra-PEG based 3D modified PR material.

Transparent and conductive polyethylene oxide film by the introduction of individualized single-walled carbon nanotubes.

PubMed

Jung, Yong Chae; Muramatsu, Hiroyuki; Park, Ki Chul; Shimamoto, Daisuke; Kim, Jin Hee; Hayashi, Takuya; Song, Sung Moo; Kim, Yoong Ahm; Endo, Morinobu; Dresselhaus, Mildred S

2009-12-16

It is demonstrated that an optically transparent and electrically conductive polyethylene oxide (PEO) film is fabricated by the introduction of individualized single-walled carbon nanotubes (SWNTs). The incorporated SWNTs in the PEO film sustain their intrinsic electronic and optical properties and, in addition, the intrinsic properties of the polymer matrix are retained. The individualized SWNTs with smaller diameter provide high transmittance as well as good electrical conductivity in PEO films. Copyright © 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spectrofluorimetric determination of hydrogen peroxide with 2-hydroxy-1-naphthaldehyde salicyloylhydrazone (HNSH) as the substrate for horseradish peroxidase (HRP).

PubMed

Tang, Bo; Wang, Yan; Sun, Ying; Shen, Han Xi

2002-01-01

The oxidation reaction of HNSH with H2O2 under the catalysis of HRP was studied in detail. The possible reaction mechanism was discussed. Under optimum experimental conditions, the oxidized product of HNSH had excitation and emission maxima at 296 and 414 nm, respectively. A study to prove the existence of -O-O-H in polyethylene glycols was carried out. The proposed method was successfully applied to the determination of -O-O-H in polyethylene glycols.

THE STIMULATING EFFECT OF GLYCOLS AND THEIR POLYMERS ON THE TARSAL RECEPTORS OF BLOWFLIES

PubMed Central

Dethier, V. G.; Chadwick, L. E.

1948-01-01

The rejection thresholds of Phormia regina Meigen for twenty-four glycols have been determined. A definite relationship between the concentration of the test material and the distribution of thresholds has been noted regularly in samples of flies selected at random from a population of known age which had been reared under standard conditions. The scattering of thresholds is normal with respect to the logarithm of concentration. Recalculation of the data of other workers reveals the same sort of relationship with other species of insects and the minnow Phoxinus. The underlying reason for the phenomenon is not known. The glycols in common with other series of homologous alipbatic compounds are rejected at logarithmically decreasing concentrations as the chain length is increased. In general the straight chain diols are more stimulating than the corresponding polyethylene and polypropylene glycols. This difference is related in some manner to the presence of ether linkages in the latter. Polypropylene glycols, with chains of three carbon atoms between the ether linkages are more stimulating than polyethylene glycols, where the spacing is —O—C—C—O—. Unipolymers are more stimulating than mixtures of homologues with the same average molecular weights. Polyethylene glycol 1540 is the largest molecule of measured molecular weight known to stimulate chemoreceptors. The introduction of a second terminal hydroxyl group into the straight hydrocarbon chain reduces the stimulating effect. Alcohols corresponding to the first three diols average about four times as stimulating as the latter while those corresponding to the higher diols average more than one hundred times as stimulating. PMID:18891141

Synthesis of cobalt stearate as oxidant additive for oxo-biodegradable polyethylene

NASA Astrophysics Data System (ADS)

Asriza, Ristika O.; Arcana, I. Made

2015-09-01

Cobalt stearate is an oxidant additives that can initiate a process of degradation in high density polyethylene (HDPE). To determine the effect of cobalt stearate in HDPE, oxo-biodegradable polyethylene film was given an irradiation with UV light or heating at various temperature. After given a heating, the FTIR spectra showed a new absorption peak at wave number 1712 cm-1 indicating the presence of carbonyl groups in polymers, whereas after irradiation with UV light is not visible the presence of this absorption peak. The increase concentration of cobalt stearate added in HDPE and the higher heating temperature, the intensity of the absorption peak of the carbonyl group increased. The increasing intensity of the carbonyl group absorption is caused the presence of damage in the film surface after heating, and this result is supported by analysis the surface properties of the film with using SEM. Biodegradation tests were performed on oxo-biodegradable polyethylene film which has been given heating or UV light with using activated sludge under optimal conditions the growth of microorganisms. After biodegradation, the maximum weight decreased by 23% in the oxo-biodegradable polyethylene film with a cobalt stearate concentration of 0.2% and after heating at a temperature of 75 °C for 10 days, and only 0.69% in the same film after irradiation UV light for 10 days. Based on the results above, cobalt stearate additive is more effective to initiate the oxidative degradation of HDPE when it is initiated by heating compared to irradiation with UV light.

Synthesis of cobalt stearate as oxidant additive for oxo-biodegradable polyethylene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Asriza, Ristika O.; Arcana, I Made, E-mail: arcana@chem.itb.ac.id

Cobalt stearate is an oxidant additives that can initiate a process of degradation in high density polyethylene (HDPE). To determine the effect of cobalt stearate in HDPE, oxo-biodegradable polyethylene film was given an irradiation with UV light or heating at various temperature. After given a heating, the FTIR spectra showed a new absorption peak at wave number 1712 cm{sup −1} indicating the presence of carbonyl groups in polymers, whereas after irradiation with UV light is not visible the presence of this absorption peak. The increase concentration of cobalt stearate added in HDPE and the higher heating temperature, the intensity of themore » absorption peak of the carbonyl group increased. The increasing intensity of the carbonyl group absorption is caused the presence of damage in the film surface after heating, and this result is supported by analysis the surface properties of the film with using SEM. Biodegradation tests were performed on oxo-biodegradable polyethylene film which has been given heating or UV light with using activated sludge under optimal conditions the growth of microorganisms. After biodegradation, the maximum weight decreased by 23% in the oxo-biodegradable polyethylene film with a cobalt stearate concentration of 0.2% and after heating at a temperature of 75 °C for 10 days, and only 0.69% in the same film after irradiation UV light for 10 days. Based on the results above, cobalt stearate additive is more effective to initiate the oxidative degradation of HDPE when it is initiated by heating compared to irradiation with UV light.« less

Infrared analysis of polyethylene wear specimens using attenuated total reflection spectroscopy. [effects of radiation on the surface properties of materials for total joint protheses

NASA Technical Reports Server (NTRS)

Jones, W. R.; Lauer, J. L.

1979-01-01

Attenuated total reflection infrared spectroscopy was used to analyze ultrahigh molecular weight polyethylene wear test specimens. Three different specimens were analyzed. One specimen was gamma irradiated to a dose of 5.0 MRad, another to a dose of 2.5 MRad, and the final specimen was unirradiated. There was no conclusive evidence of chemical changes (i.e., unsaturation or oxidation) in the surface regions of any of the polyethylene samples. Therefore, it was concluded that the gamma irradiation sterilization procedure shoud not alter the boundary lubricating properties of the polyethylene.

Surface layer modification of ion bombarded HDPE

NASA Astrophysics Data System (ADS)

Bielinski, D.; Lipinski, P.; Slusarski, L.; Grams, J.; Paryjczak, T.; Jagielski, J.; Turos, A.; Madi, N. K.

2004-08-01

Press-moulded, high density polyethylene (HDPE) samples were subjected to ion bombardment and effects of the modification studied. He + ions of energy 100 keV or Ar + ions of energy 130 keV were applied in the range of dose 1-30 × 10 15/cm 2 or 1-100 × 10 14/cm 2, respectively. This paper has been focused on structural changes of the surface layer. The consequences of the modification were studied with TOF-SIMS and FTIR-IRS techniques. The results point on two mechanisms taking place simultaneously: ionization of polymer macromolecules and chain scission--resulting in creation of macroradicals. Both of them produce oxidation and lead to significant release of hydrogen. The former diminishes for the highest ion doses, however, creation of molecular oxygen cannot be excluded. The latter in the case of Ar + ion bombardment is reflected by prevailing degradation of the surface layer of HDPE. Contrary to the effect of heavy ions, He + ion bombardment was found to produce significant increase of the material hardness, which was explained by crosslinking of polyethylene. A mechanism of polyacetylene formation, proceeding finally to cross-polymerization of the polymer was proposed. Apart from structural changes, the modification revealed additionally a possibility to improve the wettability of the polymer.

Effect of acid on the aggregation of poly(ethylene xide)-poly(propylene oxide)-poly(ethylene oxide) block copolymers.

PubMed

Yang, Bin; Guo, Chen; Chen, Shu; Ma, Junhe; Wang, Jing; Liang, Xiangfeng; Zheng, Lily; Liu, Huizhou

2006-11-23

The acid effect on the aggregation of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymers EO(20)PO(70)EO(20) has been investigated by transmission electron microscopy (TEM), particle size analyzer (PSA), Fourier transformed infrared, and fluorescence spectroscopy. The critical micellization temperature for Pluronic P123 in different HCl aqueous solutions increases with the increase of acid concentration. Additionally, the hydrolysis degradation of PEO blocks is observed in strong acid concentrations at higher temperatures. When the acid concentration is low, TEM and PSA show the increase of the micelle mean diameter and the decrease of the micelle polydispersity at room temperature, which demonstrate the extension of EO corona and tendency of uniform micelle size because of the charge repulsion. When under strong acid conditions, the aggregation of micelles through the protonated water bridges was observed.

Strain effects on the anisotropic thermal transport in crystalline polyethylene

NASA Astrophysics Data System (ADS)

He, Jixiong; Kim, Kyunghoon; Wang, Yangchao; Liu, Jun

2018-01-01

Thermal transport in the axial direction of polymers has been extensively studied, while the strain effect on the thermal conductivity, especially in the radial direction, remains unknown. In this work, we calculated the thermal conductivity in the radial direction of a crystalline polyethylene model and simulated the uniaxial strain effect on the thermal conductivity tensor by molecular dynamics simulations. We found a strong size effect of the thermal transport in the radial direction and estimated that the phonon mean free path can be much larger than the prediction from the classic kinetic theory. We also found that the thermal conductivity in the axial direction increases dramatically with strain, while the thermal conductivity in the radial direction decreases with uniaxial strain. We attribute the reduction of thermal conductivity in the radial direction to the decreases in inter-chain van der Waals forces with strains. The facts that the chains in the crystalline polyethylene became stiffer and more ordered along the chain direction could be the reasons for the increasing thermal conductivity in the axial direction during stretching. Besides, we observed longer phonon lifetime in acoustic branches and higher group velocity in optical branches after uniaxial stretching. Our work provides fundamental understandings on the phonon transport in crystalline polymers, the structure-property relationship in crystalline polymers, and the strain effect in highly anisotropic materials.

Interrelation of electret properties of polyethylene foam from the method of cross-linking

NASA Astrophysics Data System (ADS)

Gilmanov, I. R.; Galikhanov, M. F.; Gilmanova, A. R.

2017-09-01

The electret properties of chemically cross-linked polyethylene foam and physically cross-linked polyethylene foam have been studied. It has been shown that chemically cross-linked polyethylene foam has higher surface potential, effective surface charge density and electric field strength compared to physically bonded polyethylene foam. This is due to the presence of molecules and fragments of dicumyl peroxide, which can play the role of traps for injection charge carriers, a greater degree of cross-linking and with the oxidation of polyethylene, which occurs during irradiation during physical cross-linking. When the foam is deformed, its electret properties are reduced, and when the volume is relaxed, they are restored. This is due to the partial mutual compensation of homo- and heterocharge during compression and the return of the structure of the gas-filled polymer to its former position when the load is removed.

Forces between functionalized silica nanoparticles in solution

NASA Astrophysics Data System (ADS)

Lane, J. Matthew D.; Ismail, Ahmed E.; Chandross, Michael; Lorenz, Christian D.; Grest, Gary S.

2009-05-01

To prevent the flocculation and phase separation of nanoparticles in solution, nanoparticles are often functionalized with short chain surfactants. Here we present fully atomistic molecular dynamics simulations which characterize how these functional coatings affect the interactions between nanoparticles and with the surrounding solvent. For 5-nm-diameter silica nanoparticles coated with poly(ethylene oxide) (PEO) oligomers in water, we determined the hydrodynamic drag on two approaching nanoparticles moving through solvent and on a single nanoparticle as it approaches a planar surface. In most circumstances, macroscale fluid theory accurately predicts the drag on these nanoscale particles. Good agreement is seen with Brenner’s analytical solutions for wall separations larger than the soft nanoparticle radius. For two approaching coated nanoparticles, the solvent-mediated (velocity independent) and lubrication (velocity-dependent) forces are purely repulsive and do not exhibit force oscillations that are typical of uncoated rigid spheres.

Biosynthesis of monomers for plastics from renewable oils.

PubMed

Lu, Wenhua; Ness, Jon E; Xie, Wenchun; Zhang, Xiaoyan; Minshull, Jeremy; Gross, Richard A

2010-11-03

Omega-hydroxyfatty acids are excellent monomers for synthesizing a unique family of polyethylene-like biobased plastics. However, ω-hydroxyfatty acids are difficult and expensive to prepare by traditional organic synthesis, precluding their use in commodity materials. Here we report the engineering of a strain of the diploid yeast Candida tropicalis to produce commercially viable yields of ω-hydroxyfatty acids. To develop the strain we identified and eliminated 16 genes encoding 6 cytochrome P450s, 4 fatty alcohol oxidases, and 6 alcohol dehydrogenases from the C. tropicalis genome. We also show that fatty acids with different chain lengths and degrees of unsaturation can be more efficiently oxidized by expressing different P450s within this strain background. Biocatalysis using engineered C. tropicalis is thus a potentially attractive biocatalytic platform for producing commodity chemicals from renewable resources.

Interaction of Curcumin with PEO-PPO-PEO block copolymers: a molecular dynamics study.

PubMed

Samanta, Susruta; Roccatano, Danilo

2013-03-21

Curcumin, a naturally occurring drug molecule, has been extensively investigated for its various potential usages in medicine. Its water insolubility and high metabolism rate require the use of drug delivery systems to make it effective in the human body. Among various types of nanocarriers, block copolymer based ones are the most effective. These polymers are broadly used as drug-delivery systems, but the nature of this process is poorly understood. In this paper, we propose a molecular dynamics simulation study of the interaction of Curcumin with block copolymer based on polyethylene oxide (PEO) and polypropylene oxide (PPO). The study has been conducted considering the smallest PEO and PPO oligomers and multiple chains of the block copolymer Pluronic P85. Our study shows that the more hydrophobic 1,2-dimethoxypropane (DMP) molecules and PPO block preferentially coat the Curcumin molecule. In the case of the Pluronic P85, simulation shows formation of a drug-polymer aggregate within 50 ns. This process leaves exposed the PEO part of the polymers, resulting in better solvation and stability of the drug in water.

Radiation sterilization of medical devices. Effects of ionizing radiation on ultra-high molecular-weight polyethylene

NASA Astrophysics Data System (ADS)

Buchalla, R.; Schüttler, C.; Bögl, K. W.

1995-02-01

Sterilization by ionizing radiation has become, next to ethylene oxide treament, the most important "cold" sterilization process for medical devices made from plastics. The effects of ionizing radiation on the most important polymer for medical devices, ultra-high molecular-weight polyethylene, are briefly described in this review.

21 CFR 172.820 - Polyethylene glycol (mean molecular weight 200-9,500).

Code of Federal Regulations, 2010 CFR

2010-04-01

... ethylene oxide and water with a mean molecular weight of 200 to 9,500. (2) It contains no more than 0.2 percent total by weight of ethylene and diethylene glycols when tested by the analytical methods... the total ethylene and diethylene glycol content of polyethylene glycols having mean molecular weights...

Nanostructure of propylammonium nitrate in the presence of poly(ethylene oxide) and halide salts

NASA Astrophysics Data System (ADS)

Stefanovic, Ryan; Webber, Grant B.; Page, Alister J.

2018-05-01

Nanoscale structure of protic ionic liquids is critical to their utility as molecular electrochemical solvents since it determines the capacity to dissolve salts and polymers such as poly(ethylene oxide) (PEO). Here we use quantum chemical molecular dynamics simulations to investigate the impact of dissolved halide anions on the nanostructure of an archetypal nanostructured protic ionic liquid, propylammonium nitrate (PAN), and how this impacts the solvation of a model PEO polymer. At the molecular level, PAN is nanostructured, consisting of charged/polar and uncharged/nonpolar domains. The charged domain consists of the cation/anion charge groups, and is formed by their electrostatic interaction. This domain solvophobically excludes the propyl chains on the cation, which form a distinct, self-assembled nonpolar domain within the liquid. Our simulations demonstrate that the addition of Cl- and Br- anions to PAN disrupts the structure within the PAN charged domain due to competition between nitrate and halide anions for the ammonium charge centre. This disruption increases with halide concentration (up to 10 mol. %). However, at these concentrations, halide addition has little effect on the structure of the PAN nonpolar domain. Addition of PEO to pure PAN also disrupts the structure within the charged domain of the liquid due to hydrogen bonding between the charge groups and the terminal PEO hydroxyl groups. There is little other association between the PEO structure and the surrounding ionic liquid solvent, with strong PEO self-interaction yielding a compact, coiled polymer morphology. Halide addition results in greater association between the ionic liquid charge centres and the ethylene oxide components of the PEO structure, resulting in reduced conformational flexibility, compared to that observed in pure PAN. Similarly, PEO self-interactions increase in the presence of Cl- and Br- anions, compared to PAN, indicating that the addition of halide salts to PAN decreases its utility as a molecular solvent for polymers such as PEO.

Charge carrier dynamics and relaxation in (polyethylene oxide-lithium-salt)-based polymer electrolyte containing 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide as ionic liquid

NASA Astrophysics Data System (ADS)

Karmakar, A.; Ghosh, A.

2011-11-01

In this paper we report the dynamics of charge carriers and relaxation in polymer electrolytes based on polyethylene oxide (PEO), lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) and 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMPTFSI) ionic liquid prepared by solution cast technique. It has been observed that the incorporation of BMPTFSI into PEO-LiTFSI electrolyte is an effective way for increasing the amorphous phase to a large extent. It has also been observed that both the glass transition and melting temperatures decrease with the increase of BMPTFSI concentration. The ionic conductivity of these polymer electrolytes increases with the increase of BMPTFSI concentration. The highest ionic conductivity obtained at 25 °C is ˜3×10-4 S cm-1 for the electrolyte containing 60 wt % BMPTFSI and ethylene oxide (EO)/Li ratio of 20. The temperature dependence of the dc conductivity and the hopping frequency show Vogel-Tamman-Fulcher type behavior indicating a strong coupling between the ionic and the polymer chain segmental motions. The frequency dependence of the ac conductivity exhibits a power law with an exponent n which decreases with the increase of temperature. The scaling of the ac conductivity indicates that relaxation dynamics of charge carriers follows a common mechanism for all temperatures and BMPTFSI concentrations. We have also presented the electric modulus data which have been analyzed in the framework of a Havriliak-Negami equation and the shape parameters obtained by the analysis show slight temperature dependence, but change sharply with BMPTFSI concentration. The stretched exponent β obtained from Kohlrausch-Williams-Watts fit to the modulus data is much lower than unity signifying that the relaxation is highly nonexponential. The decay function obtained from analysis of experimental modulus data is highly asymmetric with time.

Polyethylene Glycol Modified, Cross-Linked Starch Coated Iron Oxide Nanoparticles for Enhanced Magnetic Tumor Targeting

PubMed Central

Cole, Adam J.; David, Allan E.; Wang, Jianxin; Galbán, Craig J.; Hill, Hannah L.; Yang, Victor C.

2010-01-01

While successful magnetic tumor targeting of iron oxide nanoparticles has been achieved in a number of models, the rapid blood clearance of magnetically suitable particles by the reticuloendothelial system (RES) limits their availability for targeting. This work aimed to develop a long-circulating magnetic iron oxide nanoparticle (MNP) platform capable of sustained tumor exposure via the circulation and, thus, enhanced magnetic tumor targeting. Aminated, cross-linked starch (DN) and aminosilane (A) coated MNPs were successfully modified with 5 kDa (A5, D5) or 20 kDa (A20, D20) polyethylene glycol (PEG) chains using simple N-Hydroxysuccinimide (NHS) chemistry and characterized. Identical PEG-weight analogues between platforms (A5 & D5, A20 & D20) were similar in size (140–190 nm) and relative PEG labeling (1.5% of surface amines – A5/D5, 0.4% – A20/D20), with all PEG-MNPs possessing magnetization properties suitable for magnetic targeting. Candidate PEG-MNPs were studied in RES simulations in vitro to predict long-circulating character. D5 and D20 performed best showing sustained size stability in cell culture medium at 37°C and 7 (D20) to 10 (D5) fold less uptake in RAW264.7 macrophages when compared to previously targeted, unmodified starch MNPs (D). Observations in vitro were validated in vivo, with D5 (7.29 hr) and D20 (11.75 hr) showing much longer half-lives than D (0.12 hr). Improved plasma stability enhanced tumor MNP exposure 100 (D5) to 150 (D20) fold as measured by plasma AUC0-∞ Sustained tumor exposure over 24 hours was visually confirmed in a 9L-glioma rat model (12 mg Fe/kg) using magnetic resonance imaging (MRI). Findings indicate that both D5 and D20 are promising MNP platforms for enhanced magnetic tumor targeting, warranting further study in tumor models. PMID:21176955

Light scattering evidence of selective protein fouling on biocompatible block copolymer micelles

NASA Astrophysics Data System (ADS)

Giacomelli, Fernando C.; Stepánek, Petr; Schmidt, Vanessa; Jäger, Eliézer; Jäger, Alessandro; Giacomelli, Cristiano

2012-07-01

Selective protein fouling on block copolymer micelles with well-known potential for tumour-targeting drug delivery was evidenced by using dynamic light scattering measurements. The stability and interaction of block copolymer micelles with model proteins (BSA, IgG, lysozyme and CytC) is reported for systems featuring a hydrophobic (poly[2-(diisopropylamino)-ethyl methacrylate]) (PDPA) core and hydrophilic coronas comprising poly(ethylene oxide)/poly(glycerol monomethacrylate) (PEO-b-PG2MA) or poly[2-(methacryloyloxy)ethyl phosphorylcholine] (PMPC). The results revealed that protein size and hydrophilic chain density play important roles in the observed interactions. The PEO113-b-PG2MA30-b-PDPA50 nanoparticles are stable and protein adsorption is prevented at all investigated protein environments. The successful protein-repellent characteristic of these nanoparticles is attributed to a high hydrophilic surface chain density (>0.1 chains per nm2) and to the length of the hydrophilic chains. On the other hand, although PMPC also has protein-repellent characteristics, the low surface chain density of the hydrophilic shell is supposed to enable interactions with small proteins. The PMPC40-b-PDPA70 micelles are stable in BSA and IgG environments due to weak repulsion forces between PMPC and the proteins, to the hydration layer, and particularly to a size-effect where the large BSA (RH = 4.2 nm) and IgG (RH = 7.0 nm) do not easily diffuse within the PMPC shell. Conversely, a clear interaction was observed with the 2.1 nm radius lysozyme. The lysozyme protein can diffuse within the PMPC micellar shell towards the PDPA hydrophobic core in a process favored by its smaller size and the low hydrophilic PMPC surface chain density (~0.049 chains per nm2) as compared to PEO-b-PG2MA (~0.110 chains per nm2). The same behavior was not evidenced with the 2.3 nm radius positively charged CytC, probably due to its higher surface hydrophilicity and the consequent chemical incompatibility with PDPA.Selective protein fouling on block copolymer micelles with well-known potential for tumour-targeting drug delivery was evidenced by using dynamic light scattering measurements. The stability and interaction of block copolymer micelles with model proteins (BSA, IgG, lysozyme and CytC) is reported for systems featuring a hydrophobic (poly[2-(diisopropylamino)-ethyl methacrylate]) (PDPA) core and hydrophilic coronas comprising poly(ethylene oxide)/poly(glycerol monomethacrylate) (PEO-b-PG2MA) or poly[2-(methacryloyloxy)ethyl phosphorylcholine] (PMPC). The results revealed that protein size and hydrophilic chain density play important roles in the observed interactions. The PEO113-b-PG2MA30-b-PDPA50 nanoparticles are stable and protein adsorption is prevented at all investigated protein environments. The successful protein-repellent characteristic of these nanoparticles is attributed to a high hydrophilic surface chain density (>0.1 chains per nm2) and to the length of the hydrophilic chains. On the other hand, although PMPC also has protein-repellent characteristics, the low surface chain density of the hydrophilic shell is supposed to enable interactions with small proteins. The PMPC40-b-PDPA70 micelles are stable in BSA and IgG environments due to weak repulsion forces between PMPC and the proteins, to the hydration layer, and particularly to a size-effect where the large BSA (RH = 4.2 nm) and IgG (RH = 7.0 nm) do not easily diffuse within the PMPC shell. Conversely, a clear interaction was observed with the 2.1 nm radius lysozyme. The lysozyme protein can diffuse within the PMPC micellar shell towards the PDPA hydrophobic core in a process favored by its smaller size and the low hydrophilic PMPC surface chain density (~0.049 chains per nm2) as compared to PEO-b-PG2MA (~0.110 chains per nm2). The same behavior was not evidenced with the 2.3 nm radius positively charged CytC, probably due to its higher surface hydrophilicity and the consequent chemical incompatibility with PDPA. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr30623a

How Low Can You Go? Low Densities of Poly(ethylene glycol) Surfactants Attract Stealth Proteins.

PubMed

Seneca, Senne; Simon, Johanna; Weber, Claudia; Ghazaryan, Arthur; Ethirajan, Anitha; Mailaender, Volker; Morsbach, Svenja; Landfester, Katharina

2018-06-25

It is now well-established that the surface chemistry and "stealth" surface functionalities such as poly(ethylene glycol) (PEG) chains of nanocarriers play an important role to decrease unspecific protein adsorption of opsonizing proteins, to increase the enrichment of specific stealth proteins, and to prolong the circulation times of the nanocarriers. At the same time, PEG chains are used to provide colloidal stability for the nanoparticles. However, it is not clear how the chain length and density influence the unspecific and specific protein adsorption keeping at the same time the stability of the nanoparticles in a biological environment. Therefore, this study aims at characterizing the protein adsorption patterns depending on PEG chain length and density to define limits for the amount of PEG needed for a stealth effect by selective protein adsorption as well as colloidal stability during cell experiments. PEG chains are introduced using the PEGylated Lutensol AT surfactants, which allow easy modification of the nanoparticle surface. These findings indicate that a specific enrichment of stealth proteins already occurs at low PEG concentrations; for the decrease of unspecific protein adsorption and finally the colloidal stability a full surface coverage is advised. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface Plasmon Resonance Study of the Binding of PEO-PPO-PEO Triblock Copolymer and PEO Homopolymer to Supported Lipid Bilayers.

PubMed

Kim, Mihee; Vala, Milan; Ertsgaard, Christopher T; Oh, Sang-Hyun; Lodge, Timothy P; Bates, Frank S; Hackel, Benjamin J

2018-06-12

Poloxamer 188 (P188), a poly(ethylene oxide)- b-poly(propylene oxide)- b-poly(ethylene oxide) triblock copolymer, protects cell membranes against various external stresses, whereas poly(ethylene oxide) (PEO; 8600 g/mol) homopolymer lacks protection efficacy. As part of a comprehensive effort to elucidate the protection mechanism, we used surface plasmon resonance (SPR) to obtain direct evidence of binding of the polymers onto supported lipid bilayers. Binding kinetics and coverage of P188 and PEO were examined and compared. Most notably, PEO exhibited membrane association comparable to that of P188, evidenced by comparable association rate constants and coverage. This result highlights the need for additional mechanistic understanding beyond simple membrane association to explain the differential efficacy of P188 in therapeutic applications.

Morphology of Thermally Degraded PU and Irradiated PE

NASA Astrophysics Data System (ADS)

Harris, Douglas; Gillen, Kenneth; Celina, Mathias; Assink, Roger

2001-03-01

Several 1H and 13C NMR techniques have been applied to study the morphology and chemical structure of thermally degraded polyurethane rubber and irradiated polyethylene cable insulation. The combination of heat and presence of air results in oxidation of the hydroxyl-terminated polybutadiene/isophorone diisocyanate polyurethane and the gel content increases. The oxidation is inhomogeneous: pristine regions remain with a length scale of approximately 20 nm. The morphology and oxidation products were characterized by 1H spin diffusion with 13C detection. In addition, dynamics were probed with 1H and 2D WISE experiments. Radiation of cross-linked polyethylene cable insulation obeys anomalous aging behavior where lower temperature can result in a greater loss in ultimate tensile elongation. Annealing of the irradiated polyethylene allows significant recovery of mechanical properties. Analysis of 13C NMR data was used to study this "Lazarus effect" and the inverse temperature relationship. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy under Contract DE-AC04-94AL8500.

Polymer chain dynamics under nanoscopic confinements.

PubMed

Kimmich, Rainer; Fatkullin, Nail; Mattea, Carlos; Fischer, Elmar

2005-02-01

It is shown that the confinement of polymer melts in nanopores leads to chain dynamics dramatically different from bulk behavior. This so-called corset effect occurs both above and below the critical molecular mass and induces the dynamic features predicted for reptation. A spinodal demixing technique was employed for the preparation of linear poly(ethylene oxide) (PEO) confined to nanoscopic strands that are in turn embedded in a quasi-solid and impenetrable methacrylate matrix. Both the molecular weight of the PEO and the mean diameter of the strands were varied to a certain degree. The chain dynamics of the PEO in the molten state was examined with the aid of field-gradient NMR diffusometry (time scale, 10(-2)-10(0) s) and field-cycling NMR relaxometry (time scale, 10(-9)-10(-4) s). The dominating mechanism for translational displacements probed in the nanoscopic strands by either technique is shown to be reptation. On the time scale of spin-lattice relaxation time measurements, the frequency dependence signature of reptation (i.e., T1 approximately nu(3/4)) showed up in all samples. A "tube" diameter of only 0.6 nm was concluded to be effective on this time scale even when the strand diameter was larger than the radius of gyration of the PEO random coils. This corset effect is traced back to the lack of the local fluctuation capacity of the free volume in nanoscopic confinements. The confinement dimension is estimated at which the crossover from confined to bulk chain dynamics is expected.

Modification of graphene oxide with amphiphilic double-crystalline block copolymer polyethylene-b-poly(ethylene oxide) with assistance of supercritical CO2 and its further functionalization.

PubMed

Zheng, Xiaoli; Xu, Qun; He, Linghao; Yu, Ning; Wang, Shanshan; Chen, Zhimin; Fu, JianWei

2011-05-19

Graphene oxide (GO) sheets were noncovalently modified with an amphiphilic double-crystalline block copolymer, polyethylene-b-poly(ethylene oxide) (PE-b-PEO) with assistance of supercritical CO(2) (SC CO(2)) in this work. The resulting PE-b-PEO/GO nanohybrids were characterized by transmission electron microscopy (TEM), wide-angle X-ray diffraction (WAXD), Fourier transform infrared spectroscopy (FTIR), and Raman spectra. Distinct morphologies of PE-b-PEO decorating on the surface of GO were obtained in different solvent systems and at different SC CO(2) pressures. We found that the solvent system and the SC CO(2) have significant influence on the crystallization, aggregation, or assembly behaviors of PE-b-PEO molecular chains on the GO sheets. The formation mechanism of the distinct nanohybrid structures is attributed to a relevant easy heteronucleation and the limited crystal growth of the block polymer on the surface of GO. The resulting modified GO sheets could find a broad spectrum of applications not only in producing graphene-based nanocomposites but also being used as a template to fabricate multifunctional structures due to the unique properties of PE-b-PEO. As a proof-of-concept, we further decorated the GO sheets with the as-prepared Au nanoparticles (Au NPs) and CdTe nanoparticles (CdTe NPs) with PE-b-PEO as the interlinker. Using the thiol-terminated PE-b-PEO as an interlinker, Au NPs can be densely assembled on the surface of GO via robust Au-S bonds. Furthermore, the photoluminescence quenching of CdTe NPs was more notable for PE-b-PEO/GO-CdTe hybrid compared to the GO-CdTe hybrid, suggesting that the electron transfer from the CdTe NPs to the GO sheets was enhanced with the PE-b-PEO interlinker. The availability of these affordable graphene-based multifunctional structures and their fundamental properties will open up new opportunities for nanoscience and nanotechnology and accelerate their applications. © 2011 American Chemical Society

Ionic conductivity of β-cyclodextrin-polyethylene-oxide/alkali-metal-salt complex.

PubMed

Yang, Ling-Yun; Fu, Xiao-Bin; Chen, Tai-Qiang; Pan, Li-Kun; Ji, Peng; Yao, Ye-Feng; Chen, Qun

2015-04-20

Highly conductive, crystalline, polymer electrolytes, β-cyclodextrin (β-CD)-polyethylene oxide (PEO)/LiAsF6 and β-CD-PEO/NaAsF6 , were prepared through supramolecular self-assembly of PEO, β-CD, and LiAsF6 /NaAsF6 . The assembled β-CDs form nanochannels in which the PEO/X(+) (X=Li, Na) complexes are confined. The nanochannels provide a pathway for directional motion of the alkali metal ions and, at the same time, separate the cations and the anions by size exclusion. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Poly(ethylene oxide) functionalization

DOEpatents

Pratt, Russell Clayton

2014-04-08

A simple procedure is provided by which the hydroxyl termini of poly(ethylene oxide) can be appended with functional groups to a useful extent by reaction and precipitation. The polymer is dissolved in warmed toluene, treated with an excess of organic base and somewhat less of an excess of a reactive acylating reagent, reacted for several hours, then precipitated in isopropanol so that the product can be isolated as a solid, and salt byproducts are washed away. This procedure enables functionalization of the polymer while not requiring laborious purification steps such as solvent-solvent extraction or dialysis to remove undesirable side products.

Dynamics of poly(ethylene oxide) in a blend with poly(methyl methacrylate): a quasielastic neutron scattering and molecular dynamics simulations study.

PubMed

Genix, A-C; Arbe, A; Alvarez, F; Colmenero, J; Willner, L; Richter, D

2005-09-01

In this paper, we have addressed the question of the dynamic miscibility in a blend characterized by very different glass-transition temperatures, Tg, for the components: poly(ethylene oxide) and poly(methyl methacrylate) (PEO/PMMA). The combination of quasielastic neutron scattering with isotopic labeling and fully atomistic molecular dynamics simulations has allowed us to selectively investigate the dynamics of the two components in the picosecond-10 nanoseconds scale at temperatures close and above the Tg of the blend. The main focus was on the PEO component, i.e., that of the lowest Tg, but first we have characterized the dynamics of the other component in the blend and of the pure PEO homopolymer as reference. In the region investigated, the dynamics of PMMA in the blend is strongly affected by the alpha-methyl rotation; an additional process detected in the experimental window 65 K above the blend-Tg can be identified as the merged alphabeta process of this component that shows strong deviations from Gaussian behavior. On the other hand, pure PEO displays entropy driven dynamics up to very large momentum transfers. Such kind of motion seems to freeze when the PEO chains are in the blend. There, we have directly observed a very heterogeneous and moreover confined dynamics for the PEO component. The presence of the hardly moving PMMA matrix leads to the creation of little pockets of mobility where PEO can move. The characteristic size of such confined islands of mobility might be estimated to be of approximately 1 nm. These findings are corroborated by the simulation study, which has been an essential support and guide in our data analysis procedure.

Coordination Chemistry Inside Polymeric Nanoreactors: Interparticle Metal Exchange and Ionic Compound Vectorization in Phosphine-Functionalized Amphiphilic Polymer Latexes.

PubMed

Chen, Si; Gayet, Florence; Manoury, Eric; Joumaa, Ahmad; Lansalot, Muriel; D'Agosto, Franck; Poli, Rinaldo

2016-04-25

Stable latexes of hierarchically organized core-cross-linked polymer micelles that are functionalized at the core with triphenylphosphine (TPP@CCM) have been investigated by NMR spectroscopic analysis at both natural (ca. pH 5) and strongly basic (pH 13.6) pH values after core swelling with toluene. The core-shell interface structuring forces part of the hydrophilic poly(ethylene oxide) (PEO) chains to reside inside the hydrophobic core at both pH values. Loading the particle cores with [Rh(acac)(CO)2 ] (acac=acetylacetonate) at various Rh/P ratios yielded polymer-supported [Rh(acac)(CO)(TPP)] (TPP=triphenylphosphine). The particle-to-particle rhodium migration is very fast at natural pH, but slows down dramatically at high pH, whereas the size distribution of the nanoreactors remains unchanged. The slow migration at pH 13.6 leads to the generation of polymer-anchored [Rh(OH)(CO)(TPP)2 ], which is also generated immediately upon the addition of NaOH to the particles with a [Rh(acac)(CO)] loading of 50 %. Similarly, treatment of the same particles with NaCl yielded polymer-anchored [RhCl(CO)(TPP)2 ]. Interparticle coupling occurs during these rapid processes. These experiments prove that the major contribution to metal migration is direct core-core contact. The slow migration at the high pH value, however, must result from a pathway that does not involve core-core contact. The facile penetration of the polymer cores by NaOH and NaCl results from the presence of shell-linked poly(ethylene oxide) methyl ether functions both outside and inside the polymer core-shell interface. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Biodegradation of Low-Density Polyethylene (LDPE) by Mixed Culture of Lysinibacillus xylanilyticus and Aspergillus niger in Soil

PubMed Central

Esmaeili, Atefeh; Pourbabaee, Ahmad Ali; Alikhani, Hossein Ali; Shabani, Farzin; Esmaeili, Ensieh

2013-01-01

In this study, two strains of Aspergillus sp. and Lysinibacillus sp. with remarkable abilities to degrade low-density polyethylene (LDPE) were isolated from landfill soils in Tehran using enrichment culture and screening procedures. The biodegradation process was performed for 126 days in soil using UV- and non-UV-irradiated pure LDPE films without pro-oxidant additives in the presence and absence of mixed cultures of selected microorganisms. The process was monitored by measuring the microbial population, the biomass carbon, pH and respiration in the soil, and the mechanical properties of the films. The carbon dioxide measurements in the soil showed that the biodegradation in the un-inoculated treatments were slow and were about 7.6% and 8.6% of the mineralisation measured for the non-UV-irradiated and UV-irradiated LDPE, respectively, after 126 days. In contrast, in the presence of the selected microorganisms, biodegradation was much more efficient and the percentages of biodegradation were 29.5% and 15.8% for the UV-irradiated and non-UV-irradiated films, respectively. The percentage decrease in the carbonyl index was higher for the UV-irradiated LDPE when the biodegradation was performed in soil inoculated with the selected microorganisms. The percentage elongation of the films decreased during the biodegradation process. The Fourier transform infra-red (FT-IR), x-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to determine structural, morphological and surface changes on polyethylene. These analyses showed that the selected microorganisms could modify and colonise both types of polyethylene. This study also confirmed the ability of these isolates to utilise virgin polyethylene without pro-oxidant additives and oxidation pretreatment, as the carbon source. PMID:24086254

Biodegradation of low-density polyethylene (LDPE) by mixed culture of Lysinibacillus xylanilyticus and Aspergillus niger in soil.

PubMed

Esmaeili, Atefeh; Pourbabaee, Ahmad Ali; Alikhani, Hossein Ali; Shabani, Farzin; Esmaeili, Ensieh

2013-01-01

In this study, two strains of Aspergillus sp. and Lysinibacillus sp. with remarkable abilities to degrade low-density polyethylene (LDPE) were isolated from landfill soils in Tehran using enrichment culture and screening procedures. The biodegradation process was performed for 126 days in soil using UV- and non-UV-irradiated pure LDPE films without pro-oxidant additives in the presence and absence of mixed cultures of selected microorganisms. The process was monitored by measuring the microbial population, the biomass carbon, pH and respiration in the soil, and the mechanical properties of the films. The carbon dioxide measurements in the soil showed that the biodegradation in the un-inoculated treatments were slow and were about 7.6% and 8.6% of the mineralisation measured for the non-UV-irradiated and UV-irradiated LDPE, respectively, after 126 days. In contrast, in the presence of the selected microorganisms, biodegradation was much more efficient and the percentages of biodegradation were 29.5% and 15.8% for the UV-irradiated and non-UV-irradiated films, respectively. The percentage decrease in the carbonyl index was higher for the UV-irradiated LDPE when the biodegradation was performed in soil inoculated with the selected microorganisms. The percentage elongation of the films decreased during the biodegradation process. The Fourier transform infra-red (FT-IR), x-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to determine structural, morphological and surface changes on polyethylene. These analyses showed that the selected microorganisms could modify and colonise both types of polyethylene. This study also confirmed the ability of these isolates to utilise virgin polyethylene without pro-oxidant additives and oxidation pretreatment, as the carbon source.

Surfactant-directed synthesis of mesoporous films made single-step by a tandem photosol-gel/photocalcination route

NASA Astrophysics Data System (ADS)

De Paz-Simon, Héloïse; Chemtob, Abraham; Croutxé-Barghorn, Céline; Rigolet, Séverinne; Michelin, Laure; Vidal, Loïc; Lebeau, Bénédicte

2014-11-01

In view of their technological impact in materials chemistry, a simplified and more efficient synthetic route to mesoporous films is highly sought. We report, herein, a smart UV-mediated approach coupling in a one-stage process sol-gel photopolymerization and photoinduced template decomposition/ablation to making mesoporous silica films. Performed at room temperature with a solvent-free solution of silicate precursor and amphiphilic poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymer, the synthesis relies on photoacid generation to induce the fast formation (≈10 min) of mesostructured silica/surfactant domains. Continuation of UV exposure for three additional hours enables subsequent and complete photodegradation of the polyether copolymer, resulting in ordered or disordered mesoporous silica film. One of the most attractive features is that the one-step procedure relies on a continuous illumination provided by the same conventional medium-pressure Hg-Xe arc lamp equipped with a 254 nm reflector to enhance the emission of energetic photons <300 nm. In addition to X-ray diffraction and transmission electron microscopy, time-resolved Fourier transform infrared spectroscopy has proved to be a powerful in situ technique to probe the different chemical transformations accompanying irradiation. Photocalcination strengthens the inorganic network, while allowing to preserve a higher fraction of residual silanol groups compared with thermal calcination. A polyether chain degradation mechanism based on oxygen reactive species-mediated photo-oxidation is proposed.

Separating effective high density polyethylene segments from olefin block copolymers using high temperature liquid chromatography with a preloaded discrete adsorption promoting solvent barrier.

PubMed

Chatterjee, Tirtha; Rickard, Mark A; Pearce, Eric; Pangburn, Todd O; Li, Yongfu; Lyons, John W; Cong, Rongjuan; deGroot, A Willem; Meunier, David M

2016-09-23

Recent advances in catalyst technology have enabled the synthesis of olefin block copolymers (OBC). One type is a "hard-soft" OBC with a high density polyethylene (HDPE) block and a relatively low density polyethylene (VLDPE) block targeted as thermoplastic elastomers. Presently, one of the major challenges is to fractionate HDPE segments from the other components in an experimental OBC sample (block copolymers and VLDPE segments). Interactive high temperature liquid chromatography (HTLC) is ineffective for OBC separation as the HDPE segments and block copolymer chains experience nearly identical enthalpic interactions with the stationary phase and co-elute. In this work we have overcome this challenge by using liquid chromatography under the limiting conditions of desorption (LC LCD). A solvent plug (discrete barrier) is introduced in front of the sample which specifically promotes the adsorption of HDPE segments on the stationary phase (porous graphitic carbon). Under selected thermodynamic conditions, VLDPE segments and block copolymer chains crossed the barrier while HDPE segments followed the pore-included barrier solvent and thus enabled separation. The barrier solvent composition was optimized and the chemical composition of fractionated polymer chains was investigated as a function of barrier solvent strength using an online Fourier-transform infrared (FTIR) detector. Our study revealed that both the HDPE segments as well as asymmetric block copolymer chains (HDPE block length≫VLDPE block length) are retained in the separation and the barrier strength can be tailored to retain a particular composition. At the optimum barrier solvent composition, this method can be applied to separate effective HDPE segments from the other components, which has been demonstrated using an experimental OBC sample. Copyright © 2016 Elsevier B.V. All rights reserved.

Oxidation and biodegradation of polyethylene films containing pro-oxidantadditives: Synergistic effects of sunlight exposure, thermal aging and fungal biodegradation

USDA-ARS?s Scientific Manuscript database

Synergistic effects of sunlight exposure, thermal aging and fungal biodegradation on the oxidation and biodegradation of linear low density poly (ethylene) PE-LLD films containing pro-oxidant were examined. To achieve oxidation and degradation, films were first exposed to the sunlight for 93 days du...

Excess entropy scaling for the segmental and global dynamics of polyethylene melts.

PubMed

Voyiatzis, Evangelos; Müller-Plathe, Florian; Böhm, Michael C

2014-11-28

The range of validity of the Rosenfeld and Dzugutov excess entropy scaling laws is analyzed for unentangled linear polyethylene chains. We consider two segmental dynamical quantities, i.e. the bond and the torsional relaxation times, and two global ones, i.e. the chain diffusion coefficient and the viscosity. The excess entropy is approximated by either a series expansion of the entropy in terms of the pair correlation function or by an equation of state for polymers developed in the context of the self associating fluid theory. For the whole range of temperatures and chain lengths considered, the two estimates of the excess entropy are linearly correlated. The scaled bond and torsional relaxation times fall into a master curve irrespective of the chain length and the employed scaling scheme. Both quantities depend non-linearly on the excess entropy. For a fixed chain length, the reduced diffusion coefficient and viscosity scale linearly with the excess entropy. An empirical reduction to a chain length-independent master curve is accessible for both dynamic quantities. The Dzugutov scheme predicts an increased value of the scaled diffusion coefficient with increasing chain length which contrasts physical expectations. The origin of this trend can be traced back to the density dependence of the scaling factors. This finding has not been observed previously for Lennard-Jones chain systems (Macromolecules, 2013, 46, 8710-8723). Thus, it limits the applicability of the Dzugutov approach to polymers. In connection with diffusion coefficients and viscosities, the Rosenfeld scaling law appears to be of higher quality than the Dzugutov approach. An empirical excess entropy scaling is also proposed which leads to a chain length-independent correlation. It is expected to be valid for polymers in the Rouse regime.

Effect of thermal modification on rheological properties of polyethylene blends

DOE Office of Scientific and Technical Information (OSTI.GOV)

Siriprumpoonthum, Monchai; Nobukawa, Shogo; Yamaguchi, Masayuki, E-mail: m-yama@jaist.ac.jp

2014-03-15

We examined the effects of thermal modification under flow field on the rheological properties of linear low-density polyethylene (LLDPE) with high molecular weight, low-density polyethylene (LDPE), and their blends, without thermal stabilizer. Although structural changes during processing are not detected by size extrusion chromatography or nuclear magnetic resonance spectroscopy, linear viscoelastic properties changed greatly, especially for the LLDPE. A cross-linking reaction took place, leading to, presumably, star-shaped long-chain branches. Consequently, the modified LLDPE, having high zero-shear viscosity, became a thermorheologically complex melt. Moreover, it should be noted that the drawdown force, defined as the uniaxial elongational force at a constantmore » draw ratio, was significantly enhanced for the blends. Enhancement of elongational viscosity was also detected. The drawdown force and elongational viscosity are marked for the thermally modified blend as compared with those for the blend of thermally modified pure components. Intermolecular cross-linking reactions between LDPE and LLDPE, yielding polymers with more than two branch points per chain, result in marked strain-hardening in the elongational viscosity behavior even at small strain. The recovery curve of the oscillatory modulus after the shear modification is further evidence of a branched structure.« less

Thermodynamics of single polyethylene and polybutylene glycols with hydrogen-bonding ends: A transition from looped to open conformations

NASA Astrophysics Data System (ADS)

Lee, Eunsang; Paul, Wolfgang

2018-02-01

A variety of linear polymer precursors with hydrogen bonding motifs at both ends enable us to design supramolecular polymer systems with tailored macroscopic properties including self-healing. In this study, we investigate thermodynamic properties of single polyethylene and polybutylene glycols with hydrogen bonding motifs. In this context, we first build a coarse-grained model of building blocks of the supramolecular polymer system based on all-atom molecular structures. The density of states of the single precursor is obtained using the stochastic approximation Monte Carlo method. Constructing canonical partition functions from the density of states, we find the transition from looped to open conformations at transition temperatures which are non-monotonously changing with an increasing degree of polymerization due to the competition between chain stiffness and loop-forming entropy penalty. In the complete range of chain length under investigation, a coexistence of the looped and open morphologies at the transition temperature is shown regardless of whether the transition is first-order-like or continuous. Polyethylene and polybutylene glycols show similar behavior in all the thermodynamic properties but the transition temperature of the more flexible polybutylene glycol is shown to change more gradually.

Computational method for analysis of polyethylene biodegradation

NASA Astrophysics Data System (ADS)

Watanabe, Masaji; Kawai, Fusako; Shibata, Masaru; Yokoyama, Shigeo; Sudate, Yasuhiro

2003-12-01

In a previous study concerning the biodegradation of polyethylene, we proposed a mathematical model based on two primary factors: the direct consumption or absorption of small molecules and the successive weight loss of large molecules due to β-oxidation. Our model is an initial value problem consisting of a differential equation whose independent variable is time. Its unknown variable represents the total weight of all the polyethylene molecules that belong to a molecular-weight class specified by a parameter. In this paper, we describe a numerical technique to introduce experimental results into analysis of our model. We first establish its mathematical foundation in order to guarantee its validity, by showing that the initial value problem associated with the differential equation has a unique solution. Our computational technique is based on a linear system of differential equations derived from the original problem. We introduce some numerical results to illustrate our technique as a practical application of the linear approximation. In particular, we show how to solve the inverse problem to determine the consumption rate and the β-oxidation rate numerically, and illustrate our numerical technique by analyzing the GPC patterns of polyethylene wax obtained before and after 5 weeks cultivation of a fungus, Aspergillus sp. AK-3. A numerical simulation based on these degradation rates confirms that the primary factors of the polyethylene biodegradation posed in modeling are indeed appropriate.

Immobilization of natural anti-oxidants on carbon nanotubes and aging behavior of ultra-high molecular weight polyethylene-based nanocomposites

NASA Astrophysics Data System (ADS)

Dintcheva, Nadka Tzankova; Arrigo, Rossella; Gambarotti, Cristian; Guenzi, Monica; Carroccio, Sabrina; Cicogna, Francesca; Filippone, Giovanni

2014-05-01

The use of natural antioxidants is an attractive way to formulate nanocomposites with extended durability and with potential applications in bio-medical field. In this work, Vitamin E (VE) in the form of α-tocopherol and Quercetin (Q) are physically immobilized on the outer surface of multi-walled carbon nanotubes (CNTs). Afterward, the CNTs-VE and CNTs-Q are used to formulate thermally stable ultra high molecular weight polyethylene based nanocomposites. The obtained results in the study of the thermo-oxidation behavior suggest a beneficial effect of the natural anti-oxidant carbon nanotubes systems. The unexpected excellent thermo-resistance of the nanocomposites seems to be due to a synergistic effect of the natural anti-oxidant and carbon nanotubes, i.e. strong interaction between CNT surface and anti-oxidant molecules. Particularly, these interactions cause the formation of structural defects onto outer CNT surfaces, which, in turn, increase the CNT radical scavenging activity.

Polymer-ionic liquid ternary systems for Li-battery electrolytes: Molecular dynamics studies of LiTFSI in a EMIm-TFSI and PEO blend

NASA Astrophysics Data System (ADS)

Costa, Luciano T.; Sun, Bing; Jeschull, Fabian; Brandell, Daniel

2015-07-01

This paper presents atomistic molecular dynamics simulation studies of lithium bis(trifluoromethane)sulfonylimide (LiTFSI) in a blend of 1-ethyl-3-methylimidazolium (EMIm)-TFSI and poly(ethylene oxide) (PEO), which is a promising electrolyte material for Li- and Li-ion batteries. Simulations of 100 ns were performed for temperatures between 303 K and 423 K, for a Li:ether oxygen ratio of 1:16, and for PEO chains with 26 EO repeating units. Li+ coordination and transportation were studied in the ternary electrolyte system, i.e., PEO16LiTFSIṡ1.0 EMImTFSI, by applying three different force field models and are here compared to relevant simulation and experimental data. The force fields generated significantly different results, where a scaled charge model displayed the most reasonable comparisons with previous work and overall consistency. It is generally seen that the Li cations are primarily coordinated to polymer chains and less coupled to TFSI anion. The addition of EMImTFSI in the electrolyte system enhances Li diffusion, associated to the enhanced TFSI dynamics observed when increasing the overall TFSI anion concentration in the polymer matrix.

Polymer-ionic liquid ternary systems for Li-battery electrolytes: Molecular dynamics studies of LiTFSI in a EMIm-TFSI and PEO blend.

PubMed

Costa, Luciano T; Sun, Bing; Jeschull, Fabian; Brandell, Daniel

2015-07-14

This paper presents atomistic molecular dynamics simulation studies of lithium bis(trifluoromethane)sulfonylimide (LiTFSI) in a blend of 1-ethyl-3-methylimidazolium (EMIm)-TFSI and poly(ethylene oxide) (PEO), which is a promising electrolyte material for Li- and Li-ion batteries. Simulations of 100 ns were performed for temperatures between 303 K and 423 K, for a Li:ether oxygen ratio of 1:16, and for PEO chains with 26 EO repeating units. Li(+) coordination and transportation were studied in the ternary electrolyte system, i.e., PEO16LiTFSI⋅1.0 EMImTFSI, by applying three different force field models and are here compared to relevant simulation and experimental data. The force fields generated significantly different results, where a scaled charge model displayed the most reasonable comparisons with previous work and overall consistency. It is generally seen that the Li cations are primarily coordinated to polymer chains and less coupled to TFSI anion. The addition of EMImTFSI in the electrolyte system enhances Li diffusion, associated to the enhanced TFSI dynamics observed when increasing the overall TFSI anion concentration in the polymer matrix.

Adsorption and Exchange Dynamics in Aging Hydroxyethylcellulose Layers on Silica.

PubMed

Mubarekyan; Santore

2000-07-15

The adsorption kinetics of hydroxyethylcellulose (HEC) on silica and relaxations in adsorbed HEC layers were probed using total internal reflectance fluorescence and near-Brewster reflectivity. Like many random-coil polymers, HEC was found to adsorb at the transport-limited rate. Relaxations occurred at nearly constant interfacial mass when HEC layers were exposed to aqueous solvent, causing the subsequent exchange of chains between the layer and the free solution to become increasingly hindered. Eventually, on the time scale of a day, layers became immobilized and unable to accommodate chains from free solution. A continued fluorescence decay, beyond time scales that could be probed with self exchange, suggested further relaxations of the adsorbed HEC. The polydisperse HEC system (with an average molecular weight near 450,000) behaved qualitatively similar to molecular weight standard polyethylene oxide (PEO) layers on silica. For instance, relaxations in PEO layers occurred on a time scale of 10-20 h, like the HEC layers. Young layers of the latter, however, exhibited self-exchange kinetics that were an order of magnitude slower than PEO layers of similar age. This difference in adsorbed layer dynamics was attributed to HEC's stiffer backbone, compared with flexible PEO. Copyright 2000 Academic Press.

Polymer-ionic liquid ternary systems for Li-battery electrolytes: Molecular dynamics studies of LiTFSI in a EMIm-TFSI and PEO blend

DOE Office of Scientific and Technical Information (OSTI.GOV)

Costa, Luciano T., E-mail: ltcosta@id.uff.br; Sun, Bing; Jeschull, Fabian

2015-07-14

This paper presents atomistic molecular dynamics simulation studies of lithium bis(trifluoromethane)sulfonylimide (LiTFSI) in a blend of 1-ethyl-3-methylimidazolium (EMIm)-TFSI and poly(ethylene oxide) (PEO), which is a promising electrolyte material for Li- and Li-ion batteries. Simulations of 100 ns were performed for temperatures between 303 K and 423 K, for a Li:ether oxygen ratio of 1:16, and for PEO chains with 26 EO repeating units. Li{sup +} coordination and transportation were studied in the ternary electrolyte system, i.e., PEO{sub 16}LiTFSI⋅1.0 EMImTFSI, by applying three different force field models and are here compared to relevant simulation and experimental data. The force fields generatedmore » significantly different results, where a scaled charge model displayed the most reasonable comparisons with previous work and overall consistency. It is generally seen that the Li cations are primarily coordinated to polymer chains and less coupled to TFSI anion. The addition of EMImTFSI in the electrolyte system enhances Li diffusion, associated to the enhanced TFSI dynamics observed when increasing the overall TFSI anion concentration in the polymer matrix.« less

Modeling Primary Atomization Processes

DTIC Science & Technology

1999-02-01

consumable , catalytic igniter has shown to provide reliable, reproducible ignition in hydrogen peroxide/polyethylene hybrid engines. Currently, a...verified in a hybrid rocket using hydrogen peroxide as oxidizer and polyethylene as fuel. The engine made use of a unique Consumable Catalytic Bed (CCB...interest to the liquid and hybrid rocket engine community. TECHNOLOGY TRANSFER Performer Customer Result Application 1 S. D. Heister Purdue University

Insulin compatibility with polymer materials used in external pump infusion systems.

PubMed

Melberg, S G; Havelund, S; Villumsen, J; Brange, J

1988-04-01

In a study designed to mimic actual user conditions for external insulin pump infusion, the insulin quality after passage through the infusion set was assessed by various analytical methods, including high performance liquid chromatography. The two infusion sets tested consisted of, firstly, a polyvinylchloride/rubber syringe and a polyvinylchloride catheter sterilized by gamma irradiation and, secondly, a polyethylene/polypropylene syringe connected to a polyethylene catheter and sterilized by ethylene oxide. The insulin solution delivered through the PVC infusion set showed a reduction of preservative to less than 30% of the initial content and increased formation of chemical transformation products of insulin varying from twice the reference level during the first day to more than three times on the third day. By contrast, the polyethylene/polypropylene infusion system showed only a minor decrease in preservative content and no increase in chemical transformation. These effects were observed irrespective of the brand of insulin and were not affected by increase of the zinc content of the insulin solution. Investigation of the influence of the sterilization methods performed on polyvinylchloride and polyethylene catheters revealed that gamma irradiated polyvinylchloride catheters were markedly harmful to the insulin solution, whereas ethylene oxide sterilization did not influence the chemical stability of insulin.

Ionic-Liquid-Based Polymer Electrolytes for Battery Applications.

PubMed

Osada, Irene; de Vries, Henrik; Scrosati, Bruno; Passerini, Stefano

2016-01-11

The advent of solid-state polymer electrolytes for application in lithium batteries took place more than four decades ago when the ability of polyethylene oxide (PEO) to dissolve suitable lithium salts was demonstrated. Since then, many modifications of this basic system have been proposed and tested, involving the addition of conventional, carbonate-based electrolytes, low molecular weight polymers, ceramic fillers, and others. This Review focuses on ternary polymer electrolytes, that is, ion-conducting systems consisting of a polymer incorporating two salts, one bearing the lithium cation and the other introducing additional anions capable of plasticizing the polymer chains. Assessing the state of the research field of solid-state, ternary polymer electrolytes, while giving background on the whole field of polymer electrolytes, this Review is expected to stimulate new thoughts and ideas on the challenges and opportunities of lithium-metal batteries. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fast Lithium-Ion Transportation in Crystalline Polymer Electrolytes.

PubMed

Fu, Xiao-Bin; Yang, Guang; Wu, Jin-Ze; Wang, Jia-Chen; Chen, Qun; Yao, Ye-Feng

2018-01-05

Fast lithium-ion transportation is found in the crystalline polymer electrolytes, α-CD-PEO n /Li + (n=12, 40), prepared by self-assembly of α-cyclodextrin (CD), polyethylene oxide (PEO) and Li + salts. A detailed solid-state NMR study combined with the X-ray diffraction technique reveals the unique structural features of the samples, that is, a) the tunnel structure formed by the assembled CDs, providing the ordered long-range pathway for Li + ion transportation; b) the all-trans conformational sequence of the PEO chains in the tunnels, attenuating significantly the coordination between Li + and the EO segments. The origin of the fast lithium-ion transportation has been attributed to these unique structural features. This work demonstrates the first example in solid polymer electrolytes (SPEs) for "creating" fast ion transportation through material design and will find potential applications in the design of new ionconducting SPE materials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen Bond Induces Hierarchical Self-Assembly in Liquid-Crystalline Block Copolymers.

PubMed

Huang, Shuai; Pang, Linlin; Chen, Yuxuan; Zhou, Liming; Fang, Shaoming; Yu, Haifeng

2018-03-01

Microphase-separated structures of block copolymers (BCs) with a size of sub-10 nm are usually obtained by hydrogen-bond-induced self-assembly of BCs through doping with small molecules as functional additives. Here, fabrication of hierarchically self-assembled sub-10 nm structures upon microphase separation of amphiphilic liquid-crystalline BCs (LCBCs) at the existence of hydrogen bonds but without any dopants is reported. The newly introduced urethane groups in the side chain of the hydrophobic block of LCBCs interact with the ether groups of the hydrophilic poly(ethylene oxide) (PEO) block, leading to imperfect crystallization of the PEO blocks. Both crystalline and amorphous domains coexist in the separated PEO phase, enabling a lamellar structure to appear inside the PEO nanocylinders. This provides an elegant method to fabricate controllable sub-10 nm microstructures in well-defined polymer systems without the introduction of any dopants. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Measurements of Attractive Forces between Proteins and End-Grafted Poly(Ethylene Glycol) Chains

NASA Astrophysics Data System (ADS)

Sheth, S. R.; Leckband, D.

1997-08-01

The surface force apparatus was used to measure directly the molecular forces between streptavidin and lipid bilayers displaying grafted Mr 2,000 poly(ethylene glycol) (PEG). These measurements provide direct evidence for the formation of relatively strong attractive forces between PEG and protein. At low compressive loads, the forces were repulsive, but they became attractive when the proteins were pressed into the polymer layer at higher loads. The adhesion was sufficiently robust that separation of the streptavidin and PEG uprooted anchored polymer from the supporting membrane. These interactions altered the properties of the grafted chains. After the onset of the attraction, the polymer continued to bind protein for several hours. The changes were not due to protein denaturation. These data demonstrate directly that the biological activity of PEG is not due solely to properties of simple polymers such as the excluded volume. It is also coupled to the competitive interactions between solvent and other materials such as proteins for the chain segments and to the ability of this material to adopt higher order intrachain structures.

Sol-gel immobilized short-chain poly(ethylene glycol) coating for capillary microextraction of underivatized polar analytes.

PubMed

Kulkarni, Sameer; Shearrow, Anne M; Malik, Abdul

2007-12-07

Sol-gel coating with covalently bonded low-molecular-weight (MW<300 Da) poly(ethylene glycol) (PEG) chains was developed for capillary microextraction (CME). The sol-gel chemistry proved effective in the immobilization of low-molecular-weight PEGs thanks to the formation of chemical bonds between the organic-inorganic hybrid sol-gel PEG coating and the fused silica capillary inner surface. This chemical anchorage provided excellent thermal and solvent stability to the created sol-gel PEG coating as is evidenced by its high upper limit of allowable conditioning temperature (340 degrees C) and its practically identical performance before and after rinsing with various solvents. The prepared sol-gel PEG coating provided simultaneous extraction of moderately polar and highly polar analytes from aqueous samples without requiring derivatization, pH adjustment or salting-out procedures. Detection limits on the order of nanogram per liter (ng/L) were achieved in CME-GC-flame ionization detection experiments designed for the preconcentration and trace analysis of both highly polar and moderately polar compounds extracted directly from aqueous media using sol-gel short-chain PEG coated microextraction capillaries.

12-crown-4 ether-assisted enhancement of ionic conductivity and interfacial kinetics in polyethylene oxide electrolytes

NASA Technical Reports Server (NTRS)

Nagasubramanian, G.; Di Stefano, S.

1990-01-01

The electrical and electrochemical properties of thin films of polyethylene oxide electrolytes with and without 12-crown-4 ether (12Cr4) are studied as a function of temperature and in the frequency regime from 100 kHz to 0.1 Hz. These measurements were made on electrolytes containing LiCF3SO3, LiBF4, or LiClO4 salts. At a given temperature, the bulk conductivity for a particular salt depends on the 12Cr4 concentration, reaching a maximum for a ratio of 12Cr4 to Li of 0.003.

Ion conducting polymers and polymer blends for alkali metal ion batteries

DOEpatents

DeSimone, Joseph M.; Pandya, Ashish; Wong, Dominica; Vitale, Alessandra

2017-08-29

Electrolyte compositions for batteries such as lithium ion and lithium air batteries are described. In some embodiments the compositions are liquid compositions comprising (a) a homogeneous solvent system, said solvent system comprising a perfluropolyether (PFPE) and polyethylene oxide (PEO); and (b) an alkali metal salt dissolved in said solvent system. In other embodiments the compositions are solid electrolyte compositions comprising: (a) a solid polymer, said polymer comprising a crosslinked product of a crosslinkable perfluropolyether (PFPE) and a crosslinkable polyethylene oxide (PEO); and (b) an alkali metal ion salt dissolved in said polymer. Batteries containing such compositions as electrolytes are also described.

Field Effect Transistor Behavior in Electrospun Polyaniline/Polyethylene Oxide Nanofibers

NASA Technical Reports Server (NTRS)

Miranda, Felix A.; Theofylaktos, Noulle; Robinson, Daryl C.; Mueller, Carl H.; Pinto, Nicholas J.

2004-01-01

Novel translators and logic devices based on nanotechnology concepts are under intense development. The potential for ultra-low power circuitry makes nanotechnology attractive for applications such as digital electronics and sensors. Furthermore, the ability to form devices on flexible substrates expands the range of applications where electronic circuitry can be introduced. For NASA, nonotechndogy offers opportunities for increased onboard data processing and thus autonomous decision-making ability, ad novel sensors that detect and respond to external stimuli with few oversight requirements. The goat of this work is to demonstrate transistor behavior in polyaniline/ polyethylene oxide nanofibers, thus creating a foundation for future logic devices.

Prediction of solubility parameters and miscibility of pharmaceutical compounds by molecular dynamics simulations.

PubMed

Gupta, Jasmine; Nunes, Cletus; Vyas, Shyam; Jonnalagadda, Sriramakamal

2011-03-10

The objectives of this study were (i) to develop a computational model based on molecular dynamics technique to predict the miscibility of indomethacin in carriers (polyethylene oxide, glucose, and sucrose) and (ii) to experimentally verify the in silico predictions by characterizing the drug-carrier mixtures using thermoanalytical techniques. Molecular dynamics (MD) simulations were performed using the COMPASS force field, and the cohesive energy density and the solubility parameters were determined for the model compounds. The magnitude of difference in the solubility parameters of drug and carrier is indicative of their miscibility. The MD simulations predicted indomethacin to be miscible with polyethylene oxide and to be borderline miscible with sucrose and immiscible with glucose. The solubility parameter values obtained using the MD simulations values were in reasonable agreement with those calculated using group contribution methods. Differential scanning calorimetry showed melting point depression of polyethylene oxide with increasing levels of indomethacin accompanied by peak broadening, confirming miscibility. In contrast, thermal analysis of blends of indomethacin with sucrose and glucose verified general immiscibility. The findings demonstrate that molecular modeling is a powerful technique for determining the solubility parameters and predicting miscibility of pharmaceutical compounds. © 2011 American Chemical Society

Thiourea incorporated poly(ethylene oxide) as transparent gel polymer electrolyte for dye sensitized solar cell applications

NASA Astrophysics Data System (ADS)

Pavithra, Nagaraj; Velayutham, David; Sorrentino, Andrea; Anandan, Sambandam

2017-06-01

A new series of transparent gel polymer electrolytes are prepared by adding various weight percent of thiourea coupled with poly(ethylene oxide) for the application of dye-sensitized solar cells. Coupling of thiourea in the presence of iodine undergoes dimerization reaction to produce formamidine disulfide. Fourier Transform Infrared spectroscopy shows that the interactions of thiourea and formamidine disulfide with electronegative ether linkage of poly(ethylene oxide) results in conformational changes of gel polymer electrolytes. Electrochemical impedance spectroscopy and linear sweep voltammetry experiments reveal an increment in ionic conductivity and tri-iodide diffusion coefficient, for thiourea modified gel polymer electrolytes. Finally, the prepared electrolytes are used as a redox mediator in dye-sensitized solar cells and the photovoltaic properties were studied. Apart from transparency, the gel polymer electrolytes with thiorurea show higher photovoltaic properties compared to bare gel polymer electrolyte and a maximum photocurrent efficiency of 7.17% is achieved for gel polymer electrolyte containing 1 wt% of thiourea with a short circuit current of 11.79 mA cm-2 and open circuit voltage of 834 mV. Finally, under rear illumination, almost 90% efficiency is retained upon compared to front illumination.

Pyrolysis of polyethylene terephthalate containing real waste plastics using Ni loaded zeolite catalysts

NASA Astrophysics Data System (ADS)

Al-asadi, M.; Miskolczi, N.

2018-05-01

In this work the pyrolysis of polyethylene terephthalate (PET) containing real waste plastic was investigated using different Ni loaded catalysts: Ni/ZSM-5, Ni/y-zeolite, Ni/β-zeolite and Ni/natural zeolite (clinoptilolite). Raw materials were pyrolyzed in a horizontal tubular reactor between 600 and 900°C using 10% of catalysts. It was found, that both temperature increasing and catalysts presence can increase the gas yields, however owing to gasification reactions, the pyrolysis oil yield decreased with increasing temperature. Ni/y-zeolite catalyst had the most benefit in gas yield increasing at low temperature; however Ni/ZSM-5 showed advanced property in gas yield increasing at high temperature. Gases contained hydrogen, carbon oxides and hydrocarbons, which composition was significantly affected by catalysts. Ni loaded zeolites favoured to the formation of hydrogen and branched hydrocarbons; furthermore the concentrations of both CO and CO2 were also increased as function of elevated temperature. That phenomenon was attributed to the further decomposition of PET, especially to the side chain scission reactions. Owing to the Boudouard reaction, the ratio of CO2/CO can increased with temperature. Pyrolysis oils were the mixtures of n-saturated, n-unsaturated, branched, oxygen free aromatics and oxygenated hydrocarbons. Temperature increasing has a significant effect to the aromatization and isomerization reactions, while the catalysts can efficiently decreased the concentration of oxygen containing compounds.

Formation and stability of water-soluble, molecular polyelectrolyte complexes: effects of charge density, mixing ratio, and polyelectrolyte concentration.

PubMed

Shovsky, Alexander; Varga, Imre; Makuska, Ricardas; Claesson, Per M

2009-06-02

The formation of complexes with stoichiometric (1:1) as well as nonstoichiometric (2:1) and (1:2) compositions between oppositely charged synthetic polyelectrolytes carrying strong ionic groups and significantly different molecular weights is reported in this contribution. Poly(sodium styrenesulfonate) (NaPSS) was used as polyanion, and a range of copolymers with various molar ratios of the poly(methacryloxyethyltrimethylammonium) chloride, poly(METAC), and the nonionic poly(ethylene oxide) ether methacrylate, poly(PEO45MEMA), were used as polycations. Formation and stability of PECs have been investigated by dynamic and static light scattering (LS), turbidity, and electrophoretic mobility measurements as a function of polyelectrolyte solution concentration, charge density of the cationic polyelectrolyte, and mixing ratio. The data obtained demonstrate that in the absence of PEO45 side chains the 100% charged polymer (polyMETAC) formed insoluble PECs with PSS that precipitate from solution when exact stoichiometry is achieved. In nonstoichiometric complexes (1:2) and (2:1) large colloidally stable aggregates were formed. The presence of even a relatively small amount of PEO45 side chains (25%) in the cationic copolymer was sufficient for preventing precipitation of the formed stoichiometric and nonstoichiometric complexes. These PEC's are sterically stabilized by the PEO45 chains. By further increasing the PEO45 side-chain content (50 and 75%) of the cationic copolymer, small, water-soluble molecular complexes could be formed. The data suggest that PSS molecules and the charged backbone of the cationic brush form a compact core, and with sufficiently high PEO45 chain density (above 25%) molecular complexes are formed that are stable over prolonged times.

Influence of Polyethylene Glycol Lipid Desorption Rates on Pharmacokinetics and Pharmacodynamics of siRNA Lipid Nanoparticles

PubMed Central

Mui, Barbara L; Tam, Ying K; Jayaraman, Muthusamy; Ansell, Steven M; Du, Xinyao; Tam, Yuen Yi C; Lin, Paulo JC; Chen, Sam; Narayanannair, Jayaprakash K; Rajeev, Kallanthottathil G; Manoharan, Muthiah; Akinc, Akin; Maier, Martin A; Cullis, Pieter; Madden, Thomas D; Hope, Michael J

2013-01-01

Lipid nanoparticles (LNPs) encapsulating short interfering RNAs that target hepatic genes are advancing through clinical trials, and early results indicate the excellent gene silencing observed in rodents and nonhuman primates also translates to humans. This success has motivated research to identify ways to further advance this delivery platform. Here, we characterize the polyethylene glycol lipid (PEG-lipid) components, which are required to control the self-assembly process during formation of lipid particles, but can negatively affect delivery to hepatocytes and hepatic gene silencing in vivo. The rate of transfer from LNPs to plasma lipoproteins in vivo is measured for three PEG-lipids with dialkyl chains 14, 16, and 18 carbons long. We show that 1.5 mol % PEG-lipid represents a threshold concentration at which the chain length exerts a minimal effect on hepatic gene silencing but can still modify LNPs pharmacokinetics and biodistribution. Increasing the concentration to 2.5 and 3.5 mol % substantially compromises hepatocyte gene knockdown for PEG-lipids with distearyl (C18) chains but has little impact for shorter dimyristyl (C14) chains. These data are discussed with respect to RNA delivery and the different rates at which the steric barrier disassociates from LNPs in vivo. PMID:24345865

Comparison of biodegradation of poly(ethylene glycol)s and poly(propylene glycol)s.

PubMed

Zgoła-Grześkowiak, Agnieszka; Grześkowiak, Tomasz; Zembrzuska, Joanna; Łukaszewski, Zenon

2006-07-01

The biodegradation of poly(ethylene glycol)s (PEGs) and poly(propylene glycol)s (PPGs), both being major by-products of non-ionic surfactants biodegradation, was studied under the conditions of the River Water Die-Away Test. PEGs were isolated from a water matrix using solid-phase extraction with graphitized carbon black sorbent, then derivatized with phenyl isocyanate and determined by HPLC with UV detection. PPGs were isolated from a water matrix by liquid-liquid extraction with chloroform, then derivatized with naphthyl isocyanate and determined by HPLC with fluorescence detection. The primary biodegradation of both PEGs and PPGs reached approximately 99% during the test. The tests show different biodegradation pathways of PEG and PPG. During PEG biodegradation, their chains are shortened leading to the formation of ethylene glycol and diethylene glycol. During PPG biodegradation, no short-chained biodegradation products were found.

Molecular origins of anisotropic shock propagation in crystalline and amorphous polyethylene

NASA Astrophysics Data System (ADS)

O'Connor, Thomas C.; Elder, Robert M.; Sliozberg, Yelena R.; Sirk, Timothy W.; Andzelm, Jan W.; Robbins, Mark O.

2018-03-01

Molecular dynamics simulations are used to analyze shock propagation in amorphous and crystalline polyethylene. Results for the shock velocity Us are compared to predictions from Pastine's equation of state and hydrostatic theory. The results agree with Pastine at high impact velocities. At low velocities the yield stress becomes important, increasing the shock velocity and leading to anisotropy in the crystalline response. Detailed analysis of changes in atomic order reveals the origin of the anisotropic response. For shock along the polymer backbone, an elastic front is followed by a plastic front where chains buckle with a characteristic wavelength. Shock perpendicular to the chain backbone can produce plastic deformation or transitions to different orthorhombic or monoclinic structures, depending on the impact speed and direction. Tensile loading does not produce stable shocks: Amorphous systems craze and fracture while for crystals the front broadens linearly with time.

Molar mass fractionation in aqueous two-phase polymer solutions of dextran and poly(ethylene glycol).

PubMed

Zhao, Ziliang; Li, Qi; Ji, Xiangling; Dimova, Rumiana; Lipowsky, Reinhard; Liu, Yonggang

2016-06-24

Dextran and poly(ethylene glycol) (PEG) in phase separated aqueous two-phase systems (ATPSs) of these two polymers, with a broad molar mass distribution for dextran and a narrow molar mass distribution for PEG, were separated and quantified by gel permeation chromatography (GPC). Tie lines constructed by GPC method are in excellent agreement with those established by the previously reported approach based on density measurements of the phases. The fractionation of dextran during phase separation of ATPS leads to the redistribution of dextran of different chain lengths between the two phases. The degree of fractionation for dextran decays exponentially as a function of chain length. The average separation parameters, for both dextran and PEG, show a crossover from mean field behavior to Ising model behavior, as the critical point is approached. Copyright © 2016 Elsevier B.V. All rights reserved.

Biomechanical modeling of acetabular component polyethylene stresses, fracture risk, and wear rate following press-fit implantation.

PubMed

Ong, Kevin L; Rundell, Steve; Liepins, Imants; Laurent, Ryan; Markel, David; Kurtz, Steven M

2009-11-01

Press-fit implantation may result in acetabular component deformation between the ischial-ilial columns ("pinching"). The biomechanical and clinical consequences of liner pinching due to press-fit implantation have not been well studied. We compared the effects of pinching on the polyethylene fracture risk, potential wear rate, and stresses for two different thickness liners using computational methods. Line-to-line ("no pinch") reaming and 2 mm underreaming press fit ("pinch") conditions were examined for Trident cups with X3 polyethylene liner wall thicknesses of 5.9 mm (36E) and 3.8 mm (40E). Press-fit cup deformations were measured from a foam block configuration. A hybrid material model, calibrated to experimentally determined stress-strain behavior of sequentially annealed polyethylene, was applied to the computational model. Molecular chain stretch did not exceed the fracture threshold in any cases. Nominal shell pinch of 0.28 mm was estimated to increase the volumetric wear rate by 70% for both cups and peak contact stresses by 140 and 170% for the 5.9 and 3.8 mm-thick liners, respectively. Although pinching increases liner stresses, polyethylene fracture is highly unlikely, and the volumetric wear rates are likely to be low compared to conventional polyethylene. (c) 2009 Orthopaedic Research Society. Published by Wiley Periodicals, Inc.

Thermal conductivity of a single polymer chain

NASA Astrophysics Data System (ADS)

Freeman, J. J.; Morgan, G. J.; Cullen, C. A.

1987-05-01

Numerical experiments have been performed with use of a fairly realistic model for polyethylene which has enabled the effects of anharmonicity, temperature, and positional disorder on the thermal conductivity to be investigated. It has been shown that the classical conductivity may be substantially increased by both increasing the strength of the anharmonic forces and by decreasing the chain temperature. Although the conductivity of individual chains is found to be high, realistic values for the conductivity of a bulk material may be understood provided that due account is taken of the polymer conformation and interchain coupling.

Surface modification of polyethylene by radiation-induced grafting for adhesive bonding. V. Comparison with other surface treatments. [Gamma radiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yamakawa, S.; Yamamoto, F.

1980-01-01

Helium gas plasma treatment of low-density polyethylene (LDPE) yields much lower peel strength than oxidative treatment using chromic acid and oxygen gas plasma. The practical adhesion, the bondability retention, and the bond durability of oxidatively treated LDPE sheets, bonded with epoxy adhesives, have been compared with those of partially hydrolyzed LDPE-methyl acrylate surface grafts. The oxidized surfaces easily lose the bondability by light rubbing with tissue paper, solvent extraction, heat aging, and artificial weathering, whereas the grafted surfaces retain the bondability. The bondability loss is due to removal of the oxidized layer, and the bondability retention is due to retentionmore » of the surface homopolymer layer. Conventional antioxidants stabilize the grafted but not the oxidized surfaces against thermal oxidative degradation. The grafted LDPE joints have much higher bond durability in humid environments than those of the oxidized LDPE joints. The dry and wet peel strengths of oxidized LDPE joints are greatly improved by application of primers consisting of a base epoxy resin and organic solvents. An adhesion mechanism involving penetration of epoxy adhesives into the oxidized layers and subsequent reinforcement of the layers by curing of the penetrated epoxy is proposed. 5 figures, 5 tables.« less

Study of the desorption of ethylene oxide fixed on various materials during sterilization by a new procedure

NASA Technical Reports Server (NTRS)

Lacomme, M.; Chaigneau, M.; Lemoan, G.

1977-01-01

A continuous sterilization process using ethylene oxide was studied in comparison with a classical method in order to evaluate gas retention as a function of time and temperature on polyethylene, PVC, and rubber materials.

Effect of HDPE plastic waste towards batako properties

NASA Astrophysics Data System (ADS)

Nursyamsi, N.; Indrawan, I.; Theresa, V.

2018-02-01

Indonesia is the world’s second largest producer of plastic waste to the sea, after China. Most of the plastic waste is polyethylene. Polyethylene is a polymer consisting of long chains of ethylene monomers. Moreover, polyethylene is plastic that has characteristics such as; thermoplastic, elastic, non-translucent, odorless, slightly opaque and transparent, resistant to impact and has a resistance of up to 135 degrees Celsius. The type of HDPE plastic (high-density polyethylene), which has been cleaned and chopped as a substitute of fine aggregate, is used in the brick’s making process. HDPE has a stronger, harder, smoother and more resistant to high-temperature properties. In this study, a weight variation of 0%, 10%, and 20% of HDPE plastic wastes was used from the total weight of sand as a substitution. Furthermore, the tensile and compressive strength were tested on day 7. Based on the research, the quality of the specimen achieved was categorized in quality III according to SNI 03-0349-1989.

Micro X-Ray Computed Tomography Mass Loss Assessment of Different UHMWPE: A Hip Joint Simulator Study on Standard vs. Cross-Linked Polyethylene

PubMed Central

Zanini, Filippo; Carmignato, Simone

2017-01-01

More than 60.000 hip arthroplasty are performed every year in Italy. Although Ultra-High-Molecular-Weight-Polyethylene remains the most used material as acetabular cup, wear of this material induces over time in vivo a foreign-body response and consequently osteolysis, pain, and the need of implant revision. Furthermore, oxidative wear of the polyethylene provoke several and severe failures. To solve these problems, highly cross-linked polyethylene and Vitamin-E-stabilized polyethylene were introduced in the last years. In in vitro experiments, various efforts have been made to compare the wear behavior of standard PE and vitamin-E infused liners. In this study we compared the in vitro wear behavior of two different configurations of cross-linked polyethylene (with and without the add of Vitamin E) vs. the standard polyethylene acetabular cups. The aim of the present study was to validate a micro X-ray computed tomography technique to assess the wear of different commercially available, polyethylene’s acetabular cups after wear simulation; in particular, the gravimetric method was used to provide reference wear values. The agreement between the two methods is documented in this paper. PMID:28107468

Mid-term survivorship and clinical outcomes of cobalt-chrome and oxidized zirconium on highly crosslinked polyethylene.

PubMed

Petis, Stephen M; Vasarhelyi, Edward M; Lanting, Brent A; Howard, James L; Naudie, Douglas D R; Somerville, Lyndsay E; McCalden, Richard W

2016-02-01

The choice of bearing articulation for total hip arthroplasty in younger patients is amenable to debate. We compared mid-term patient-reported outcomes and survivorship across 2 different bearing articulations in a young patient cohort. We reviewed patients with cobalt-chrome or oxidized zirconium on highly crosslinked polyethylene who were followed prospectively between 2004 and 2012. Kaplan-Meier analysis was used to determine predicted cumulative survivorship at 5 years with all-cause and aseptic revisions as the outcome. We compared patient-reported outcomes, including the Harris hip score (HHS), Western Ontario and McMaster University Osteoarthritis Index (WOMAC) and Short-form 12 (SF-12) scores. A total of 622 patients were followed during the study period. Mean follow-up was 8.2 (range 2.0-10.6) years for cobalt-chrome and 7.8 (range 2.1-10.7) years for oxidized zirconium. Mean age was 54.9 ± 10.6 years for cobalt-chrome and 54.8 ± 10.7 years for oxidized zirconium. Implant survivorship was 96.0% (95% confidence interval [CI] 94.9%-97.1%) for cobalt-chrome and 98.7% (95% CI 98.0%-99.4%) for oxidized zirconium on highly crosslinked polyethylene for all-cause revisions, and 97.2% (95% CI 96.2%-98.2%) for cobalt-chrome and 99.0% (95% CI 98.4%-99.6%) for oxidized zirconium for aseptic revisions. An age-, sex- and diagnosis-matched comparison of the HHS, WOMAC and SF-12 scores demonstrated no significant changes in clinical outcomes across the groups. Both bearing surface couples demonstrated excellent mid-term survivorship and outcomes in young patient cohorts. Future analyses on wear and costs are warranted to elicit differences between the groups at long-term follow-up.

Non-destructive evaluation of polyolefin thermal aging using infrared spectroscopy

NASA Astrophysics Data System (ADS)

Fifield, Leonard S.; Shin, Yongsoon; Simmons, Kevin L.

2017-04-01

Fourier transform infrared (FTIR) spectroscopy is an information-rich method that reveals chemical bonding near the surface of polymer composites. FTIR can be used to verify composite composition, identify chemical contaminants and expose composite moisture content. Polymer matrix changes due to thermal exposure including loss of additives, chain scission, oxidation and changes in crystallinity may also be determined using FTIR spectra. Portable handheld instruments using non-contact reflectance or surface contact attenuated total reflectance (ATR) may be used for nondestructive evaluation (NDE) of thermal aging in polymer and composite materials of in-service components. We report the use of ATR FTIR to track oxidative thermal aging in ethylene-propylene rubber (EPR) and chlorinated polyethylene (CPE) materials used in medium voltage nuclear power plant electrical cable insulation and jacketing. Mechanical property changes of the EPR and CPE materials with thermal degradation for correlation with FTIR data are tracked using indenter modulus (IM) testing. IM is often used as a local NDE metric of cable jacket health. The FTIR-determined carbonyl index was found to increase with IM and may be a valuable NDE metric with advantages over IM for assessing cable remaining useful life.

Non-Destructive Evaluation of Polyolefin Thermal Aging Using Infrared Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fifield, Leonard S.; Shin, Yongsoon; Simmons, Kevin L.

Fourier transform infrared (FTIR) spectroscopy is an information-rich method that reveals chemical bonding near the surface of polymer composites. FTIR can be used to verify composite composition, identify chemical contaminants and expose composite moisture content. Polymer matrix changes due to thermal exposure including loss of additives, chain scission, oxidation and changes in crystallinity may also be determined using FTIR spectra. Portable handheld instruments using non-contact reflectance or surface contact attenuated total reflectance (ATR) may be used for non-destructive evaluation (NDE) of thermal aging in polymer and composite materials of in-service components. We report the use of ATR FTIR to trackmore » oxidative thermal aging in ethylene-propylene rubber (EPR) and chlorinated polyethylene (CPE) materials used in medium voltage nuclear power plant electrical cable insulation and jacketing. Mechanical property changes of the EPR and CPE materials with thermal degradation for correlation with FTIR data are tracked using indenter modulus (IM) testing. IM is often used as a local NDE metric of cable jacket health. The FTIR-determined carbonyl index was found to increase with IM and may be a valuable NDE metric with advantages over IM for assessing cable remaining useful life.« less

Mass-action model analysis of the apparent molar volume and heat capacity of pluronics in water and liposome suspensions at 25 °C.

PubMed

Quirion, François; Meilleur, Luc; Lévesque, Isabelle

2013-07-09

Pluronics are block copolymers composed of a central block of polypropylene oxide and two side chains of polyethylene oxide. They are used in water to generate aggregates and gels or added to phospholipid suspensions to prepare microparticles for drug delivery applications. The structure of these systems has been widely investigated. However, little is known about the mechanisms leading to these structures. This investigation compares the apparent molar volumes and heat capacities of Pluronics F38, F108, F127, P85, P104, and P103 at 25 °C in water and in the presence of lecithin liposomes. The changes in molar volumes, heat capacities, and enthalpies generated by a mass-action model are in good agreement with the loss of hydrophobic hydration of the polypropylene oxide central block of the Pluronics. However, the molecularity of the endothermic transitions is much smaller than the aggregation numbers reported in the literature for the same systems. It is suggested that Pluronics go through dehydration of their central block to form unimolecular or small entities having a hydrophobic polypropylene oxide core. In water, these entities would assemble athermally to form larger aggregates. In the presence of liposomes, they would be transferred into the hydrophobic lecithin bilayers of the liposomes. Light transmission experiments suggest that the liposome suspensions are significantly altered only when the added Pluronics are in the dehydrated state.

Surfactant-directed synthesis of mesoporous films made single-step by a tandem photosol-gel/photocalcination route

DOE Office of Scientific and Technical Information (OSTI.GOV)

De Paz-Simon, Héloïse; Chemtob, Abraham, E-mail: abraham.chemtob@uha.fr; Croutxé-Barghorn, Céline

2014-11-01

In view of their technological impact in materials chemistry, a simplified and more efficient synthetic route to mesoporous films is highly sought. We report, herein, a smart UV-mediated approach coupling in a one-stage process sol-gel photopolymerization and photoinduced template decomposition/ablation to making mesoporous silica films. Performed at room temperature with a solvent-free solution of silicate precursor and amphiphilic poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymer, the synthesis relies on photoacid generation to induce the fast formation (≈10 min) of mesostructured silica/surfactant domains. Continuation of UV exposure for three additional hours enables subsequent and complete photodegradation of the polyether copolymer, resulting inmore » ordered or disordered mesoporous silica film. One of the most attractive features is that the one-step procedure relies on a continuous illumination provided by the same conventional medium-pressure Hg-Xe arc lamp equipped with a 254 nm reflector to enhance the emission of energetic photons <300 nm. In addition to X-ray diffraction and transmission electron microscopy, time-resolved Fourier transform infrared spectroscopy has proved to be a powerful in situ technique to probe the different chemical transformations accompanying irradiation. Photocalcination strengthens the inorganic network, while allowing to preserve a higher fraction of residual silanol groups compared with thermal calcination. A polyether chain degradation mechanism based on oxygen reactive species-mediated photo-oxidation is proposed.« less

Understanding the interaction of block copolymers with DMPC lipid bilayer using coarse-grained molecular dynamics simulations.

PubMed

Hezaveh, Samira; Samanta, Susruta; De Nicola, Antonio; Milano, Giuseppe; Roccatano, Danilo

2012-12-13

In this paper, we present a computational model of the adsorption and percolation mechanism of poloxamers (poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) triblock copolymers) across a 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) lipid bilayer. A coarse-grained model was used to cope with the long time scale of the percolation process. The simulations have provided details of the interaction mechanism of Pluronics with lipid bilayer. In particular, the results have shown that polymer chains containing a PPO block with a length comparable to the DMPC bilayer thickness, such as P85, tends to percolate across the lipid bilayer. On the contrary, Pluronics with a shorter PPO chain, such as L64 and F38, insert partially into the membrane with the PPO block part while the PEO blocks remain in water on one side of the lipid bilayer. The percolation of the polymers into the lipid tail groups reduces the membrane thickness and increases the area per lipid. These effects are more evident for P85 than L64 or F38. Our findings are qualitatively in good agreement with published small-angle X-ray scattering experiments that have evidenced a thinning effect of Pluronics on the lipid bilayer as well as the role of the length of the PPO block on the permeation process of the polymer through the lipid bilayer. Our theoretical results complement the experimental data with a detailed structural and dynamic model of poloxamers at the interface and inside the lipid bilayer.

Biocompatible Polysiloxane-Containing Diblock Copolymer PEO-b-PγMPS for Coating Magnetic Nanoparticles

PubMed Central

Chen, Hongwei; Wu, Xinying; Duan, Hongwei; Wang, Y. Andrew; Wang, Liya; Zhang, Minming; Mao, Hui

2009-01-01

We report a biocompatible polysiloxane containing amphiphilic diblock copolymer, poly(ethylene oxide)-block-poly(γ-methacryloxypropyltrimethoxysilane) (PEO-b-PγMPS), for coating and stabilizing nanoparticles for biomedical applications. Such amphiphilic diblock copolymer which comprises both a hydrophobic segment with “surface anchoring moiety” (silane group) and a hydrophilic segment with PEO (Mn=5000 g/mol) was obtained by the reversible addition fragmentation chain transfer (RAFT) polymerization using the PEO macromolecular chain transfer agent. When used for coating paramagnetic iron oxide nanoparticles (IONPs), copolymers were mixed with hydrophobic oleic acid coated core size uniformed IONPs (D=13 nm) in co-solvent tetrahydrofuran. After being aged over a period of time, resulting monodispersed IONPs can be transferred into aqueous medium. With proper PγMPS block length (Mn=10,000 g/mol), polysiloxane containing diblock copolymers formed a thin layer of coating (~3 nm) around monocrystalline nanoparticles as measured by transmission electron microscopy (TEM). Magnetic resonance imaging (MRI) experiments showed excellent T2 weighted contrast effect from coated IONPs with a transverse relaxivity r2=98.6 mM−1s−1 (at 1.5 Tesla). Such thin coating layer has little effect on the relaxivity when compared to that of IONPs coated with conventional amphiphilic copolymer. Polysiloxane containing diblock copolymer coated IONPs are stable without aggregation or binding to proteins in serum when incubated for 24 h in culture medium containing 10% serum. Furthermore, much lower level of intracellular uptake by macrophage cells was observed with polysiloxane containing diblock copolymers coated IONPs, suggesting the reduction of non-specific cell uptakes and antibiofouling effect. PMID:20161520

Electrospun Polyaniline/Polyethylene Oxide Nanofiber Field Effect Transistor

NASA Technical Reports Server (NTRS)

Pinto, N. J.; Johnson, A. T.; MacDiarmid, A. G.; Mueller, C. H.; Theofylaktos, N.; Robinson, D. C.; Miranda, F. A.

2003-01-01

We report on the observation of field effect transistor (FET) behavior in electrospun camphorsulfonic acid doped polyaniline(PANi)/polyethylene oxide(PE0) nanofibers. Saturation channel currents are observed at surprisingly low source/drain voltages. The hole mobility in the depletion regime is 1.4 x 10(exp -4) sq cm/V s while the 1-D charge density (at zero gate bias) is calculated to be approximately 1 hole per 50 two-ring repeat units of polyaniline, consistent with the rather high channel conductivity (approx. 10(exp -3) S/cm). Reducing or eliminating the PEO content in the fiber is expected to enhance device parameters. Electrospinning is thus proposed as a simple method of fabricating 1-D polymer FET's.

Ultrastructural investigation of intact orbital implant surfaces using atomic force microscopy.

PubMed

Choi, Samjin; Lee, Seung Jun; Shin, Jae-Ho; Cheong, Youjin; Lee, Hui-Jae; Paek, Joo Hee; Kim, Jae Sik; Jin, Kyung-Hyun; Park, Hun-Kuk

2011-01-01

This study examined the surface nanostructures of three orbital implants: nonporous poly(methyl methacrylate) (PMMA), porous aluminum oxide and porous polyethylene. The morphological characteristics of the orbital implants surfaces were observed by atomic force microscopy (AFM). The AFM topography, phase shift and deflection images of the intact implant samples were obtained. The surface of the nonporous PMMA implant showed severe scratches and debris. The surface of the aluminum oxide implant showed a porous structure with varying densities and sizes. The PMMA implant showed nodule nanostructures, 215.56 ± 52.34 nm in size, and the aluminum oxide implant showed crystal structures, 730.22 ± 341.02 nm in size. The nonporous PMMA implant showed the lowest roughness compared with other implant biomaterials, followed by the porous aluminum oxide implant. The porous polyethylene implant showed the highest roughness and severe surface irregularities. Overall, the surface roughness of orbital implants might be associated with the rate of complications and cell adhesion. Copyright © 2011 Wiley Periodicals, Inc.

Investigation of mechanical, thermal and recycled characteristics of reinforced ternary blends of LDPE/LLDPE/HDPE by ANOVA

NASA Astrophysics Data System (ADS)

Maleki, Mahnam; Farzin, Mahmud; Mosaddegh, Peiman

2018-06-01

In this study, the effect of high density polyethylene (HDPE) and calcium carbonate (CaCO3) addition into constant amount of low density polyethylene/linear low density polyethylene (LDPE/LLDPE) matrix was investigated by using different mechanical and thermal parameters. Then, analysis of variance (ANOVA) was used to investigate the normal distribution of obtained data. Finally, sample containing 50 Phr of HDPE and 7 Phr of CaCO3 microparticles, was determined as optimized sample. The effect of different process parameters such as injecting back pressure, cooling and retention time, on mechanical and thermal properties of optimized sample was investigated as well. Also to investigate the effect of the number of recycling processes on the mechanical and thermal properties, two dominant degradation mechanisms were suggested. The first was the decreasing of chains molecular weight and formation of short length chains and the later was the formation of crosslinks and three dimensional networks. Results indicated that by increasing the number of recycling processes, crystallinity, melting point, modulus, strength at yielding point and toughness in comparison to pristine sample decreased at first and then showed an ascending trend. Elongation at break by increasing of the number of recycling processes, generally increased in comparison with initial sample.

Side-chain amino-acid-based pH-responsive self-assembled block copolymers for drug delivery and gene transfer.

PubMed

Kumar, Sonu; Acharya, Rituparna; Chatterji, Urmi; De, Priyadarsi

2013-12-10

Developing safe and effective nanocarriers for multitype of delivery system is advantageous for several kinds of successful biomedicinal therapy with the same carrier. In the present study, we have designed amino acid biomolecules derived hybrid block copolymers which can act as a promising vehicle for both drug delivery and gene transfer. Two representative natural chiral amino acid-containing (l-phenylalanine and l-alanine) vinyl monomers were polymerized via reversible addition-fragmentation chain transfer (RAFT) process in the presence of monomethoxy poly(ethylene glycol) based macro-chain transfer agents (mPEGn-CTA) for the synthesis of well-defined side-chain amino-acid-based amphiphilic block copolymers, monomethoxy poly(ethylene glycol)-b-poly(Boc-amino acid methacryloyloxyethyl ester) (mPEGn-b-P(Boc-AA-EMA)). The self-assembled micellar aggregation of these amphiphilic block copolymers were studied by fluorescence spectroscopy, atomic force microscopy (AFM) and scanning electron microscopy (SEM). Potential applications of these hybrid polymers as drug carrier have been demonstrated in vitro by encapsulation of nile red dye or doxorubicin drug into the core of the micellar nanoaggregates. Deprotection of side-chain Boc- groups in the amphiphilic block copolymers subsequently transformed them into double hydrophilic pH-responsive cationic block copolymers having primary amino groups in the side-chain terminal. The DNA binding ability of these cationic block copolymers were further investigated by using agarose gel retardation assay and AFM. The in vitro cytotoxicity assay demonstrated their biocompatible nature and these polymers can serve as "smart" materials for promising bioapplications.

Raman Spectroscopy of Novel UHMW Polyethylene-Based Nanocomposites with Nanographite and Nanoclay

NASA Astrophysics Data System (ADS)

Prokhorov, K. A.; Sagitova, E. A.; Averin, A. A.; Nikolaeva, G. Yu; Baimova, A. V.; Novokshonova, L. A.; Brevnov, P. N.; Pashinin, P. P.

2018-04-01

We analyze the Raman spectra of nanocomposites based on ultrahigh-molecular-weight polyethylene with nanoclay, thermoexpanded graphite, and reduced graphite oxide fillers. We discuss the potential of Raman spectroscopy for quantitative analysis of the nanocomposite structure, the influence of the fillers on the phase and conformation compositions of the polymer matrix, as well as for the monitoring of dispersion of the nanographite fillers in the nanocomposites.

Development of radiation resistant electrical cable insulations

NASA Technical Reports Server (NTRS)

Lee, B. S.; Soo, P.; Mackenzie, D. R.

1994-01-01

Two new polyethylene cable insulations have been formulated for nuclear applications and have been tested under gamma radiation. Both insulations are based on low density polyethylene, one with PbO and the other with Sb2O3 as additives. The test results show that the concept of using inorganic antioxidants to retard radiation initiated oxidation (RIO) is viable. PbO is more effective than Sb2O3 in minimizing RIO.

Ionic liquid compatibility in polyethylene oxide/siloxane ion gel membranes

DOE PAGES

Kusuma, Victor A.; Macala, Megan K.; Liu, Jian; ...

2018-10-02

Ion gel films were prepared by incorporating eight commercially available ionic liquids in two different cross-linked polymer matrices to evaluate their phase miscibility, gas permeability and ionic conductivity for potential applications as gas separation membranes and solid electrolyte materials. The ionic liquids cations were 1-ethyl-3-methylimidazolium, 1-ethyl-3-methylpyridinium, 1-butyl-1-methylpyrrolidinium, tributylmethylphosphonium, and butyltrimethylammonium with a common anion (bis(trifluoromethylsulfonyl)imide). In addition, ionic liquids with 1-ethyl-3-methylimidazolium cation with acetate, dicyanamide and tetrafluoroborate counterions were evaluated. The two polymers were cross-linked poly(ethylene oxide) and cross-linked poly(ethylene oxide)/siloxane copolymer. Differential scanning calorimetry, X-ray diffractometry and visual observations were performed to evaluate the ion gels’ miscibility, thermal stabilitymore » and homogeneity. Ionic liquids with the least basic anion (bis(trifluoromethylsulfonyl)imide) and aromatic cations containing acidic proton (e.g. imidazolium and pyridinium) gave the most stable and miscible ion gels. Phase stability was shown to be a function of both ionic liquid content and temperature, with phase separation observed at elevated temperatures. In conclusion, gas permeability testing with carbon dioxide and nitrogen and ionic conductivity measurements confirmed that these ionic liquids increased the gas permeability and ionic conductivity of the polymers.« less

Ionic liquid compatibility in polyethylene oxide/siloxane ion gel membranes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kusuma, Victor A.; Macala, Megan K.; Liu, Jian

Ion gel films were prepared by incorporating eight commercially available ionic liquids in two different cross-linked polymer matrices to evaluate their phase miscibility, gas permeability and ionic conductivity for potential applications as gas separation membranes and solid electrolyte materials. The ionic liquids cations were 1-ethyl-3-methylimidazolium, 1-ethyl-3-methylpyridinium, 1-butyl-1-methylpyrrolidinium, tributylmethylphosphonium, and butyltrimethylammonium with a common anion (bis(trifluoromethylsulfonyl)imide). In addition, ionic liquids with 1-ethyl-3-methylimidazolium cation with acetate, dicyanamide and tetrafluoroborate counterions were evaluated. The two polymers were cross-linked poly(ethylene oxide) and cross-linked poly(ethylene oxide)/siloxane copolymer. Differential scanning calorimetry, X-ray diffractometry and visual observations were performed to evaluate the ion gels’ miscibility, thermal stabilitymore » and homogeneity. Ionic liquids with the least basic anion (bis(trifluoromethylsulfonyl)imide) and aromatic cations containing acidic proton (e.g. imidazolium and pyridinium) gave the most stable and miscible ion gels. Phase stability was shown to be a function of both ionic liquid content and temperature, with phase separation observed at elevated temperatures. In conclusion, gas permeability testing with carbon dioxide and nitrogen and ionic conductivity measurements confirmed that these ionic liquids increased the gas permeability and ionic conductivity of the polymers.« less

Polyethylene oxide-polytetrahydrofurane-PEDOT conducting interpenetrating polymer networks for high speed actuators

NASA Astrophysics Data System (ADS)

Plesse, C.; Khaldi, A.; Wang, Q.; Cattan, E.; Teyssié, D.; Chevrot, C.; Vidal, F.

2011-12-01

In recent years, numerous studies on electro-active polymer (EAP) actuators have been reported. One promising technology is the elaboration of electronic conducting polymer-based actuators with interpenetrating polymer network (IPNs) architecture. In this study, the synthesis and characterisation of conducting IPNs for actuator applications is described. The IPNs are synthesised from polyethylene oxide (PEO) and polytetrahydrofurane (PTHF) networks in which the conducting polymer (poly(3,4-ethylenedioxythiophene)) is incorporated. In a first step, PEO/PTHF IPNs were prepared via an 'in situ' process using poly(ethylene glycol) methacrylate and dimethacrylate and hydroxytelechelic PTHF as starting materials. The IPN mechanical properties were examined by DMA and tensile strength tests. N-ethylmethylimidazolium bis(trifluoromethanesulfonyl)imide (EMITFSI) swollen PEO/PTHF IPNs show ionic conductivities up to 10-3 S cm-1 at 30 °C. In a second step, the conducting IPN actuators were prepared by oxidative polymerisation of 3,4-ethylenedioxithiophene (EDOT) using FeCl3 as an oxidising agent within the PEO/PTHF IPN host matrix. The frequency response performance of the bending conducting IPN actuator was then evaluated. The resulting actuator exhibits a mechanical resonance frequency of up to 125 Hz with 0.75% strain for an applied potential of ± 5 V.

Differences in the adsorption behaviour of poly(ethylene oxide) copolymers onto model polystyrene nanoparticles assessed by isothermal titration microcalorimetry correspond to the biological differences.

PubMed

Stolnik, S; Heald, C R; Garnett, M G; Illum, L; Davis, S S

2005-01-01

The adsorption behaviour of a tetrafunctional copolymer of poly (ethylene oxide)-poly (propylene oxide) ethylene diamine (commercially available as Poloxamine 908) and a diblock copolymer of poly (lactic acid)-poly (ethylene oxide) (PLA/PEG 2:5) onto a model colloidal drug carrier (156 nm sized polystyrene latex) is described. The adsorption isotherm, hydrodynamic thickness of the adsorbed layers and enthalpy of the adsorption were assessed. The close similarity in the conformation of the poly (ethylene oxide) (PEO) chains (molecular weight 5,000 Da) in the adsorbed layers of these two copolymers was demonstrated by combining the adsorption data with the adsorbed layer thickness data. In contrast, the results from isothermal titration microcalorimetry indicated a distinct difference in the interaction of the copolymers with the polystyrene colloid surface. Poloxamine 908 adsorption to polystyrene nanoparticles is dominated by an endothermic heat effect, whereas, PLA/PEG 2:5 adsorption is entirely an exothermic process. This difference in adsorption behaviour could provide an explanation for differences in the biodistribution of Poloxamine 908 and PLA/PEG 2:5 coated polystyrene nanoparticles observed in previous studies. A comparison with the interaction enthalpy for several other PEO-containing copolymers onto the same polystyrene colloid was made. The results demonstrate the importance of the nature of the anchoring moiety on the interaction of the adsorbing copolymer with the colloid surface. An endothermic contribution is found when an adsorbing molecule contains a poly (propylene oxide) (PPO) moiety (e.g. Poloxamine 908), whilst the adsorption is exothermic (i.e. enthalpy driven) for PEO copolymers with polylactide (PLA/PEG 2:5) or alkyl moieties.

Role of hydration and water coordination in micellization of Pluronic block copolymers.

PubMed

Šturcová, Adriana; Schmidt, Pavel; Dybal, Jiří

2010-12-15

Raman, attenuated total reflectance FTIR, near-infrared spectroscopy, and DFT calculations have been used in a study of aqueous solutions of three tri-block copolymers poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) or PEO-PPO-PEO with commercial names Pluronic PE6200, PE6400 and F68. It is shown that the process of micellization as a response to increased temperature is reflected in the hydroxyl stretching region of infrared and Raman spectra, which contains information both about restructuring of water and changes of polymer chains in polymer/water aggregates. Raman spectra exhibit differences between individual Pluronics even at temperatures below the critical micellization temperature (CMT). According to the attenuated total reflection (ATR) FTIR spectra, the same five water coordination types defined by the number of donated/accepted hydrogen bonds are present in interacting water as in bulk water. It indicates that models considering mixed states of water with different hydrogen bonding environments provide appropriate descriptions of bound water both below and above the CMT. Above the CMT, aggregate hydration increases in the order PE6400 < PE6200 < F68, although that does not fully correspond to the EO/PO ratio, and points to the differences in microstructure of aggregates formed by each copolymer. This study relates nanoscale phenomena (hydrophobic and hydrophilic hydration) with the mesoscale phenomenon of micellization. Copyright © 2010 Elsevier Inc. All rights reserved.

FETs Based on Doped Polyaniline/Polyethylene Oxide Fibers

NASA Technical Reports Server (NTRS)

Theofylaktos, Noulie; Robinson, Daryl; Miranda, Felix; Pinto, Nicholas; Johnson, Alan, Jr.; MacDiarmid, Alan; Mueller, Carl

2006-01-01

A family of experimental highly miniaturized field-effect transistors (FETs) is based on exploitation of the electrical properties of nanofibers of polyaniline/ polyethylene oxide (PANi/PEO) doped with camphorsulfonic acid. These polymer-based FETs have the potential for becoming building blocks of relatively inexpensive, low-voltage, highspeed logic circuits that could supplant complementary metal oxide/semiconductor (CMOS) logic circuits. The development of these polymerbased FETs offers advantages over the competing development of FETs based on carbon nanotubes. Whereas it is difficult to control the molecular structures and, hence, the electrical properties of carbon nanotubes, it is easy to tailor the electrical properties of these polymerbased FETs, throughout the range from insulating through semiconducting to metallic, through choices of doping levels and chemical manipulation of polymer side chains. A further advantage of doped PANi/PEO nanofibers is that they can be made to draw very small currents and operate at low voltage levels, and thus are promising for applications in which there are requirements to use many FETs to obtain large computational capabilities while minimizing power demands. Fabrication of an experimental FET in this family begins with the preparation of a substrate as follows: A layer of silicon dioxide between 50 and 200 nm thick is deposited on a highly doped (resistivity 0.01 W.cm) silicon substrate, then gold electrodes/contact stripes are deposited on the oxide. Next, one or more fibers of camphorsulphonic acid-doped PANi/PEO having diameters of the order of 100 nm are electrospun onto the substrate so as to span the gap between the gold electrodes (see Figure 1). Figure 2 depicts measured current-versus-voltage characteristics of the device of Figure 1, showing that saturation channel currents occur at source-todrain potentials that are surprisingly low, relative to those of CMOS FETs. The hole mobility in the depletion regime in this transistor was found to be 1.4 10(exp -4) sq cm/(V.s), while the one-dimensional charge density at zero gate bias was estimated to be approximately one hole per 50 two-ring repeat units of polyaniline, consistent with the rather high channel conductivity (approx. 10(exp -3) S/cm). Reducing or eliminating the PEO content of the fibers is expected to enhance the properties of future versions of this transistor.

Tuning the superstructure of ultrahigh-molecular-weight polyethylene/low-molecular-weight polyethylene blend for artificial joint application.

PubMed

Xu, Ling; Chen, Chen; Zhong, Gan-Ji; Lei, Jun; Xu, Jia-Zhuang; Hsiao, Benjamin S; Li, Zhong-Ming

2012-03-01

An easy approach was reported to achieve high mechanical properties of ultrahigh-molecular-weight polyethylene (UHMWPE)-based polyethylene (PE) blend for artificial joint application without the sacrifice of the original excellent wear and fatigue behavior of UHMWPE. The PE blend with desirable fluidity was obtained by melt mixing UHMWPE and low molecular weight polyethylene (LMWPE), and then was processed by a modified injection molding technology-oscillatory shear injection molding (OSIM). Morphological observation of the OSIM PE blend showed LMWPE contained well-defined interlocking shish-kebab self-reinforced superstructure. Addition of a small amount of long chain polyethylene (2 wt %) to LMWPE greatly induced formation of rich shish-kebabs. The ultimate tensile strength considerably increased from 27.6 MPa for conventional compression molded UHMWPE up to 78.4 MPa for OSIM PE blend along the flow direction and up to 33.5 MPa in its transverse direction. The impact strength of OSIM PE blend was increased by 46% and 7% for OSIM PE blend in the direction parallel and vertical to the shear flow, respectively. Wear and fatigue resistance were comparable to conventional compression molded UHMWPE. The superb performance of the OSIM PE blend was originated from formation of rich interlocking shish-kebab superstructure while maintaining unique properties of UHMWPE. The present results suggested the OSIM PE blend has high potential for artificial joint application. © 2012 American Chemical Society

Influence of Polyethylene Glycol Lipid Desorption Rates on Pharmacokinetics and Pharmacodynamics of siRNA Lipid Nanoparticles.

PubMed

Mui, Barbara L; Tam, Ying K; Jayaraman, Muthusamy; Ansell, Steven M; Du, Xinyao; Tam, Yuen Yi C; Lin, Paulo Jc; Chen, Sam; Narayanannair, Jayaprakash K; Rajeev, Kallanthottathil G; Manoharan, Muthiah; Akinc, Akin; Maier, Martin A; Cullis, Pieter; Madden, Thomas D; Hope, Michael J

2013-12-17

Lipid nanoparticles (LNPs) encapsulating short interfering RNAs that target hepatic genes are advancing through clinical trials, and early results indicate the excellent gene silencing observed in rodents and nonhuman primates also translates to humans. This success has motivated research to identify ways to further advance this delivery platform. Here, we characterize the polyethylene glycol lipid (PEG-lipid) components, which are required to control the self-assembly process during formation of lipid particles, but can negatively affect delivery to hepatocytes and hepatic gene silencing in vivo. The rate of transfer from LNPs to plasma lipoproteins in vivo is measured for three PEG-lipids with dialkyl chains 14, 16, and 18 carbons long. We show that 1.5 mol % PEG-lipid represents a threshold concentration at which the chain length exerts a minimal effect on hepatic gene silencing but can still modify LNPs pharmacokinetics and biodistribution. Increasing the concentration to 2.5 and 3.5 mol % substantially compromises hepatocyte gene knockdown for PEG-lipids with distearyl (C18) chains but has little impact for shorter dimyristyl (C14) chains. These data are discussed with respect to RNA delivery and the different rates at which the steric barrier disassociates from LNPs in vivo.Molecular Therapy-Nucleic Acids (2013) 2, e139; doi:10.1038/mtna.2013.66; published online 17 December 2013.

Surface decoration of red blood cells with maleimidophenyl-polyethylene glycol facilitated by thiolation with iminothiolane: an approach to mask A, B, and D antigens to generate universal red blood cells.

PubMed

Nacharaju, Parimala; Boctor, Fouad N; Manjula, Belur N; Acharya, Seetharama A

2005-03-01

The surface decoration of red blood cells (RBCs) by polyethylene glycol (PEG) chains has been an approach developed to camouflage the blood group antigens from their antibodies. A PEGylation protocol, however, that can mask the antigens appropriately to inhibit the agglutination of RBCs with the respective antibodies is not available so far. A new approach for PEGylation of RBC membrane proteins has been designed with thiolation-mediated maleimide chemistry. The accessibility of the surface lysine residues of membrane proteins to bulky PEG reagents was increased by linking an extension arm carrying a thiol group. RBCs have been PEGylated by thiolation-mediated chemistry with maleimidophenyl-PEG (Mal-Phe-PEG) reagents of different chain lengths. Mal-Phe-PEG-5000 chains alone masked the most important antigens of the Rh system (C, c, E, e, and D) from their antibodies. The masking of the A and B antigens needed a combination of Mal-Phe-PEG-5000 and Mal-Phe-PEG-20000 chains to inhibit the agglutination of RBCs completely with anti-A or anti-B. Thiolation-mediated PEGylation of RBCs with Mal-Phe-PEG-5000 and Mal-Phe-PEG-20000 converts Group A Rh(D)+ and B Rh(D)+ RBCs into RBCs with serologic behavior comparable to Group O Rh(D)- RBCs that are considered as universal RBCs for transfusion.

Tunable Surface Repellency Maintains Stemness and Redox Capacity of Human Mesenchymal Stem Cells.

PubMed

Balikov, Daniel A; Crowder, Spencer W; Boire, Timothy C; Lee, Jung Bok; Gupta, Mukesh K; Fenix, Aidan M; Lewis, Holley N; Ambrose, Caitlyn M; Short, Philip A; Kim, Chang Soo; Burnette, Dylan T; Reilly, Matthew A; Murthy, N Sanjeeva; Kang, Mi-Lan; Kim, Won Shik; Sung, Hak-Joon

2017-07-12

Human bone marrow derived mesenchymal stem cells (hMSCs) hold great promise for regenerative medicine due to their multipotent differentiation capacity and immunomodulatory capabilities. Substantial research has elucidated mechanisms by which extracellular cues regulate hMSC fate decisions, but considerably less work has addressed how material properties can be leveraged to maintain undifferentiated stem cells. Here, we show that synthetic culture substrates designed to exhibit moderate cell-repellency promote high stemness and low oxidative stress-two indicators of naïve, healthy stem cells-in commercial and patient-derived hMSCs. Furthermore, the material-mediated effect on cell behavior can be tuned by altering the molar percentage (mol %) and/or chain length of poly(ethylene glycol) (PEG), the repellant block linked to hydrophobic poly(ε-caprolactone) (PCL) in the copolymer backbone. Nano- and angstrom-scale characterization of the cell-material interface reveals that PEG interrupts the adhesive PCL domains in a chain-length-dependent manner; this prevents hMSCs from forming mature focal adhesions and subsequently promotes cell-cell adhesions that require connexin-43. This study is the first to demonstrate that intrinsic properties of synthetic materials can be tuned to regulate the stemness and redox capacity of hMSCs and provides new insight for designing highly scalable, programmable culture platforms for clinical translation.

Structural and elastic properties and stability characteristics of oxygenated carbon nanotubes under physical adsorption of polymers

NASA Astrophysics Data System (ADS)

Ansari, R.; Ajori, S.; Rouhi, S.

2015-03-01

The importance of covalent and non-covalent functionalization approaches for modification the properties of carbon nanotubes is being more widely recognized. To this end, elastic properties and buckling behavior of oxygenated CNT with atomic oxygen and hydroxyl under physical adsorption of PE (Polyethylene) and PEO (Poly (ethylene oxide)) are determined through employing the molecular dynamics (MD) simulations. The results demonstrate that non-covalent bonding of polymer on the surface of oxygenated CNT causes reductions in the variations of critical buckling load and critical strain compared to oxygenated CNTs. Critical buckling load and critical strain of oxygenated CNT/polymer are higher than those of oxygenated CNT. Also, it is demonstrated that critical buckling load and critical strain values in the case of oxygenated CNT/polymer are independent of polymer type unlike the value of Young's modulus. It is shown that variations of Young's modulus decrease as PE adsorbed on the surface of oxygenated CNT. Moreover, the presence of oxygen atom on PEO chain leads to bigger variations of Young's modulus with weight percentage of chemisorbed component, i.e. atomic oxygen and hydroxyl. It is also demonstrated that Young's modulus reduces more considerably in the presence of PEO chain compared to PE one.

Investigation of the interaction of copper(II) oxide and electron beam irradiation crosslinkable polyethylene

NASA Astrophysics Data System (ADS)

Bee, Soo-Tueen; Sin, Lee Tin; Ratnam, C. T.; Haraveen, K. J. S.; Tee, Tiam-Ting; Rahmat, A. R.

2015-10-01

In this study, the effects of electron beam irradiation on the properties of copper(II) oxide when added to low-density polyethylene (LDPE) blends were investigated. It was found that the addition of low loading level of copper(II) oxide (⩽2 phr) to LDPE results in significantly poorer gel content and hot set results. However, the incorporation of higher loading level of copper(II) oxide (⩾3 phr) could slightly increase the degree of crosslinking in all irradiated LDPE composites. This is due to the fact that higher amounts of copper(II) oxide could slightly induce the formation of free radicals in LDPE matrix. Besides, increasing irradiation doses was also found to gradually increase the gel content of LDPE composites by generating higher amounts of free radicals. As a consequence, these higher amounts of free radicals released in the LDPE matrix could significantly increase the degree of crosslinking. The addition of copper(II) oxide could reduce the tensile strength and fracture strain (elongation at break) of LDPE composites because of poorer interfacial adhesion effect between copper(II) oxide particles and LDPE matrix. Meanwhile, increasing irradiation doses on all copper(II) oxide added LDPE composites could marginally increase the tensile strength. In addition, increasing irradiation dose could enhance the thermal stability of LDPE composites by increasing the decomposition temperature. The oxidation induction time (OIT) analysis showed that, because of the crosslinking network in the copper(II) oxide added LDPE composites, oxidation reaction is much delayed.

Wear performance of neat and vitamin E blended highly cross-linked PE under severe conditions: The combined effect of accelerated ageing and third body particles during wear test.

PubMed

Affatato, Saverio; De Mattia, Jonathan Salvatore; Bracco, Pierangiola; Pavoni, Eleonora; Taddei, Paola

2016-12-01

The objective of this study is to evaluate the effects of third-body particles on the in vitro wear behaviour of three different sets of polyethylene acetabular cups after prolonged testing in a hip simulator and accelerated ageing. Vitamin E-blended, cross-linked polyethylene (XLPE_VE), cross-linked polyethylene (XLPE) and conventional polyethylene (STD_PE) acetabular cups were simulator tested for two million cycles under severe conditions (i.e. by adding third-body particles to the bovine calf serum lubricant). Micro-Fourier Transform Infrared and micro-Raman spectroscopic analyses, differential scanning calorimetry, and crosslink density measurements were used to characterize the samples at a molecular level. The STD_PE cups had twice mass loss than the XLPE_VE components and four times than the XLPE samples; statistically significant differences were found between the mass losses of the three sets of cups. The observed wear trend was justified on the basis of the differences in cross-link density among the samples (XLPE>XLPE_VE>STD_PE). FTIR crystallinity profiles, bulk DSC crystallinity and surface micro-Raman crystallinity seemed to have a similar behaviour upon testing: all of them (as well as the all-trans and ortho-trans contents) revealed the most significant changes in XLPE and XLPE_VE samples. The more severe third-body wear testing conditions determined more noticeable changes in all spectroscopic markers with respect to previous tests. Unexpectedly, traces of bulk oxidation were found in both STD_PE (unirradiated) and XLPE (remelting-stabilized), which were expected to be stable to oxidation; on the contrary, XLPE_VE demonstrated a high oxidative stability in the present, highly demanding conditions. Copyright © 2016 Elsevier Ltd. All rights reserved.

Adsorption of poly(ethylene oxide) on smectite: Effect of layer charge.

PubMed

Su, Chia-Chi; Shen, Yun-Hwei

2009-04-01

The adsorption of polymers on clay is important in many applications. However the mechanisms of poly(ethylene oxide) (PEO) adsorption on smectite is not well elucidated at present. The aim of this study was to investigate the effect of layer charge density on the adsorption of PEO by smectite. The results indicated that both the hydrophobic interaction (between CH(2)CH(2) groups and siloxane surface) and the hydrogen bonding (between ether oxygen of PEO and structure OH of smectite) lead to PEO preferential adsorption on the surface of low-charge smectite. In addition, the delamination of low-charge smectite in water is enhanced upon PEO adsorption presumably due to the hydrophilic ether oxygen of adsorbed PEO.

Water and UV degradable lactic acid polymers

DOEpatents

Bonsignore, Patrick V.; Coleman, Robert D.

1996-01-01

A water and UV light degradable copolymer of monomers of lactic acid and a modifying monomer selected from the class consisting of ethylene glycol, propylene glycol, P-dioxanone, 1,5 dioxepan-2-one, 1,4-oxathialan-2-one, 1,4-dioxide and mixtures thereof. These copolymers are useful for waste disposal and agricultural purposes. Also disclosed is a water degradable blend of polylactic acid or modified polylactic acid and high molecular weight polyethylene oxide wherein the high molecular weight polyethylene oxide is present in the range of from about 2 by weight to about 50% by weight, suitable for films. A method of applying an active material selected from the class of seeds, seedlings, pesticides, herbicides, fertilizers and mixtures thereof to an agricultural site is also disclosed.

Ethylene-Propylene Terpolymer Rubber Processing by Electron Beam Irradiation

NASA Astrophysics Data System (ADS)

Manaila, Elena N.; Zuga, Maria Daniela T.; Martin, Diana I.; Craciun, Gabriela D.; Ighigeanu, Daniel I.; Matei, Constantin I.

2007-04-01

The investigations on the cross-linking by accelerated electrons of 6.23 MeV in lowly unsaturated elastomers of EPDM (ethylene-propylene terpolymer rubber) type are presented. Two rubber blends based EPDM were prepared and irradiated at different doses up to 250kGy: blend A - based on EPDM maleinized with polyethylene, zinc oxide, plasticizers, filler, and blend B - based on EPDM / PE (50 % EPDM and 50% polyethylene). Blends were prepared on a laboratory electrically heated rubber mill at temperatures of 150-160°C to enable the polyethylene (PE) melting to be reached. Plates of 150 × 150 × 2 mm were obtained in a laboratory electrical press at 170°C.

Processing of ultra-high molecular weight polyethylene/graphite composites by ultrasonic injection moulding: Taguchi optimization.

PubMed

Sánchez-Sánchez, Xavier; Elias-Zuñiga, Alex; Hernández-Avila, Marcelo

2018-06-01

Ultrasonic injection moulding was confirmed as an efficient processing technique for manufacturing ultra-high molecular weight polyethylene (UHMWPE)/graphite composites. Graphite contents of 1 wt%, 5 wt%, and 7 wt% were mechanically pre-mixed with UHMWPE powder, and each mixture was pressed at 135 °C. A precise quantity of the pre-composites mixtures cut into irregularly shaped small pieces were subjected to ultrasonic injection moulding to fabricate small tensile specimens. The Taguchi method was applied to achieve the optimal level of ultrasonic moulding parameters and to maximize the tensile strength of the composites; the results showed that mould temperature was the most significant parameter, followed by the graphite content and the plunger profile. The observed improvement in tensile strength in the specimen with 1 wt% graphite was of 8.8% and all composites showed an increase in the tensile modulus. Even though the presence of graphite produced a decrease in the crystallinity of all the samples, their thermal stability was considerably higher than that of pure UHMWPE. X-ray diffraction and scanning electron microscopy confirmed the exfoliation and dispersion of the graphite as a function of the ultrasonic processing. Fourier transform infrared spectra showed that the addition of graphite did not influence the molecular structure of the polymer matrix. Further, the ultrasonic energy led oxidative degradation and chain scission in the polymer. Copyright © 2018 Elsevier B.V. All rights reserved.

Interphase and particle dispersion correlations in polymer nanocomposites

NASA Astrophysics Data System (ADS)

Senses, Erkan

Particle dispersion in polymer matrices is a major parameter governing the mechanical performance of polymer nanocomposites. Controlling particle dispersion and understanding aging of composites under large shear and temperature variations determine the processing conditions and lifetime of composites which are very important for diverse applications in biomedicine, highly reinforced materials and more importantly for the polymer composites with adaptive mechanical responses. This thesis investigates the role of interphase layers between particles and polymer matrices in two bulk systems where particle dispersion is altered upon deformation in repulsive composites, and good-dispersion of particles is retained after multiple oscillatory shearing and aging cycles in attractive composites. We demonstrate that chain desorption and re-adsorption processes in attractive composites under shear can effectively enhance the bulk microscopic mechanical properties, and long chains of adsorbed layers lead to a denser entangled interphase layer. We further designed experiments where particles are physically adsorbed with bimodal lengths of homopolymer chains to underpin the entanglement effect in interphases. Bimodal adsorbed chains are shown to improve the interfacial strength and used to modulate the elastic properties of composites without changing the particle loading, dispersion state or polymer conformation. Finally, the role of dynamic asymmetry (different mobilities in polymer blends) and chemical heterogeneity in the interphase layer are explored in systems of poly(methyl methacrylate) adsorbed silica nanoparticles dispersed in poly(ethylene oxide) matrix. Such nanocomposites are shown to exhibit unique thermal-stiffening behavior at temperatures above glass transitions of both polymers. These interesting findings suggest that the mobility of the surface-bound polymer is essential for reinforcement in polymer nanocomposites, contrary to existing glassy layer theories for polymers on attractive particle surfaces. The shown thermally-induced stiffening behavior is reversible and makes this interfacial mechanism highly attractive in developing new active, remotely controllable engineered materials from non-responsive components.

Elasticity and photoelasticity relationships for polyethylene terephthalate fiber networks by molecular simulation

NASA Astrophysics Data System (ADS)

Nayak, Kapileswar; Das, Sushanta; Nanavati, Hemant

2008-01-01

We present a framework for the development of elasticity and photoelasticity relationships for polyethylene terephthalate fiber networks, incorporating aspects of the primary molecular structure. Semicrystalline polymeric fiber networks are modeled as sequentially arranged crystalline and amorphous regions. Rotational isomeric states-Monte Carlo simulations of amorphous chains of up to 360 bonds (degree of polymerization, DP =60), confined between and bridging infinite impenetrable crystalline walls, have been characterized by Ω, the probability density of the intercrystal separation h, and Δβ, the polarizability anisotropy. lnΩ and Δβ have been modeled as functions of h, yielding the chain deformation relationships. The development has been extended to the fiber network to yield the photoelasticity relationships. We execute our framework by fitting to experimental stress-elongation data and employing the single fitted parameter to directly predict the birefringence-elongation behavior, without any further fitting. Incorporating the effect of strain-induced crystallization into the framework makes it physically more meaningful and yields accurate predictions of the birefringence-elongation behavior.

Molecular Dynamics Study on Nucleation Behavior and Lamellar Mergence of Polyethylene Globule Crystallization

NASA Astrophysics Data System (ADS)

Yang, Xiaozhen; Wang, Simiao

2012-02-01

The site order parameter (SOP) has been adopted to analyze various order structure formation and distribution during the crystallization of a multi-chain polyethylene globule simulated by molecular dynamics. We found that the nucleation relies on crystallinity fluctuation with increase of amplitude, and the baby nucleus in the fluctuation suddenly appears with different shape and increasing size. In the growth stage, a number of lamellar mergence was observed and their selective behaviors were suggested to be related to the orientation difference between the merging lamellae. We obtained that SOP distribution of all atoms in the system during crystallization appears with two peaks: one for the amorphous phase and the other for the crystalline phase. Mesomorphic structures with medium orders locate between the two peaks as an order promotion pathway. Obtained data show that the medium order structure fluctuates at the growth front and does not always be available; the medium order structure existing at the front is not always good for developing. It is possibly caused by chain entanglement.

Effects of UV Aging on the Cracking of Titanium Oxide Layer on Poly(ethylene terephthalate) Substrate: Preprint

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Chao; Gray, Matthew H.; Tirawat, Robert

Thin oxide and metal films deposited on polymer substrates is an emerging technology for advanced reflectors for concentrated solar power applications, due to their unique combination of light weight, flexibility and inexpensive manufacture. Thus far, there is little knowledge on the mechanical integrity or structural persistence of such multi-layer thin film systems under long-term environmental aging. In this paper, the cracking of a brittle titanium dioxide layer deposited onto elasto-plastic poly(ethylene terephthalate) (PET) substrate is studied through a combination of experiment and modeling. In-situ fragmentation tests have been conducted to monitor the onset and evolution of cracks both on pristinemore » and on samples aged with ultraviolet (UV) light. An analytical model is presented to simulate the cracking behavior and to predict the effects of UV aging. Based on preliminary experimental observation, the effect of aging is divided into three aspects and analyzed independently: mechanical property degradation of the polymer substrate; degradation of the interlayer between substrate and oxide coating; and internal stress-induced cracks on the oxide coating.« less

Monitoring refolding of tailspike endorhamnosidase using capillary electrophoresis-laser induced tryptophan fluorescence

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jensen, P.K.; Lee, Cheng S.; King, J.A.

1997-12-31

The use of capillary electrophoresis equipped with laser-induced tryptophan fluorescence detection is presented for monitoring the refolding pathway of phage P22 tailspike endorhamnosidase. Upon initiation of refolding, tailspike polypeptides rapidly fold into structured monomeric intermediates with a high content of secondary structure. These monomeric species associate to form the triple-chain defined folding intermediates, the protrimers. Conversion of the protrimer into the native, sodium dodecyl sulfate (SDS) resistant tailspike protein is the rate-limiting step in the refolding pathway. Refolding kinetics and yield measured by capillary electrophoresis are in good agreement with those obtained via native gel electrophoresis, SDS polyacrylamide gel electrophoresismore » (SDS-PAGE) and fluorescence spectrophotometry. To enhance separation resolution between protrimer and native protein in capillary electrophoresis, the use of poly(ethylene oxide) is investigated for the introduction of a sieving separation mechanism. The increased viscosity of the electrophoresis buffer may also play a role in resolution enhancement.« less

Resveratrol derivatives as a pharmacological tool.

PubMed

Biasutto, Lucia; Mattarei, Andrea; Azzolini, Michele; La Spina, Martina; Sassi, Nicola; Romio, Matteo; Paradisi, Cristina; Zoratti, Mario

2017-09-01

Prodrugs of resveratrol are under development. Among the long-term goals, still largely elusive, are (1) modulating physical properties (e.g., water-soluble derivatives bearing polyethylene glycol chains), (2) changing distribution in the body (e.g., galactosyl derivatives restricted to the intestinal lumen), (3) increasing absorption from the gastrointestinal tract (e.g., derivatives imitating the natural substrates of endogenous transporters), and (4) hindering phase II metabolism (e.g., temporarily blocking the hydroxyls), all contributing to (5) increasing bioavailability. The chemical bonds that have been tested for functionalization include carboxyester, acetal, and carbamate groups. A second approach, which can be combined with the first, seeks to reinforce or modify the biochemical activities of resveratrol by concentrating the compound at specific subcellular sites. An example is provided by mitochondria-targeted derivatives. These proved to be pro-oxidant and cytotoxic in vitro, selectively killing fast-growing and tumor cells when supplied in the low micromolar range. This suggests the possibility of anticancer applications. © 2017 New York Academy of Sciences.

Morphology and conductivity of PEO-based polymers having various end functional groups

NASA Astrophysics Data System (ADS)

Jung, Ha Young; Mandal, Prithwiraj; Park, Moon Jeong

Poly(ethylene oxide) (PEO)-based polymers have been considered most promising candidates of polymer electrolytes for lithium batteries owing to the high ionic conductivity of PEO/lithium salt complexes. This positive aspect prompted researchers to investigate PEO-containing block copolymers prepared by linking mechanically robust block to PEO covalently. Given that the microphase separation of block copolymers can affect both mechanical properties and ion transport properties, various strategies have been reported to tune the morphology of PEO-containing block copolymers. In the present study, we describe a simple means for modulating the morphologies of PEO-based block copolymers with an aim to improve ion transport properties. By varying terminal groups of PEO in block copolymers, the disordered morphology can be readily transformed into ordered lamellae or gyroid phases, depending on the type and number density of end group. In particular, the existence of terminal groups resulted in a large reduction in crystallinity of PEO chains and thereby increasing room temperature ionic conductivity.

Coarse-grained molecular simulation of self-assembly for nonionic surfactants on graphene nanostructures.

PubMed

Wu, Dan; Yang, Xiaoning

2012-10-04

Self-assembly of amphiphilic molecules on the surfaces of nanoscale materials has an important application in a variety of nanotechnology. Here, we report a coarse-grained molecular dynamics simulation on the structure and morphology of the nonionic surfactant, n-alkyl poly(ethylene oxide) (PEO), adsorbed on planar graphene nanostructures. The effects of concentration, surfactant structure, and size of graphene sheet are explored. Because of the finite dimension effect, various morphological hemimicelles can be formed on nanoscale graphene surfaces, which is somewhat different from the self-assembly structures on infinite carbon surfaces. The aggregate morphology is highly dependent on the concentration, the chain lengths, and the size of graphene nanosheets. For the nonionic surfactant, the PEO headgroups show strong dispersion interaction with the carbon surface, leading to a side edge adsorption behavior. This simulation provides insight into the supramolecular self-assembly nanostructures and the adsorption mechanism for the nonionic surfactants aggregated on graphene nanostructures, which could be exploited to guide fabrication of graphene-based nanocomposites.

Single-ion triblock copolymer electrolytes based on poly(ethylene oxide) and methacrylic sulfonamide blocks for lithium metal batteries

NASA Astrophysics Data System (ADS)

Porcarelli, Luca; Aboudzadeh, M. Ali; Rubatat, Laurent; Nair, Jijeesh R.; Shaplov, Alexander S.; Gerbaldi, Claudio; Mecerreyes, David

2017-10-01

Single-ion conducting polymer electrolytes represent the ideal solution to reduce concentration polarization in lithium metal batteries (LMBs). This paper reports on the synthesis and characterization of single-ion ABA triblock copolymer electrolytes comprising PEO and poly(lithium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethylsulfonyl)imide) blocks, poly(LiMTFSI). Block copolymers are prepared by reversible addition-fragmentation chain transfer polymerization, showing low glass transition temperature (-55 to 7 °C) and degree of crystallinity (51-0%). Comparatively high values of ionic conductivity are obtained (up to ≈ 10-4 S cm-1 at 70 °C), combined with a lithium-ion transference number close to unity (tLi+ ≈ 0.91) and a 4 V electrochemical stability window. In addition to these promising features, solid polymer electrolytes are successfully tested in lithium metal cells at 70 °C providing long lifetime up to 300 cycles, and stable charge/discharge cycling at C/2 (≈100 mAh g-1).

Effect of electrostatic interaction on the location of molecular probe in polymer-surfactant supramolecular assembly: a solvent relaxation study.

PubMed

Singh, Prabhat K; Kumbhakar, Manoj; Pal, Haridas; Nath, Sukhendu

2008-07-03

Effect of electrostatic interaction on the location of a solubilized molecular probe with ionic character in a supramolecular assembly composed of a triblock copolymer, P123 ((ethylene oxide) 20-(propylene oxide) 70-(ethylene oxide) 20) and a cosurfactant cetyltrimethylammonium chloride (CTAC) in aqueous medium has been studied using steady-state and time-resolved fluorescence measurements. Coumarin-343 dye in its anionic form has been used as the molecular probe. In the absence of the surfactant, CTAC, the probe C343 prefers to reside at the surface region of the P123 micelle, showing a relatively less dynamic Stokes' shift, as a large part of the Stokes' shift is missed in the present measurements due to faster solvent relaxation at micellar surface region. As the concentration of CTAC is increased in the solution, the percentage of the total dynamic Stokes' shift observed from time-resolved measurements gradually increases until it reaches a saturation value. Observed results have been rationalized on the basis of the mixed micellar structure of the supramolecular assembly, where the hydrocarbon chain of the CTAC surfactant dissolves into the nonpolar poly(propylene oxide) (PPO) core of the P123 micelle and the positively charged headgroup of CTAC resides at the interfacial region between the central PPO core and the surrounding hydrated poly(ethylene oxide) (PEO) shell or the corona region. The electrostatic attraction between the anionic probe molecule and the positively charged surface of the PPO core developed by the presence of CTAC results in a gradual shift of the probe in the deeper region of the micellar corona region with an increase in the CTAC concentration, as clearly manifested from the solvation dynamics results.

Combined effects of microwaves, electron beams and polyfunctional monomers on rubber vulcanization.

PubMed

Manaila, Elena; Martin, Diana; Stelescu, Daniela Zuga; Craciun, Gabriela; Ighigeanu, Daniel; Matei, Constantin

2009-01-01

This paper presents comparative results obtained by conventional vulcanization with benzoyl peroxide (CV-BP), separate electron beam vulcanization (EB-V) and simultaneous electron beam and microwave vulcanization (EB+MW-V) applied to two kind of rubber samples: EVA (ethylene vinyl acetate) rubber-sample (EVA-sample) and EPDM (ethylene-propylene terpolymer) rubber-sample (EPDM-sample). The EVA-samples contain 61.54% EVA Elvax 260, 30.77% carbon black, 1.85% TAC (triallylcyanurate) polyfunctional monomer and 5.84% filler (zinc oxide, stearic acid, polyethylene glycol and antioxidant). The EPDM-samples contain 61.54% EPDM Nordel 4760, 30.77% carbon black, 1.85% TMPT (trimethylopropane trimethacrylate) polyfunctional monomer and 5.84% filler (zinc oxide, stearic acid, polyethylene glycol and antioxidant). The rubber samples designed for different vulcanization methods were obtained from raw rubber mixtures, as compressed sheets of 2 mm in the polyethylene foils to minimize oxidation. For EB and EB + MW treatments the sheets were cut in rectangular shape 0.15 x 0.15 m2. The physical properties of samples obtained by CV-BP EV-Vand EB + MW-V methods were evaluated by measuring the tearing strength, residual elongation, elongation at break, tensile strength, 300% modulus, 100% modulus, elasticity and hardness. The obtained results demonstrate an improvement of rubber several properties obtained by EB and EB + MW processing as compared to classical procedure using benzoyl peroxide.

Electrospun-sodiumtetrafluoroborate-polyethylene oxide membranes for solvent-free sodium ion transport in solid state sodium ion batteries

NASA Astrophysics Data System (ADS)

Freitag, K. M.; Walke, P.; Nilges, T.; Kirchhain, H.; Spranger, R. J.; van Wüllen, L.

2018-02-01

Electrospinning is used to fabricate sodium ion conducting fiber membranes composed of polyethylene oxide (PEO), sodium tetrafluoroborate (NaBF4), and succinonitrile (SN) as plasticizer. As compared to conventionally prepared lithium electrolyte membranes with identical composition (PEO:SN:LiBF4), those membranes exhibit conductivities up to 10-4 S cm-1 at 328 K (activation energy ∼36 kJ mol-1, 36:8:1 membrane), which favors such systems as a solid-state electrolyte alternative for batteries. The conduction mechanism is evaluated and the ion mobility are examined. We identified the segment mobility of the polyethylene oxide as the main driving force for the enhanced ion mobility in the membranes. The introduction of SN has only a minor influence on the conductivity and segment mobility at room temperature, but extents the anion and cation mobility to temperatures below ambient. For the 36:8:1 (PEO:SN:NaBF4) membrane we found the highest ion mobility of all membranes under investigation. A comparison of the present sodium membranes with lithium systems of the same composition shows that the overall performance of the sodium systems is comparable. Taking plasticizer-free sodium membranes into account they perform even better than the lithium containing counterparts, and plasticizer-modified membranes show only half an order of magnitude lower conductivities than comparable lithium ones.

Evaluating the suitability of highly cross-linked and remelted materials for use in posterior stabilized knees.

PubMed

Huot, J Caitlin; Van Citters, Douglas W; Currier, John H; Currier, Barbara H; Mayor, Michael B; Collier, John P

2010-11-01

Posterior stabilized (PS) knee designs are a popular choice for cruciate sacrificing knee arthroplasty procedures. The introduction of PS inserts fabricated from highly cross-linked and remelted Ultra High Molecular Weight Polyethylene (UHMWPE) has recently generated concern as these materials have been shown to possess reduced mechanical properties. This study investigated whether highly cross-linked and remelted UHMWPE material (referred to as XRP) can be expected to perform similarly to historical gamma-air polyethylene, which has suffered few reported incidences of tibial post failure. Never-implanted gamma-air PS tibial inserts shelf-aged 14 years were examined and compared to XRP materials. Evaluation of oxidation levels, impact toughness, and fatigue strength demonstrated never-implanted gamma-air PS tibial inserts to possess nonuniform mechanical properties. Despite severe oxidation along the exterior of gamma-air tibial posts, comparatively low oxidation levels at the center of the tibial posts corresponded to sufficiently high mechanical properties. XRP material (75 kGy) showed superior impact toughness over shelf aged gamma-air material; however, tibial post fatigue testing demonstrated XRP material (100 kGy) to be less resistant to fatigue failure than historical gamma-air material. Results from this study indicate that XRP materials (100 kGy) may demonstrate an inferior resistance to tibial post failure than historical polyethylene. © 2010 Wiley Periodicals, Inc.

Polymeric micellar pH-sensitive drug delivery system for doxorubicin.

PubMed

Hrubý, Martin; Konák, Cestmír; Ulbrich, Karel

2005-03-02

A novel polymeric micellar pH-sensitive system for delivery of doxorubicin (DOX) is described. Polymeric micelles were prepared by self-assembly of amphiphilic diblock copolymers in aqueous solutions. The copolymers consist of a biocompatible hydrophilic poly(ethylene oxide) (PEO) block and a hydrophobic block containing covalently bound anthracycline antibiotic DOX. The starting block copolymers poly(ethylene oxide)-block-poly(allyl glycidyl ether) (PEO-PAGE) with a very narrow molecular weight distribution (Mw/Mn ca. 1.05) were prepared by anionic ring opening polymerization using sodium salt of poly(ethylene oxide) monomethyl ether as macroinitiator and allyl glycidyl ether as functional monomer. The copolymers were covalently modified via reactive double bonds by the addition of methyl sulfanylacetate. The resulting ester subsequently reacted with hydrazine hydrate yielding polymer hydrazide. The hydrazide was coupled with DOX yielding pH-sensitive hydrazone bonds between the drug and carrier. The resulting conjugate containing ca. 3 wt.% DOX forms micelles with Rh(a)=104 nm in phosphate-buffered saline. After incubation in buffers at 37 degrees C DOX was released faster at pH 5.0 (close to pH in endosomes; 43% DOX released within 24 h) than at pH 7.4 (pH of blood plasma; 16% DOX released within 24 h). Cleavage of hydrazone bonds between DOX and carrier continues even after plateau in the DOX release from micelles incubated in aqueous solutions is reached.

Microstructural modifications induced by accelerated aging and lipid absorption in remelted and annealed UHMWPEs for total hip arthroplasty

PubMed Central

Puppulin, Leonardo; Zhu, Wenliang; Sugano, Nobuhiko

2014-01-01

Three types of commercially available ultra-high molecular weight polyethylene (UHMWPE) acetabular cups currently used in total hip arthroplasty have been studied by means of Raman micro-spectroscopy to unfold the microstructural modification induced by the oxidative degradation after accelerated aging with and without lipid absorption. The three investigated materials were produced by three different manufacturing procedures, as follows: irradiation followed by remelting, one-step irradiation followed by annealing, 3-step irradiation and annealing. Clear microstructural differences were observed in terms of phase contents (i.e. amorphous, crystalline and intermediate phase fraction). The three-step annealed material showed the highest crystallinity fraction in the bulk, while the remelted polyethylene is clearly characterized by the lowest content of crystalline phase and the highest content of amorphous phase. After accelerated aging either with or without lipids, the amount of amorphous phase decreased in all the samples as a consequence of the oxidation-induced recrystallization. The most remarkable variations of phase contents were detected in the remelted and in the single-step annealed materials. The presence of lipids triggered oxidative degradation especially in the remelted polyethylene. Such experimental evidence might be explained by the highest amount of amorphous phase in which lipids can be absorbed prior to accelerated aging. The results of these spectroscopic characterizations help to rationalize the complex effect of different irradiation and post-irradiation treatments on the UHMWPE microstructure and gives useful information on how significantly any single step of the manufacturing procedures might affect the oxidative degradation of the polymer. PMID:25179830

FTIR spectroscopy supported by statistical techniques for the structural characterization of plastic debris in the marine environment: Application to monitoring studies.

PubMed

Mecozzi, Mauro; Pietroletti, Marco; Monakhova, Yulia B

2016-05-15

We inserted 190 FTIR spectra of plastic samples in a digital database and submitted it to Independent Component Analysis (ICA) to extract the "pure" plastic polymers present. These identified plastics were polypropylene (PP), high density polyethylene (HDPE), low density polyethylene (LDPE), high density polyethylene terephthalate (HDPET), low density polyethylene terephthalate (LDPET), polystyrene (PS), Nylon (NL), polyethylene oxide (OPE), and Teflon (TEF) and they were used to establish the similarity with unknown plastics using the correlation coefficient (r), and the crosscorrelation function (CC). For samples with r<0.8 we determined the Mahalanobis Distance (MD) as additional tool of identification. For instance, for the four plastic fragments found in the Carretta carretta, one plastic sample was assigned to OPE due to its r=0.87; for all the other three plastic samples, due to the r values ranging between 0.83 and0.70, the support of MD suggested LDPET and OPE as co-polymer constituents. Copyright © 2016 Elsevier Ltd. All rights reserved.

Mid-term survivorship and clinical outcomes of cobalt-chrome and oxidized zirconium on highly crosslinked polyethylene

PubMed Central

Petis, Stephen M.; Vasarhelyi, Edward M.; Lanting, Brent A.; Howard, James L.; Naudie, Douglas D.R.; Somerville, Lyndsay E.; McCalden, Richard W.

2016-01-01

Background The choice of bearing articulation for total hip arthroplasty in younger patients is amenable to debate. We compared mid-term patient-reported outcomes and survivorship across 2 different bearing articulations in a young patient cohort. Methods We reviewed patients with cobalt-chrome or oxidized zirconium on highly crosslinked polyethylene who were followed prospectively between 2004 and 2012. Kaplan–Meier analysis was used to determine predicted cumulative survivorship at 5 years with all-cause and aseptic revisions as the outcome. We compared patient-reported outcomes, including the Harris hip score (HHS), Western Ontario and McMaster University Osteoarthritis Index (WOMAC) and Short-form 12 (SF-12) scores. Results A total of 622 patients were followed during the study period. Mean follow-up was 8.2 (range 2.0–10.6) years for cobalt-chrome and 7.8 (range 2.1–10.7) years for oxidized zirconium. Mean age was 54.9 ± 10.6 years for cobalt-chrome and 54.8 ± 10.7 years for oxidized zirconium. Implant survivorship was 96.0% (95% confidence interval [CI] 94.9%–97.1%) for cobalt-chrome and 98.7% (95% CI 98.0%–99.4%) for oxidized zirconium on highly crosslinked polyethylene for all-cause revisions, and 97.2% (95% CI 96.2%–98.2%) for cobalt-chrome and 99.0% (95% CI 98.4%–99.6%) for oxidized zirconium for aseptic revisions. An age-, sex- and diagnosis-matched comparison of the HHS, WOMAC and SF-12 scores demonstrated no significant changes in clinical outcomes across the groups. Conclusion Both bearing surface couples demonstrated excellent mid-term survivorship and outcomes in young patient cohorts. Future analyses on wear and costs are warranted to elicit differences between the groups at long-term follow-up. PMID:26812409

Investigation of Non-Conventional Bio-Derived Fuels for Hybrid Rocket Motors

DTIC Science & Technology

2007-08-01

been demonstrated that a hybrid rocket system using 85% hydrogen peroxide ( HTP ) as the oxidizer and polyethylene as the solid fuel can serve as a cost...As with the tests at Surrey, they used a catalyst pack to decompose the HTP for the ignition. This type of process provides a self-ignition behavior...low regression rate as HTP and polyethylene, so it is difficult to obtain high thrust levels. MARS has the distinction of launching the first

Radiation cross-linking in ultra-high molecular weight polyethylene for orthopaedic applications

NASA Astrophysics Data System (ADS)

Oral, Ebru; Muratoglu, Orhun K.

2007-12-01

The motivation for radiation cross-linking of ultra-high molecular weight polyethylene (UHMWPE) is to increase its wear resistance to be used as bearing surfaces for total joint arthroplasty. However, radiation also leaves behind long-lived residual free radicals in this polymer, the reactions of which can detrimentally affect mechanical properties. In this review, we focus on the radiation cross-linking and oxidative stability of first and second generation highly cross-linked UHMWPEs developed in our laboratory.

Highly stable biocompatible inorganic nanoparticles by self-assembly of triblock-copolymer ligands.

PubMed

Pöselt, Elmar; Fischer, Steffen; Foerster, Stephan; Weller, Horst

2009-12-15

A novel type of ligand for biofunctionalization of nanoparticles is presented that comprises tailor-made triblock-copolymers consisting of a polyethylene imine binding block, a hydrophobic polycaprolactone and a terminal functionalized polyethelene oxide block. Phase transfer to water occurs simply by ligand and water addition and removal of the organic solvents. It is shown that the intermediate polycaprolacton block favors the attachment to the particle surface and shields the binding groups effectively from the solution. As a consequence, the particles exhibit an outstanding stability in various aqueous media for biological studies and give easy access to specific coupling reactions at the terminal end groups of the polyethylene oxide block. Controlling the ligand exchange parameters leads to self-assembly to either individual encapsulated nanoparticles or to multifunctional nanobeads.

Water and UV degradable lactic acid polymers

DOEpatents

Bonsignore, P.V.; Coleman, R.D.

1996-10-08

A water and UV light degradable copolymer is described made from monomers of lactic acid and a modifying monomer selected from the class consisting of ethylene glycol, propylene glycol, P-dioxanone, 1,5 dioxepan-2-one, 1,4-oxathialan-2-one, 1,4-dioxide and mixtures thereof. These copolymers are useful for waste disposal and agricultural purposes. Also disclosed is a water degradable blend of polylactic acid or modified polylactic acid and high molecular weight polyethylene oxide wherein the high molecular weight polyethylene oxide is present in the range of from about 2 by weight to about 50% by weight, suitable for films. A method of applying an active material selected from the class of seeds, seedlings, pesticides, herbicides, fertilizers and mixtures thereof to an agricultural site is also disclosed.

Effect of degrading yellow oxo-biodegradable low-density polyethylene films to water quality

NASA Astrophysics Data System (ADS)

Requejo, B. A.; Pajarito, B. B.

2017-05-01

Polyethylene (PE) contributes largely to plastic wastes that are disposed in aquatic environment as a consequence of its widespread use. In this study, yellow oxo-biodegradable low-density PE films were immersed in deionized water at 50°C for 49 days. Indicators of water quality: pH, oxidation-reduction potential, turbidity, and total dissolved solids (TDS), were monitored at regular intervals. It was observed that pH initially rises and then slowly decreases with time, oxidation-reduction potential decreases then slowly increases with time, turbidity rises above the control at varied rates, and TDS increases abruptly and rises at a hindered rate. Moreover, the films potentially leach out lead chromate. The results imply that degrading oxo-biodegradable LDPE films results to significant reduction of water quality.

Nitric Oxide-Releasing Chitosan Oligosaccharides as Antibacterial Agents

PubMed Central

Lu, Yuan; Slomberg, Danielle L.; Schoenfisch, Mark H.

2014-01-01

Secondary amine-functionalized chitosan oligosaccharides of different molecular weights (i.e., ~2500, 5000, 10000) were synthesized by grafting 2-methyl aziridine from the primary amines on chitosan oligosaccharides, followed by reaction with nitric oxide (NO) gas under basic conditions to yield N-diazeniumdiolate NO donors. The total NO storage, maximum NO flux, and half-life of the resulting NO-releasing chitosan oligosaccharides were controlled by the molar ratio of 2-methyl aziridine to primary amines (e.g., 1:1, 2:1) and the functional group surrounding the N-diazeniumdiolates (e.g., polyethylene glycol (PEG) chains), respectively. The secondary amine-modified chitosan oligosaccharides greatly increased the NO payload over existing biodegradable macromolecular NO donors. In addition, the water-solubility of the chitosan oligosaccharides enabled their penetration across the extracellular polysaccharides matrix of Pseudomonas aeruginosa biofilms and association with embedded bacteria. The effectiveness of these chitosan oligosaccharides at biofilm eradication was shown to depend on both the molecular weight and ionic characteristics. Low molecular weight and cationic chitosan oligosaccharides exhibited rapid association with bacteria throughout the entire biofilm, leading to enhanced biofilm killing. At concentrations resulting in 5-log killing of bacteria in Pseudomonas aeruginosa biofilms, the NO-releasing and control chitosan oligosaccharides elicited no significant cytotoxicity to mouse fibroblast L929 cells in vitro. PMID:24268196

Phase behavior and dynamics of a micelle-forming triblock copolymer system

NASA Astrophysics Data System (ADS)

Mohan, P. Harsha; Bandyopadhyay, Ranjini

2008-04-01

Synperonic F-108 (generic name, “pluronic”) is a micelle forming triblock copolymer of type ABA , where A is polyethylene oxide (PEO) and B is polypropylene oxide (PPO). At high temperatures, the hydrophobicity of the PPO chains increase, and the pluronic molecules, when dissolved in an aqueous medium, self-associate into spherical micelles with dense PPO cores and hydrated PEO coronas. At appropriately high concentrations, these micelles arrange in a face centered cubic lattice to show inverse crystallization, with the samples exhibiting high-temperature crystalline and low-temperature fluidlike phases. By studying the evolution of the elastic and viscous moduli as temperature is increased at a fixed rate, we construct the concentration-temperature phase diagram of Synperonic F-108. For a certain range of temperatures and at appropriate sample concentrations, we observe a predominantly elastic response. Oscillatory strain amplitude sweep measurements on these samples show pronounced peaks in the loss moduli, a typical feature of soft solids. The soft solidlike nature of these materials is further demonstrated by measuring their frequency-dependent mechanical moduli. The storage moduli are significantly larger than the loss moduli and are almost independent of the applied angular frequency. Finally, we perform strain rate frequency superposition experiments to measure the slow relaxation dynamics of this soft solid.

Chip PCR. I. Surface passivation of microfabricated silicon-glass chips for PCR.

PubMed Central

Shoffner, M A; Cheng, J; Hvichia, G E; Kricka, L J; Wilding, P

1996-01-01

The microreaction volumes of PCR chips (a microfabricated silicon chip bonded to a piece of flat glass to form a PCR reaction chamber) create a relatively high surface to volume ratio that increases the significance of the surface chemistry in the polymerase chain reaction (PCR). We investigated several surface passivations in an attempt to identify 'PCR friendly' surfaces and used those surfaces to obtain amplifications comparable with those obtained in conventional PCR amplification systems using polyethylene tubes. Surface passivations by a silanization procedure followed by a coating of a selected protein or polynucleotide and the deposition of a nitride or oxide layer onto the silicon surface were investigated. Native silicon was found to be an inhibitor of PCR and amplification in an untreated PCR chip (i.e. native slicon) had a high failure rate. A silicon nitride (Si(3)N(4) reaction surface also resulted in consistent inhibition of PCR. Passivating the PCR chip using a silanizing agent followed by a polymer treatment resulted in good amplification. However, amplification yields were inconsistent and were not always comparable with PCR in a conventional tube. An oxidized silicon (SiO(2) surface gave consistent amplifications comparable with reactions performed in a conventional PCR tube. PMID:8628665

Highly tunable porous organic polymer (POP) supports for metallocene-based ethylene polymerization

NASA Astrophysics Data System (ADS)

Wang, Xiong; Li, Zhenyou; Han, Xiaoyu; Han, Zhengang; Bai, Yongxiao

2017-10-01

Porous organic Polymers (POPs) can not only exhibit high specific surface area and pore volume, but also tunable pore size distribution. Herein, copolymers of 2-hydroxyethylmethylacrylate (HEMA) and divinylbenzene (DVB) with specific pore structure were synthesized via a dispersion polymerization strategy, and then immobilized metallocene catalysts with well-defined pore structure were obtained on the produced POP supports. The nitrogen sorption and Gel permeation chromatography (GPC) results demonstrate that the pore structure of the immobilized metallocene catalyst is highly dependent on the pore structure of the POPs, and the pore structure of metallocene catalysts or the POPs has a significant influence on the molecular chain growth of the produced polyethylene. By tuning the distribution of the active species scattered in the micro- and the narrow meso-pore range (roughly ≤4 nm), the chain growth of the polyolefin can be tailored effectively during the polymerization process, although differential scanning calorimetry (DSC) and temperature rising elution fractionation (TREF) results show that the chemical composition distributions (CCDs) of produced PE from the POPs-supported metallocene catalysts are not determined by polymerization activity or molecule chain length, but mainly by the active site species scattered in the supported catalysts. Scanning electron micrograph (SEM) shows that the produced polyethylene has highly porous fabric which consists of nanofiber and spherical beads of micron dimension.

X-ray computed tomography imaging of a tumor with high sensitivity using gold nanoparticles conjugated to a cancer-specific antibody via polyethylene glycol chains on their surface

NASA Astrophysics Data System (ADS)

Nakagawa, Tomohiko; Gonda, Kohsuke; Kamei, Takashi; Cong, Liman; Hamada, Yoh; Kitamura, Narufumi; Tada, Hiroshi; Ishida, Takanori; Aimiya, Takuji; Furusawa, Naoko; Nakano, Yasushi; Ohuchi, Noriaki

2016-01-01

Contrast agents are often used to enhance the contrast of X-ray computed tomography (CT) imaging of tumors to improve diagnostic accuracy. However, because the iodine-based contrast agents currently used in hospitals are of low molecular weight, the agent is rapidly excreted from the kidney or moves to extravascular tissues through the capillary vessels, depending on its concentration gradient. This leads to nonspecific enhancement of contrast images for tissues. Here, we created gold (Au) nanoparticles as a new contrast agent to specifically image tumors with CT using an enhanced permeability and retention (EPR) effect. Au has a higher X-ray absorption coefficient than does iodine. Au nanoparticles were supported with polyethylene glycol (PEG) chains on their surface to increase the blood retention and were conjugated with a cancer-specific antibody via terminal PEG chains. The developed Au nanoparticles were injected into tumor-bearing mice, and the distribution of Au was examined with CT imaging, transmission electron microscopy, and elemental analysis using inductively coupled plasma optical emission spectrometry. The results show that specific localization of the developed Au nanoparticles in the tumor is affected by a slight difference in particle size and enhanced by the conjugation of a specific antibody against the tumor.

Low-cost optical fabrication of flexible copper electrode via laser-induced reductive sintering and adhesive transfer

NASA Astrophysics Data System (ADS)

Back, Seunghyun; Kang, Bongchul

2018-02-01

Fabricating copper electrodes on heat-sensitive polymer films in air is highly challenging owing to the need of expensive copper nanoparticles, rapid oxidation of precursor during sintering, and limitation of sintering temperature to prevent the thermal damage of the polymer film. A laser-induced hybrid process of reductive sintering and adhesive transfer is demonstrated to cost-effectively fabricate copper electrode on a polyethylene film with a thermal resistance below 100 °C. A laser-induced reductive sintering process directly fabricates a high-conductive copper electrode onto a glass donor from copper oxide nanoparticle solution via photo-thermochemical reduction and agglomeration of copper oxide nanoparticles. The sintered copper patterns were transferred in parallel to a heat-sensitive polyethylene film through self-selective surface adhesion of the film, which was generated by the selective laser absorption of the copper pattern. The method reported here could become one of the most important manufacturing technologies for fabricating low-cost wearable and disposable electronics.

Anomalous Micellization of Pluronic Block Copolymers

NASA Astrophysics Data System (ADS)

Leonardi, Amanda; Ryu, Chang Y.

2014-03-01

Poly(ethylene oxide) - poly(propylene oxide) - poly(ethylene oxide) (PEO-PPO-PEO) block copolymers, commercially known as Pluronics, are a unique family of amphiphilic triblock polymers, which self-assemble into micelles in aqueous solution. These copolymers have shown promise in therapeutic, biomedical, cosmetic, and nanotech applications. As-received samples of Pluronics contain low molecular weight impurities (introduced during the manufacturing and processing), that are ignored in most applications. It has been observed, however, that in semi-dilute aqueous solutions, at concentrations above 1 wt%, the temperature dependent micellization behavior of the Pluronics is altered. Anomalous behavior includes a shift of the critical micellization temperature and formation of large aggregates at intermediate temperatures before stable sized micelles form. We attribute this behavior to the low molecular weight impurities that are inherent to the Pluronics which interfere with the micellization process. Through the use of Dynamic Light Scattering and HPLC, we compared the anomalous behavior of different Pluronics of different impurity levels to their purified counterparts.

Extensive Bone Reaction From Catastrophic Oxidized Zirconium Wear.

PubMed

Cassar-Gheiti, Adrian J; Collins, Dennis; McCarthy, Tom

2016-01-01

The use of alternative bearing surfaces for total hip arthroplasty has become popular to minimize wear and increase longevity, especially in young patients. Oxidized zirconium (Oxinium; Smith & Nephew, Memphis, Tennessee) femoral heads were introduced in the past decade for use in total hip arthroplasty. The advantages of oxidized zirconium include less risk of fracture compared with traditional ceramic heads. This case report describes a patient with a history of bilateral avascular necrosis of the femoral head after chemotherapy for acute lymphoblastic leukemia. Nonoperative management of avascular necrosis failed, and the patient was treated with bilateral total hip arthroplasty. The patient was followed at regular intervals and had slow eccentric polyethylene wear during a 10-year period. After 10 years, the patient had accelerated wear, with femoral and acetabular bone changes as a result of Oxinium and ultrahigh-molecular-weight polyethylene wear during a 6-month period. This article highlights the unusual accelerated bone changes that occurred as a result of Oxinium wear particles. Copyright 2016, SLACK Incorporated.

Problems and solutions of polyethylene glycol co-injection method in multiresidue pesticide analysis by gas chromatography-mass spectrometry: evaluation of instability phenomenon in type II pyrethroids and its suppression by novel analyte protectants.

PubMed

Akutsu, Kazuhiko; Kitagawa, Yoko; Yoshimitsu, Masato; Takatori, Satoshi; Fukui, Naoki; Osakada, Masakazu; Uchida, Kotaro; Azuma, Emiko; Kajimura, Keiji

2018-05-01

Polyethylene glycol 300 is commonly used as a base material for "analyte protection" in multiresidue pesticide analysis via gas chromatography-mass spectrometry. However, the disadvantage of the co-injection method using polyethylene glycol 300 is that it causes peak instability in α-cyano pyrethroids (type II pyrethroids) such as fluvalinate. In this study, we confirmed the instability phenomenon in type II pyrethroids and developed novel analyte protectants for acetone/n-hexane mixture solution to suppress the phenomenon. Our findings revealed that among the examined additive compounds, three lipophilic ascorbic acid derivatives, 3-O-ethyl-L-ascorbic acid, 6-O-palmitoyl-L-ascorbic acid, and 6-O-stearoyl-L-ascorbic acid, could effectively stabilize the type II pyrethroids in the presence of polyethylene glycol 300. A mixture of the three ascorbic acid derivatives and polyethylene glycol 300 proved to be an effective analyte protectant for multiresidue pesticide analysis. Further, we designed and evaluated a new combination of analyte protectant compounds without using polyethylene glycol or the troublesome hydrophilic compounds. Consequently, we obtained a set of 10 medium- and long-chain saturated fatty acids as an effective analyte protectant suitable for acetone/n-hexane solution that did not cause peak instability in type II pyrethroids. These analyte protectants will be useful in multiresidue pesticide analysis by gas chromatography-mass spectrometry in terms of ruggedness and reliable quantitativeness. Graphical abstract Comparison of effectiveness of the addition of lipophilic derivatives of ascorbic acid in controlling the instability phenomenon of fluvalinate with polyethylene glycol 300.

Hydration of cations: a key to understanding of specific cation effects on aggregation behaviors of PEO-PPO-PEO triblock copolymers.

PubMed

Lutter, Jacob C; Wu, Tsung-yu; Zhang, Yanjie

2013-09-05

This work reports results from the interactions of a series of monovalent and divalent cations with a triblock copolymer, poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-PPO-PEO). Phase transition temperatures of the polymer in the presence of chloride salts with six monovalent and eight divalent cations were measured using an automated melting point apparatus. The polymer undergoes a two-step phase transition, consisting of micellization of the polymer followed by aggregation of the micelles, in the presence of all the salts studied herein. The results suggest that hydration of cations plays a key role in determining the interactions between the cations and the polymer. The modulation of the phase transition temperature of the polymer by cations can be explained as a balance between three interactions: direct binding of cations to the oxygen in the polymer chains, cations sharing one water molecule with the polymer in their hydration layer, and cations interacting with the polymer via two water molecules. Monovalent cations Na(+), K(+), Rb(+), and Cs(+) do not bind to the polymer, while Li(+) and NH4(+) and all the divalent cations investigated including Mg(2+), Ca(2+), Sr(2+), Ba(2+), Co(2+), Ni(2+), Cu(2+), and Cd(2+) bind to the polymer. The effects of the cations correlate well with their hydration thermodynamic properties. Mechanisms for cation-polymer interactions are discussed.

Superparamagnetic iron-oxide nanoparticles mPEG350- and mPEG2000-coated: cell uptake and biocompatibility evaluation.

PubMed

Silva, Adny H; Lima, Enio; Mansilla, Marcelo Vasquez; Zysler, Roberto D; Troiani, Horacio; Pisciotti, Mary Luz Mojica; Locatelli, Claudriana; Benech, Juan C; Oddone, Natalia; Zoldan, Vinícius C; Winter, Evelyn; Pasa, André A; Creczynski-Pasa, Tânia B

2016-05-01

Superparamagnetic iron oxide nanoparticles (SPIONS) were synthesized by thermal decomposition of an organometallic precursor at high temperature and coated with a bi-layer composed of oleic acid and methoxy-polyethylene glycol-phospholipid. The formulations were named SPION-PEG350 and SPION-PEG2000. Transmission electron microscopy, X-ray diffraction and magnetic measurements show that the SPIONs are near-spherical, well-crystalline, and have high saturation magnetization and susceptibility. FTIR spectroscopy identifies the presence of oleic acid and of the conjugates mPEG for each sample. In vitro biocompatibility of SPIONS was investigated using three cell lines; up to 100μg/ml SPION-PEG350 showed non-toxicity, while SPION-PEG2000 showed no signal of toxicity even up to 200μg/ml. The uptake of SPIONS was detected using magnetization measurement, confocal and atomic force microscopy. SPION-PEG2000 presented the highest internalization capacity, which should be correlated with the mPEG chain size. The in vivo results suggested that SPION-PEG2000 administration in mice triggered liver and kidney injury. The potential use of superparamagnetic iron oxide nanoparticles (SPIONS) in the clinical setting have been studied by many researchers. The authors synthesized two types of SPIONS here and investigated the physical properties and biological compatibility. The findings should provide more data on the design of SPIONS for clinical application in the future. Copyright © 2016 Elsevier Inc. All rights reserved.

Pyrolysis Pathways of Sulfonated Polyethylene, an Alternative Carbon Fiber Precursor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Younker, Jarod M; Saito, Tomonori; Hunt, Marcus A

2013-01-01

Sulfonated polyethylene is an emerging precursor for the production of carbon fibers. Pyrolysis of sulfonated polyethylene was characterized by thermogravimetric analysis (TGA). n-heptane-4-sulfonic acid (H4S) was selected as a model compound for the study of sulfonated polyethylene. Density functional theory and conventional transition state theory were used to determine the rate constants of pyrolysis for H4S from 300-1000 K. Multiple reaction channels from two different mechanisms were explored: 1) internal five-centered elimination (Ei 5) and 2) radical chain reaction. The pyrolysis of H4S was simulated with kinetic Monte Carlo (kMC) to obtain TGA plots that compared favorably to experiment. Wemore » observed that at tem- peratures < 550 K, the radical mechanism was dominant and yielded the trans-alkene, whereas cis-alkene was formed at higher temperatures from the internal elimination. The maximum rates of % mass loss became independent of initial OH radical concentration at 440-480 K. Experimentally, the maximum % mass loss occurred from 440-460 K (heating rate dependent). Activation energies derived from the kMC-simulated TGAs of H4S (26-29 kcal/mol) agreed with experiment for sulfonated polyethylene ( 31 kcal/mol). The simulations revealed that in this region, decomposition of radical HOSO2 became competitive to H abstraction by HOSO2, making OH the carrying radical for the reaction chain. The maximum rate of % mass loss for internal elimination was observed at temperatures > 600 K. Low-scale carbonization utilizes temperatures < 620 K; thus, internal elimination will not be competitive. Ei5 elimination has been studied for sulfoxides and sulfones, but this represents the first study of internal elimination in sulfonic acids. Nonlinear Arrhenius plots were found for all bimolecular reactions. The most significant nonlinear behavior was observed for reactions where the barrier was small. For reactions with low activation barriers, nonlinearity was traced to conflicting trends between the exponential temperature dependence of the energetic term and the temperature dependence of the vibrational partition function of the transitional modes.« less

Self-assembly of core-polyethylene glycol-lipid shell (CPLS) nanoparticles and their potential as drug delivery vehicles

NASA Astrophysics Data System (ADS)

Shen, Zhiqiang; Loe, David T.; Awino, Joseph K.; Kröger, Martin; Rouge, Jessica L.; Li, Ying

2016-08-01

Herein a new multifunctional formulation, referred to as a core-polyethylene glycol-lipid shell (CPLS) nanoparticle, has been proposed and studied in silico via large scale coarse-grained molecular dynamics simulations. A PEGylated core with surface tethered polyethylene glycol (PEG) chains is used as the starting configuration, where the free ends of the PEG chains are covalently bonded with lipid molecules (lipid heads). A complete lipid bilayer is formed at the surface of the PEGylated particle core upon addition of free lipids, driven by the hydrophobic properties of the lipid tails, leading to the formation of a CPLS nanoparticle. The self-assembly process is found to be sensitive to the grafting density and molecular weight of the tethered PEG chains, as well as the amount of free lipids added. At low grafting densities the assembly of CPLS nanoparticles cannot be accomplished. As demonstrated by simulations, a lipid bud/vesicle can be formed on the surface when an excess amount of free lipids is added at high grafting density. Therefore, the CPLS nanoparticles can only be formed under appropriate conditions of both PEG and free lipids. The CPLS nanoparticle has been recognized to be able to store a large quantity of water molecules, particularly with high molecular weight of PEG chains, indicating its capacity for carrying hydrophilic molecules such as therapeutic biomolecules or imaging agents. Under identical size and surface chemistry conditions of a liposome, it has been observed that the CPLS particle can be more efficiently wrapped by the lipid membrane, indicating its potential for a greater efficiency in delivering its hydrophilic cargo. As a proof-of-concept, the experimental realization of CPLS nanoparticles is explicitly demonstrated in this study. To test the capacity of the CPLS to store small molecule cargo a hydrophilic dye was successfully encapsulated in the particles' water soluble layer. The results of this study show the power and potential of simulation-driven approaches for guiding the design of more efficient nanomaterial delivery platforms.Herein a new multifunctional formulation, referred to as a core-polyethylene glycol-lipid shell (CPLS) nanoparticle, has been proposed and studied in silico via large scale coarse-grained molecular dynamics simulations. A PEGylated core with surface tethered polyethylene glycol (PEG) chains is used as the starting configuration, where the free ends of the PEG chains are covalently bonded with lipid molecules (lipid heads). A complete lipid bilayer is formed at the surface of the PEGylated particle core upon addition of free lipids, driven by the hydrophobic properties of the lipid tails, leading to the formation of a CPLS nanoparticle. The self-assembly process is found to be sensitive to the grafting density and molecular weight of the tethered PEG chains, as well as the amount of free lipids added. At low grafting densities the assembly of CPLS nanoparticles cannot be accomplished. As demonstrated by simulations, a lipid bud/vesicle can be formed on the surface when an excess amount of free lipids is added at high grafting density. Therefore, the CPLS nanoparticles can only be formed under appropriate conditions of both PEG and free lipids. The CPLS nanoparticle has been recognized to be able to store a large quantity of water molecules, particularly with high molecular weight of PEG chains, indicating its capacity for carrying hydrophilic molecules such as therapeutic biomolecules or imaging agents. Under identical size and surface chemistry conditions of a liposome, it has been observed that the CPLS particle can be more efficiently wrapped by the lipid membrane, indicating its potential for a greater efficiency in delivering its hydrophilic cargo. As a proof-of-concept, the experimental realization of CPLS nanoparticles is explicitly demonstrated in this study. To test the capacity of the CPLS to store small molecule cargo a hydrophilic dye was successfully encapsulated in the particles' water soluble layer. The results of this study show the power and potential of simulation-driven approaches for guiding the design of more efficient nanomaterial delivery platforms. Electronic supplementary information (ESI) available: Simulation protocol, simulation results for the self-assembly of CPLS nanoparticles, membrane wrapping and free energy change of grafted PEG polymers. See DOI: 10.1039/C6NR04134E

Do oxidized zirconium femoral heads reduce polyethylene wear in cemented THAs? A blinded randomized clinical trial.

PubMed

Zaoui, Amine; Hage, Samer El; Langlois, Jean; Scemama, Caroline; Courpied, Jean Pierre; Hamadouche, Moussa

2015-12-01

Charnley low-friction torque total hip arthroplasty (THA) remains the gold standard in THA. The main cause for failure is wear of the socket. Highly crosslinked polyethylene (HXLPE) has been associated with reduced wear rates. Also, oxidized zirconium has shown in vitro reduced wear rates. However, to our knowledge, there are no data comparing oxidized zirconium femoral heads with metal heads against HXLPE or ultrahigh-molecular-weight polyethylene (UHMWPE) when 22.25-mm bearings were used, which was the same size that performed so well in Charnley-type THAs. We hypothesized that after a minimal 4-year followup (1) use of HXLPE would result in lower radiographic wear than UHMWPE when articulating with a stainless steel head or with an oxidized zirconium head; (2) use of oxidized zirconium would result in lower radiographic wear than stainless steel when articulating with UHMWPE and HXLPE; and (3) there would be no difference in terms of Merle d'Aubigné scores between the bearing couple combinations. One hundred patients were randomized to receive cemented THA with either oxidized zirconium or a stainless steel femoral head. UHMWPE was used in the first 50 patients, whereas HXLPE was used in the next 50 patients. There were 25 patients in each of the four bearing couple combinations. All other parameters were identical in both groups. Complete followup was available in 86 of these patients. Femoral head penetration was measured using a validated computer-assisted method dedicated to all-polyethylene sockets. Clinical results were compared between the groups using the Merle d'Aubigné score. In the UHMWPE series, the median steady-state penetration rate from 1 year onward was 0.03 mm/year (range, 0.003-0.25 mm/year) in the oxidized zirconium group versus 0.11 mm/year (range, 0.03-0.29 mm/year) in the metal group (difference of medians 0.08, p < 0.001). In the HXLPE series, the median steady-state penetration rate from 1 year onward was 0.02 mm/year (range, -0.32 to 0.07 mm/year) in the oxidized zirconium group versus 0.05 mm/year (range, -0.39 to 0.11 mm/year) in the metal group (difference of medians 0.03, p < 0.001). The Merle d'Aubigné scores were no different between the groups with a median of 18 in each of the groups (range, 16-18). This study demonstrated femoral head penetration was reduced by oxidized zirconium when compared with metal on both UHMWPE and HXLPE. However, apart the metal-UHMWE group, all other groups had a steady-state penetration rate well below the osteolysis threshold with a low difference between groups that might not be clinically important at this point. Longer-term followup is needed to warrant whether wear reduction will generate less occurrence of osteolysis and aseptic loosening. Level II, therapeutic study.

Self-assembly of core-polyethylene glycol-lipid shell (CPLS) nanoparticles and their potential as drug delivery vehicles.

PubMed

Shen, Zhiqiang; Loe, David T; Awino, Joseph K; Kröger, Martin; Rouge, Jessica L; Li, Ying

2016-08-21

Herein a new multifunctional formulation, referred to as a core-polyethylene glycol-lipid shell (CPLS) nanoparticle, has been proposed and studied in silico via large scale coarse-grained molecular dynamics simulations. A PEGylated core with surface tethered polyethylene glycol (PEG) chains is used as the starting configuration, where the free ends of the PEG chains are covalently bonded with lipid molecules (lipid heads). A complete lipid bilayer is formed at the surface of the PEGylated particle core upon addition of free lipids, driven by the hydrophobic properties of the lipid tails, leading to the formation of a CPLS nanoparticle. The self-assembly process is found to be sensitive to the grafting density and molecular weight of the tethered PEG chains, as well as the amount of free lipids added. At low grafting densities the assembly of CPLS nanoparticles cannot be accomplished. As demonstrated by simulations, a lipid bud/vesicle can be formed on the surface when an excess amount of free lipids is added at high grafting density. Therefore, the CPLS nanoparticles can only be formed under appropriate conditions of both PEG and free lipids. The CPLS nanoparticle has been recognized to be able to store a large quantity of water molecules, particularly with high molecular weight of PEG chains, indicating its capacity for carrying hydrophilic molecules such as therapeutic biomolecules or imaging agents. Under identical size and surface chemistry conditions of a liposome, it has been observed that the CPLS particle can be more efficiently wrapped by the lipid membrane, indicating its potential for a greater efficiency in delivering its hydrophilic cargo. As a proof-of-concept, the experimental realization of CPLS nanoparticles is explicitly demonstrated in this study. To test the capacity of the CPLS to store small molecule cargo a hydrophilic dye was successfully encapsulated in the particles' water soluble layer. The results of this study show the power and potential of simulation-driven approaches for guiding the design of more efficient nanomaterial delivery platforms.

Room-Temperature Performance of Poly(Ethylene Ether Carbonate)-Based Solid Polymer Electrolytes for All-Solid-State Lithium Batteries.

PubMed

Jung, Yun-Chae; Park, Myung-Soo; Kim, Duck-Hyun; Ue, Makoto; Eftekhari, Ali; Kim, Dong-Won

2017-12-13

Amorphous poly(ethylene ether carbonate) (PEEC), which is a copolymer of ethylene oxide and ethylene carbonate, was synthesized by ring-opening polymerization of ethylene carbonate. This route overcame the common issue of low conductivity of poly(ethylene oxide)(PEO)-based solid polymer electrolytes at low temperatures, and thus the solid polymer electrolyte could be successfully employed at the room temperature. Introducing the ethylene carbonate units into PEEC improved the ionic conductivity, electrochemical stability and lithium transference number compared with PEO. A cross-linked solid polymer electrolyte was synthesized by photo cross-linking reaction using PEEC and tetraethyleneglycol diacrylate as a cross-linking agent, in the form of a flexible thin film. The solid-state Li/LiNi 0.6 Co 0.2 Mn 0.2 O 2 cell assembled with solid polymer electrolyte based on cross-linked PEEC delivered a high initial discharge capacity of 141.4 mAh g -1 and exhibited good capacity retention at room temperature. These results demonstrate the feasibility of using this solid polymer electrolyte in all-solid-state lithium batteries that can operate at ambient temperatures.

ESCA Study of Poly (Vinylidene Fluoride) Tetrafluoroethylene - Ethylene Copolymer and Polyethylene Exposed to Atomic Oxygen

NASA Technical Reports Server (NTRS)

Golub, Morton A.; Cormia, Robert D.

1989-01-01

The ESCA (electron spectroscopy for chemical analysis) spectra of films of poly(vinylidene fluoride) (PVDF), tetrafluoroethylene-ethylene copolymer (TFE/ET) and polyethylene (PE) exposed to atomic oxygen (O(P-3)), in or out of the glow of a radio-frequency O2 plasma, were compared. ESCA spectra of PE films exposed to (O(P-3)) in low Earth orbit (LEO) on the STS-8 Space Shuttle were also examined. Apart from O(P-3)-induced surface recession (etching), the various polymer films exhibited surface oxidation, which proceeded towards equilibrium saturation oxygen levels. The maximum surface oxygen uptakes for in-glow or out-of-glow exposures were in the order: PE greater than TFE/ET greater than PVDF; for PE itself, the oxygen uptakes were in the order: in glow greater than out of glow greater than LEO. Given prior ESCA data on poly(vinyl fluoride) and polytetrafluoroethylene films exposed to O(P-3), the extent of surface oxidation is seen to decrease regularly with increase in fluorine substitution in a family of ethylene-type polymers. (Keywords: ESCA; poly(vinylidene fluoride); tetrafluoroethylene ethylene copolymer; polyethylene; atomic oxygen; radio-frequency oxygen plasma; low Earth orbit)

Thermal transport in semicrystalline polyethylene by molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Lu, Tingyu; Kim, Kyunghoon; Li, Xiaobo; Zhou, Jun; Chen, Gang; Liu, Jun

2018-01-01

Recent research has highlighted the potential to achieve high-thermal-conductivity polymers by aligning their molecular chains. Combined with other merits, such as low-cost, corrosion resistance, and light weight, such polymers are attractive for heat transfer applications. Due to their quasi-one-dimensional structural nature, the understanding on the thermal transport in those ultra-drawn semicrystalline polymer fibers or films is still lacking. In this paper, we built the ideal repeating units of semicrystalline polyethylene and studied their dependence of thermal conductivity on different crystallinity and interlamellar topology using the molecular dynamics simulations. We found that the conventional models, such as the Choy-Young's model, the series model, and Takayanagi's model, cannot accurately predict the thermal conductivity of the quasi-one-dimensional semicrystalline polyethylene. A modified Takayanagi's model was proposed to explain the dependence of thermal conductivity on the bridge number at intermediate and high crystallinity. We also analyzed the heat transfer pathways and demonstrated the substantial role of interlamellar bridges in the thermal transport in the semicrystalline polyethylene. Our work could contribute to the understanding of the structure-property relationship in semicrystalline polymers and shed some light on the development of plastic heat sinks and thermal management in flexible electronics.

Characterization of ecofriendly polyethylene fiber from plastic bag waste

NASA Astrophysics Data System (ADS)

Soekoco, Asril S.; Noerati, Komalasari, Maya; Kurniawan, Hananto, Agus

2017-08-01

This paper presents the characterization of fiber morphology, fiber count and tenacity of polyethylene fiber which is made from plastic bag waste. Recycling plastic bag waste into textile fiber has not developed yet. Plastic bag waste was recycled into fiber by melt spinning using laboratory scale melt spinning equipment with single orifice nozzle and plunger system. The basic principle of melt spinning is by melting materials and then extruding it through small orifice of a spinning nozzle to form fibers. Diameter and cross section shape of Recycled polyethylene fiber were obtained by using scanning electron microscope (SEM) instrumentation. Linear density of the recycled fiber were analyzed by calculation using denier and dTex formulation and The mechanical strength of the fibers was measured in accordance with the ASTM D 3379-75 standard. The cross section of recycled fiber is circular taking the shape of orifice. Fiber count of 303.75 denier has 1.84 g/denier tenacity and fiber count of 32.52 has 3.44 g/denier tenacity. This conditions is affected by the growth of polymer chain alignment when take-up axial velocity become faster. Recycled polyethylene fiber has a great potential application in non-apparel textile.

Fast equilibration protocol for million atom systems of highly entangled linear polyethylene chains

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sliozberg, Yelena R.; TKC Global, Inc., Aberdeen Proving Ground, Maryland 21005; Kröger, Martin

Equilibrated systems of entangled polymer melts cannot be produced using direct brute force equilibration due to the slow reptation dynamics exhibited by high molecular weight chains. Instead, these dense systems are produced using computational techniques such as Monte Carlo-Molecular Dynamics hybrid algorithms, though the use of soft potentials has also shown promise mainly for coarse-grained polymeric systems. Through the use of soft-potentials, the melt can be equilibrated via molecular dynamics at intermediate and long length scales prior to switching to a Lennard-Jones potential. We will outline two different equilibration protocols, which use various degrees of information to produce the startingmore » configurations. In one protocol, we use only the equilibrium bond angle, bond length, and target density during the construction of the simulation cell, where the information is obtained from available experimental data and extracted from the force field without performing any prior simulation. In the second protocol, we moreover utilize the equilibrium radial distribution function and dihedral angle distribution. This information can be obtained from experimental data or from a simulation of short unentangled chains. Both methods can be used to prepare equilibrated and highly entangled systems, but the second protocol is much more computationally efficient. These systems can be strictly monodisperse or optionally polydisperse depending on the starting chain distribution. Our protocols, which utilize a soft-core harmonic potential, will be applied for the first time to equilibrate a million particle system of polyethylene chains consisting of 1000 united atoms at various temperatures. Calculations of structural and entanglement properties demonstrate that this method can be used as an alternative towards the generation of entangled equilibrium structures.« less

Biodegradation of HDPE by Aspergillus spp. from marine ecosystem of Gulf of Mannar, India.

PubMed

Sangeetha Devi, Rajendran; Rajesh Kannan, Velu; Nivas, Duraisamy; Kannan, Kanthaiah; Chandru, Sekar; Robert Antony, Arokiaswamy

2015-07-15

High density polyethylene (HDPE) is the most commonly found non-degradable solid waste among the polyethylene. In this present study, HDPE degrading various fungal strains were isolated from the polyethylene waste dumped marine coastal area and screened under in vitro condition. Based on weight loss and FT-IR Spectrophotometric analysis, two fungal strains designated as VRKPT1 and VRKPT2 were found to be efficient in HDPE degradation. Through the sequence analysis of ITS region homology, the isolated fungi were identified as Aspergillus tubingensis VRKPT1 and Aspergillus flavus VRKPT2. The biofilm formation observed under epifluorescent microscope had shown the viability of fungal strains even after one month of incubation. The biodegradation of HDPE film nature was further investigated through SEM analysis. HDPE poses severe environmental threats and hence the ability of fungal isolates was proved to utilize virgin polyethylene as the carbon source without any pre-treatment and pro-oxidant additives. Copyright © 2015 Elsevier Ltd. All rights reserved.

Polymer Grafted Nanoparticles for Designed Interfaces in Polymer Nanocomposites

NASA Astrophysics Data System (ADS)

Mohammadkhani, Mohammad

This dissertation presents the design, synthesis, and characterization of polymer nanocomposite interfaces and the property enhancement from this interface design. Through the use of reversible addition fragmentation chain transfer (RAFT) polymerization for the grafting of polymer chains to silica nanoparticles, the surface of silica nanoparticles can be manipulated to tune the properties of nanocomposites by controlling the interface between the particles and the polymer matrix. In the first part of this work, compatibility of 15 nm silica nanoparticles grafted with different alkyl methacrylates with linear low density polyethylene was investigated. SI-RAFT polymerization of hexyl, lauryl, and stearyl methacrylate on silica NPs was studied in detail and revealed living character for all these polymerizations. Composites of linear low density polyethylene filled with PHMA, PLMA, and PSMA-g-SiO2 NPs were prepared and analyzed to find the effects of side chain length on the dispersibility of particles throughout the matrix. PSMA brushes were the most "olefin-like" of the series and thus showed the highest compatibility with polyethylene. The effects of PSMA brush molecular weight and chain density on the dispersion of silica particles were investigated. Multiple characterizations such as DSC, WAXS, and SAXS were applied to study the interaction between PSMA-g-SiO2 NPs and the polyethylene matrix. In the next part, the compatibility of PSMA-g-SiO2 NPs with different molecular variables with isotactic polypropylene was investigated. Anthracene was used as a conjugated ligand to introduce to the surface of PSMA-g-SiO2 NPs to develop bimodal architecture on nanoparticles and use them in polypropylene dielectric nanocomposites. The dispersion of particles was investigated and showed that for both monomodal and bimodal particles where PSMA chains are medium density and relatively high molecular weight, they maintain an acceptable level of dispersion throughout of the matrix. Furthermore, the effects of anthracene surface modification and also level of dispersion towards improving the dielectric breakdown strength under AC and DC conditions were studied. Finally, the RAFT polymerizations of isoprene in solution and, for the first time, on the surface of silica particles using a high temperature stable trithiocarbonate RAFT agent were studied. The effects of different temperatures, initiators, and monomer feed ratios on the kinetics of the SI-RAFT polymerization were also investigated. Kinetic studies revealed that the rate of SI-RAFT polymerization increased with an increase in the density of grafted RAFT agent. Well-defined polyisoprene-grafted silica NPs (PIP-g-SiO2 NPs) were synthesized and mixed with a polyisoprene matrix to determine the compatibility and dispersion of these particles with the matrix. Hydrogenation of PIP-g-SiO2 NPs were performed using p-toluenesulfonyl hydrazide at high temperature to obtain hydrogenated (HPIP)-g-SiO2 NPs. A bimodal octadecylsilane (C18)-HPIP-g-SiO2 NPs sample was synthesized and mixed with isotactic PP matrix analyzed for the compatibility with polypropylene.

Effect of a low-density polyethylene film containing butylated hydroxytoluene on lipid oxidation and protein quality of Sierra fish (Scomberomorus sierra) muscle during frozen storage.

PubMed

Torres-Arreola, Wilfrido; Soto-Valdez, Herlinda; Peralta, Elizabeth; Cardenas-López, José Luis; Ezquerra-Brauer, Josafat Marina

2007-07-25

Fresh sierra fish (Scomberomorus sierra) fillets were packed in low-density polyethylene films with butylated hydroxytoluene (BHT-LDPE) added. Fillets packed in LDPE with no BHT were used as controls (LDPE). The packed fillets were stored at -25 degrees C for 120 days in which the film released 66.5% of the antioxidant. The influence of the antioxidant on lipid and protein quality, lipid oxidation, muscle structure changes, and shear-force resistance was recorded. As compared to LDPE films, fillets packed in BHT-LDPE films showed lower lipid oxidation, thiobarbituric acid values (4.20 +/- 0.52 vs 11.95 +/- 1.06 mg malonaldehyde/kg), peroxide values (7.20 +/- 1.38 vs 15.15 +/- 1.48 meq/kg), and free fatty acids (7.98 +/- 0.43 vs 11.83 +/- 1.26% of oleic acid). Fillets packed in BHT-LDPE films showed less tissue damage and lost less firmness than fillets packed in LDPE. A significant relationship between lipid oxidation and texture was detected (R2 adjusted, 0.70-0.73). BHT-LDPE films may be used not only to prevent lipid oxidation but also to minimize protein damage to prolong the shelf life of sierra fish.

Lithium batteries using poly(ethylene oxide)-based non-aqueous electrolytes

DOEpatents

Chen, Zonghai; Amine, Khalil

2015-09-08

Lithium-air cells employing poly(ethyleneoxide) phosphate-based electrolytes may be prepared and exhibit improved charge carrying capacity. Such PEO phosphates generally have the formulas IIa, IIb, IIc, where: ##STR00001##

Effects of vacancy defects on the interfacial shear strength of carbon nanotube reinforced polymer composite.

PubMed

Chowdhury, Sanjib Chandra; Okabe, Tomonaga; Nishikawa, Masaaki

2010-02-01

We investigate the effects of the vacancy defects (i.e., missing atoms) in carbon nanotubes (CNTs) on the interfacial shear strength (ISS) of the CNT-polyethylene composite with the molecular dynamics simulation. In the simulation, the crystalline polyethylene matrix is set up in a hexagonal array with the polymer chains parallel to the CNT axis. Vacancy defects in the CNT are introduced by removing the corresponding atoms from the pristine CNT (i.e., CNT without any defect). Three patterns of vacancy defects with three different sizes are considered. Two types of interfaces, with and without cross-links between the CNT and the matrix are also considered here. Polyethylene chains are used as cross-links between the CNT and the matrix. The Brenner potential is used for the carbon-carbon interaction in the CNT, while the polymer is modeled by a united-atom potential. The nonbonded van der Waals interaction between the CNT and the polymer matrix and within the polymer matrix itself is modeled with the Lennard-Jones potential. To determine the ISS, we conduct the CNT pull-out from the polymer matrix and the ISS has been estimated with the change of total potential energy of the CNT-polymer system. The simulation results reveal that the vacancy defects significantly influence the ISS. Moreover, the simulation clarifies that CNT breakage occurs during the pull-out process for large size vacancy defect which ultimately reduces the reinforcement.

Investigation of tribological properties of graphene oxide reinforced ultrahigh molecular weight polyethylene under artificial seawater lubricating condition

NASA Astrophysics Data System (ADS)

Pang, Wenchao; Ni, Zifeng; Wu, JiaLiang; Zhao, Yongwu

2018-03-01

A range of ultrahigh molecular weight polyethylene (UHMWPE)/graphene oxide (GO) nanocomposites were fabricated using liquid-phase ultrasonication mixing followed by hot-pressing. The wettability, water absorption and corrosion resistance of composites were studied to prove the composites were suitable for application in liquid environment. The tribological properties of composites under dry, deionized water and seawater lubricating condition were investigated. The results showed that the incorporation of GO decreased the wear rate of UHMWPE under different lubricating conditions and with the increase of GO addition, the wear rate of UHMWPE/GO composites decreased. UHMWPE/GO composites exhibited better tribological behaviors under seawater lubricating condition than other conditions, because good corrosion resistance and excellent wear resistance of UHMWPE/GO composites, and the lubricating effect of seawater is also indispensable.

Role of free radicals in aseptic loosening of hip arthroplasty.

PubMed

Kinov, Plamen; Leithner, Andreas; Radl, Roman; Bodo, Koppany; Khoschsorur, Gholam-Ali; Schauenstein, Konrad; Windhager, Reinhard

2006-01-01

Fibrous pseudocapsule around hip implants is an invariable finding at revision operations and is believed to release inflammatory mediators that stimulate bone resorption. Reactive oxygen species have been proposed to be causative factors in various disorders with tissue fibrosis. We were interested in investigating whether aseptic loosening is connected with high oxidative stress, and in showing the underlying mechanism of periprosthetic fibrosis and its role in loosening. Levels of oxidative stress markers reduced (GSH) and oxidized (GSSG) gluthatione and malondialdehyde (MDA) were assayed in 28 loose hips and in 12 stable hips revised for high rate of wear and osteolysis. Collagen in the periprosthetic tissues was measured as hydroxyproline content. Osteolysis and polyethylene wear were graded. Increased oxidative stress measured by low GSH/GSSG ratio as well as by increased MDA level was established in patients compared to controls. Oxidative stress markers intercorrelated significantly. MDA and both GSH and GSSG levels correlated significantly with hydroxyproline level. Levels of GSSG and MDA were higher in hips with greater polyethylene wear. The results suggest that high oxidative stress may play a role in formation of a fibrous membrane observed at revision of loose hips. The fibrous pseudocapsule is probably related to high intraarticular pressure and expansion of the effective joint space. This study may elicit some aspects of the pathogenesis of aseptic hip loosening and aid in future investigations aiming at prevention of this complication.

Thermal conductivity of electrospun polyethylene nanofibers.

PubMed

Ma, Jian; Zhang, Qian; Mayo, Anthony; Ni, Zhonghua; Yi, Hong; Chen, Yunfei; Mu, Richard; Bellan, Leon M; Li, Deyu

2015-10-28

We report on the structure-thermal transport property relation of individual polyethylene nanofibers fabricated by electrospinning with different deposition parameters. Measurement results show that the nanofiber thermal conductivity depends on the electric field used in the electrospinning process, with a general trend of higher thermal conductivity for fibers prepared with stronger electric field. Nanofibers produced at a 45 kV electrospinning voltage and a 150 mm needle-collector distance could have a thermal conductivity of up to 9.3 W m(-1) K(-1), over 20 times higher than the typical bulk value. Micro-Raman characterization suggests that the enhanced thermal conductivity is due to the highly oriented polymer chains and enhanced crystallinity in the electrospun nanofibers.

Investigation on electrical tree propagation in polyethylene based on etching method

NASA Astrophysics Data System (ADS)

Shi, Zexiang; Zhang, Xiaohong; Wang, Kun; Gao, Junguo; Guo, Ning

2017-11-01

To investigate the characteristic of electrical tree propagation in semi-crystalline polymers, the low-density polyethylene (LDPE) samples containing electrical trees are cut into slices by using ultramicrotome. Then the slice samples are etched by potassium permanganate etchant. Finally, the crystalline structure and the electrical tree propagation path in samples are observed by polarized light microscopy (PLM). According to the observation, the LDPE spherocrystal structure model is established on the basis of crystallization kinetics and morphology of polymers. And the electrical tree growth process in LDPE is discussed based on the free volume breakdown theory, the molecular chain relaxation theory, the electromechanical force theory, the thermal expansion effect and the space charge shielding effect.

How to polymerize ethylene in a highly controlled fashion?

PubMed

Kempe, Rhett

2007-01-01

Very fast, reversible, polyethylene (PE) chain transfer or complex-catalysed "Aufbaureaktion" describes a "living" chain-growing process on a main-group metal or zinc atom; this process is catalysed by an organo-transition-metal or lanthanide complex. PE chains are transferred very fast between the two metal sites and chain growth takes place through ethylene insertion into the transition-metal- or lanthanide-carbon bond-coordinative chain-transfer polymerisation (CCTP). The transferred chains "rest" at the main-group or zinc centre, at which chain-termination processes like beta-H transfer/elimination are of low significance. Such protocols can be used to synthesise very narrowly distributed PE materials (M(w)/M(n)<1.1 up to a molecular weight of about 4000 g mol(-1)) with differently functionalised end groups. Higher molecular-weight polymers can be obtained with a slightly increased M(w)/M(n), since diffusion control and precipitation of the polymers influences the chain-transfer process. Recently, a few transition-metal- or lanthanide-based catalyst systems that catalyse such a highly reversible chain-growing process have been described. They are summarised and compared within this contribution.

Hemoglobin extravasation in the brain of rats exchange-transfused with hemoglobin-based oxygen carriers.

PubMed

Terraneo, Laura; Bianciardi, Paola; Malavalli, Ashok; Mkrtchyan, Gnel; Spann, Stephanie N; Lohman, Jeff; Samaja, Michele; Vandegriff, Kim D

2017-06-01

Haemoglobin (Hb)-based oxygen carriers are under consideration as oxygen therapeutics. Their effect on apoptosis is critical, because the onset of pro-apoptotic pathways may lead to tissue damage. MP4OX, a polyethylene glycol-conjugated human Hb preserves the baseline level of neuron apoptosis with respect to sham. Here we develop a method for measuring Hb extravasation in brain. We exchange transfused rats by haemorrhaging 50% of their blood with simultaneous, isovolemic replacement with Hextend (negative control), MP4OX, or αα-cross-linked Hb. Animals were sacrificed 2 h after transfusion, brain tissue was harvested and processed for double-staining immunofluorescence, whereby Hb ? chain and NeuN (a neuron protein) were stained and quantitated. Whereas Hextend did not induce Hb extravasation, in both MP4OX and ??Hb brains Hb molecules were detected outside neurons. The level of extravasated Hb chains was > 3-fold higher in Hb compared to MP4OX. Western blot analysis revealed that the expression levels of protein related to redox imbalance (e.g., Nrf2, iNOS and ERK phosphorylation) were higher in ααHb than MP4OX. In conclusions, higher Hb extravasation in ααHb than MP4OX induces redox imbalance, which causes higher anti-oxidant response. Whereas Nrf2 response may be considered protective, iNOS response appears damaging.

Investigation of space charge distribution of low-density polyethylene/GO-GNF (graphene oxide from graphite nanofiber) nanocomposite for HVDC application.

PubMed

Kim, Yoon Jin; Ha, Son-Tung; Lee, Gun Joo; Nam, Jin Ho; Ryu, Ik Hyun; Nam, Su Hyun; Park, Cheol Min; In, Insik; Kim, Jiwan; Han, Chul Jong

2013-05-01

This paper reported a research on space charge distribution in low-density polyethylene (LDPE) nanocomposites with different types of graphene and graphene oxide (GO) at low filler content (0.05 wt%) under high DC electric field. Effect of addition of graphene oxide or graphene, its dispersion in LDPE polymer matrix on the ability to suppress space charge generation will be investigated and compared with MgO/LDPE nanocomposite at the same filler concentration. At an applied electric field of 80 kV/mm, a positive packet-like charge was observed in both neat LDPE, MgO/LDPE, and graphene/LDPE nanocomposites, whereas only little homogenous space charge was observed in GO/LDPE nanocomposites, especially with GO synthesized from graphite nano fiber (GNF) which is only -100 nm in diameter. Our research also suggests that dispersion of graphene oxide particles on the polymer matrix plays a significant role to the performance of nanocomposites on suppressing packet-like space charge. From these results, it is expected that nano-sized GO synthesized from GNF can be a promising filler material to LDPE composite for HVDC applications.

Multifunctional Micelles Dually Responsive to Hypoxia and Singlet Oxygen: Enhanced Photodynamic Therapy via Interactively Triggered Photosensitizer Delivery.

PubMed

Li, Juanjuan; Meng, Xuan; Deng, Jian; Lu, Di; Zhang, Xin; Chen, Yanrui; Zhu, Jundong; Fan, Aiping; Ding, Dan; Kong, Deling; Wang, Zheng; Zhao, Yanjun

2018-05-23

Nanoparticulate antitumor photodynamic therapy (PDT) has been suffering from the limited dose accumulation in tumor. Herein, we report dually hypoxia- and singlet oxygen-responsive polymeric micelles to efficiently utilize the photosensitizer deposited in the disease site and hence facilely improve PDT's antitumor efficacy. Tailored methoxy poly(ethylene glycol)-azobenzene-poly(aspartic acid) copolymer conjugate with imidazole as the side chains was synthesized. The conjugate micelles (189 ± 19 nm) obtained by self-assembly could efficiently load a model photosensitizer, chlorin e6 (Ce6) with a loading of 4.1 ± 0.5% (w/w). The facilitated cellular uptake of micelles was achieved by the triggered azobenzene collapse that provoked poly(ethylene glycol) shedding; rapid Ce6 release was enabled by imidazole oxidation that induced micelle disassembly. In addition, the singlet oxygen-mediated cargo release not only addressed the limited diffusion range and short half-life of singlet oxygen but also decreased the oxygen level, which could in turn enhance internalization and increase the intracellular Ce6 concentration. The hypoxia-induced dePEGylation and singlet oxygen-triggered Ce6 release was demonstrated both in aqueous buffer and in Lewis lung carcinoma (LLC) cells. The cellular uptake study demonstrated that the dually responsive micelles could deliver significantly more Ce6 to the cells, which resulted in a substantially improved cytotoxicity. This concurred well with the superior in vivo antitumor ability of micelles in a LLC tumor-bearing mouse model. This study presented an intriguing nanoplatform to realize interactively triggered photosensitizer delivery and improved antitumor PDT efficacy.

Conversion of post consumer polyethylene to the biodegradable polymer polyhydroxyalkanoate.

PubMed

Guzik, Maciej W; Kenny, Shane T; Duane, Gearoid F; Casey, Eoin; Woods, Trevor; Babu, Ramesh P; Nikodinovic-Runic, Jasmina; Murray, Michael; O'Connor, Kevin E

2014-05-01

A process for the conversion of post consumer (agricultural) polyethylene (PE) waste to the biodegradable polymer medium chain length polyhydroxyalkanoate (mcl-PHA) is reported here. The thermal treatment of PE in the absence of air (pyrolysis) generated a complex mixture of low molecular weight paraffins with carbon chain lengths from C8 to C32 (PE pyrolysis wax). Several bacterial strains were able to grow and produce PHA from this PE pyrolysis wax. The addition of biosurfactant (rhamnolipids) allowed for greater bacterial growth and PHA accumulation of the tested strains. Some strains were only capable of growth and PHA accumulation in the presence of the biosurfactant. Pseudomonas aeruginosa PAO-1 accumulated the highest level of PHA with almost 25 % of the cell dry weight as PHA when supplied with the PE pyrolysis wax in the presence of rhamnolipids. The change of nitrogen source from ammonium chloride to ammonium nitrate resulted in faster bacterial growth and the earlier onset of PHA accumulation. To our knowledge, this is the first report where PE is used as a starting material for production of a biodegradable polymer.

Influence of polyethylene glycol on percolation dynamics of reverse microemulsions

NASA Astrophysics Data System (ADS)

Geethu, P. M.; Yadav, Indresh; Aswal, V. K.; Satapathy, D. K.

2018-04-01

We explore the influence of a hydrophilic polymer, polyethylene glycol (PEG), on the structure and the percolation dynamics of reverse microemulsions (ME) stabilized by an anionic surfactant AOT (sodium bis(2-ethylhexyl) sulfosuccinate). The percolation transition of MEs is probed using dielectric relaxation spectroscopy (DRS). Notably, an increase in percolation temperature is observed by the incorporation of PEG-polymer into larger ME droplets which is explained by considering the model of polymer adsorption at surfactant-water interface. The stability of the droplet phase of microemulsion after the incorporation of PEG is confirmed by small-angle neutron scattering (SANS) experiment. Further, a net decrease in percolation transition temperature is observed with the addition of PEG polymer for smaller ME droplets and is discussed in relation with the destabilization of droplets owing to the polymer induced bridging and the associated clustering of droplets. We conjecture that the adsorption of PEG polymer chains at the surfactant-water interface as well as the PEG-induced bridging of droplets are due to the strong ion-dipole interaction between anionic head group of AOT surfactant and dipoles present in PEG polymer chains.

Aspirin Increases Mitochondrial Fatty Acid Oxidation

PubMed Central

Uppala, Radha; Dudiak, Brianne; Beck, Megan E.; Bharathi, Sivakama S.; Zhang, Yuxun; Stolz, Donna B.; Goetzman, Eric S.

2016-01-01

The metabolic effects of salicylates are poorly understood. This study investigated the effects of aspirin on fatty acid oxidation. Aspirin increased mitochondrial long-chain fatty acid oxidation, but inhibited peroxisomal fatty acid oxidation, in two different cell lines. Aspirin increased mitochondrial protein acetylation and was found to be a stronger acetylating agent in vitro than acetyl-CoA. However, aspirin-induced acetylation did not alter the activity of fatty acid oxidation proteins, and knocking out the mitochondrial deacetylase SIRT3 did not affect the induction of long-chain fatty acid oxidation by aspirin. Aspirin did not change oxidation of medium-chain fatty acids, which can freely traverse the mitochondrial membrane. Together, these data indicate that aspirin does not directly alter mitochondrial matrix fatty acid oxidation enzymes, but most likely exerts its effects at the level of long-chain fatty acid transport into mitochondria. The drive on mitochondrial fatty acid oxidation may be a compensatory response to altered mitochondrial morphology and inhibited electron transport chain function, both of which were observed after 24 hr incubation of cells with aspirin. These studies provide insight into the pathophysiology of Reye Syndrome, which is known to be triggered by aspirin ingestion in patients with fatty acid oxidation disorders. PMID:27856258

Boron-based nanostructures: Synthesis, functionalization, and characterization

NASA Astrophysics Data System (ADS)

Bedasso, Eyrusalam Kifyalew

Boron-based nanostructures have not been explored in detail; however, these structures have the potential to revolutionize many fields including electronics and biomedicine. The research discussed in this dissertation focuses on synthesis, functionalization, and characterization of boron-based zero-dimensional nanostructures (core/shell and nanoparticles) and one-dimensional nanostructures (nanorods). The first project investigates the synthesis and functionalization of boron-based core/shell nanoparticles. Two boron-containing core/shell nanoparticles, namely boron/iron oxide and boron/silica, were synthesized. Initially, boron nanoparticles with a diameter between 10-100 nm were prepared by decomposition of nido-decaborane (B10H14) followed by formation of a core/shell structure. The core/shell structures were prepared using the appropriate precursor, iron source and silica source, for the shell in the presence of boron nanoparticles. The formation of core/shell nanostructures was confirmed using high resolution TEM. Then, the core/shell nanoparticles underwent a surface modification. Boron/iron oxide core/shell nanoparticles were functionalized with oleic acid, citric acid, amine-terminated polyethylene glycol, folic acid, and dopamine, and boron/silica core/shell nanoparticles were modified with 3-(amino propyl) triethoxy silane, 3-(2-aminoethyleamino)propyltrimethoxysilane), citric acid, folic acid, amine-terminated polyethylene glycol, and O-(2-Carboxyethyl)polyethylene glycol. A UV-Vis and ATR-FTIR analysis established the success of surface modification. The cytotoxicity of water-soluble core/shell nanoparticles was studied in triple negative breast cancer cell line MDA-MB-231 and the result showed the compounds are not toxic. The second project highlights optimization of reaction conditions for the synthesis of boron nanorods. This synthesis, done via reduction of boron oxide with molten lithium, was studied to produce boron nanorods without any contamination and with a uniform size distribution. Various reaction parameters such as temperature, reaction time, and sonication were altered to find the optimal reaction conditions. Once these conditions were determined, boron nanorods were produced then functionalized with amine-terminated polyethylene glycol.

Modulation of Protein Adsorption and Cell Proliferation on Polyethylene Immobilized Graphene Oxide Reinforced HDPE Bionanocomposites.

PubMed

Upadhyay, Rahul; Naskar, Sharmistha; Bhaskar, Nitu; Bose, Suryasarathi; Basu, Bikramjit

2016-05-18

The uniform dispersion of nanoparticles in a polymer matrix, together with an enhancement of interfacial adhesion is indispensable toward achieving better mechanical properties in the nanocomposites. In the context to biomedical applications, the type and amount of nanoparticles can potentially influence the biocompatibility. To address these issues, we prepared high-density polyethylene (HDPE) based composites reinforced with graphene oxide (GO) by melt mixing followed by compression molding. In an attempt to tailor the dispersion and to improve the interfacial adhesion, we immobilized polyethylene (PE) onto GO sheets by nucleophilic addition-elimination reaction. A good combination of yield strength (ca. 20 MPa), elastic modulus (ca. 600 MPa), and an outstanding elongation at failure (ca. 70%) were recorded with 3 wt % polyethylene grafted graphene oxide (PE-g-GO) reinforced HDPE composites. Considering the relevance of protein adsorption as a biophysical precursor to cell adhesion, the protein adsorption isotherms of bovine serum albumin (BSA) were determined to realize three times higher equilibrium constant (Keq) for PE-g-GO-reinforced HDPE composites as compared to GO-reinforced composites. To assess the cytocompatibility, we grew osteoblast cell line (MC3T3) and human mesenchymal stem cells (hMSCs) on HDPE/GO and HDPE/PE-g-GO composites, in vitro. The statistically significant increase in metabolically active cell over different time periods in culture for up to 6 days in MC3T3 and 7 days for hMSCs was observed, irrespective of the substrate composition. Such observation indicated that HDPE with GO or PE-g-GO addition (up to 3 wt %) can be used as cell growth substrate. The extensive proliferation of cells with oriented growth pattern also supported the fact that tailored GO addition can support cellular functionality in vitro. Taken together, the experimental results suggest that the PE-g-GO in HDPE can effectively be utilized to enhance both mechanical and cytocompatibility properties and can further be explored for potential biomedical applications.

Towards aging mechanisms of cross-linked polyethylene (XLPE) cable insulation materials in nuclear power plants

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Shuaishuai; Fifield, Leonard S.; Bowler, Nicola

Cross-linked polyethylene (XLPE) cable insulation material undergoes simultaneous, accelerated thermal and gamma-radiation aging to simulate the long-term aging environment within nuclear power plants (NPPs). A variety of materials characterization tests, including scanning electron microscopy, thermo-gravimetric analysis, differential scanning calorimetry, oxidation induction time, gel-fraction and dielectric properties measurement, are conducted on pristine and differently aged XLPE samples. A preliminary model of one possible aging mechanism of XLPE cable insulation material under gamma radiation at elevated temperature of 115 °C is suggested.

Probing the Conformational Landscape of a Polyether Building Block by Raman Jet Spectroscopy

NASA Astrophysics Data System (ADS)

Bocklitz, Sebastian; Suhm, Martin A.

2015-06-01

Polyethylene oxides (Polyethylene glycoles) represent a prominent class of water-soluble polymers. Surprisingly, already 1,2-dimethoxyethane as the simplest representative of this polymer family has an undetermined conformational preference in the gas phase. Here, we address this problem by spontaneous Raman scattering in a supersonic jet. Variation of carrier gas, stagnation pressure, nozzle distance and temperature provides information on the three lowest conformations and their mutual interconversion during collisions in the expansion. The results are compared to quantum chemical calculations of the potential energy landscape and of normal modes.

Novel Bioconjugation Strategy Using Elevated Hydrostatic Pressure: A Case Study for the Site-Specific Attachment of Polyethylene Glycol (PEGylation) of Recombinant Human Ciliary Neurotrophic Factor.

PubMed

Wang, Qi; Zhang, Chun; Guo, Fangxia; Li, Zenglan; Liu, Yongdong; Su, Zhiguo

2017-11-15

In this paper, we reported a novel strategy for the site-specific attachment of polyethylene glycol (PEGylation) of proteins using elevated hydrostatic pressure. The process was similar to the conventional one except the reactor was under elevated hydrostatic pressure. The model protein was recombinant human ciliary neurotrophic factor (rhCNTF), and the reagent was monomethoxy-polyethylene glycol-maleimide (mPEG-MAL). PEGylation with mPEG (40 kDa)-MAL at pH 7.0 under normal pressure for 5 h achieved a less than 5% yield. In comparison, when the pressure was elevated, the PEGylation yield was increased dramatically, reaching nearly 90% at 250 MPa. Furthermore, the following phenomena were observed: (1) high-hydrostatic-pressure PEGylation (HHPP) could operate at a low reactant ratio of 1:1.2 (rhCNTF to mPEG-MAL), while the conventional process needs a much-higher ratio. (2) Short and long chains of PEG gave a similar yield of 90% in HHPP, while the conventional yield for the short chain of the PEG was higher than that of the long chain. (3) The reaction pH in the range of 7.0 to 8.0 had almost no influence upon the yield of HHPP, while the PEGylation yield was significantly increased by a factor of three from pH 7.0 to 8.0 at normal pressure. Surface accessibility analysis was performed using GRASP2 software, and we found that Cys17 of rhCNTF was located at the concave patches, which may have steric hindrance for the PEG to approach. The speculated benefit of HHPP was the facilitation of target-site exposure, reducing the steric hindrance and making the reaction much easier. Structure and activity analysis demonstrated that the HHPP product was comparable to the PEGylated rhCNTF prepared through a conventional method. Overall, this work demonstrated that HHPP, as we proposed, may have application potentials in various conjugations of biomacromolecules.

Curcumin Encapsulated into Methoxy Poly(Ethylene Glycol) Poly(ε-Caprolactone) Nanoparticles Increases Cellular Uptake and Neuroprotective Effect in Glioma Cells.

PubMed

Marslin, Gregory; Sarmento, Bruno Filipe Carmelino Cardoso; Franklin, Gregory; Martins, José Alberto Ribeiro; Silva, Carlos Jorge Ribeiro; Gomes, Andreia Ferreira Castro; Sárria, Marisa Passos; Coutinho, Olga Maria Fernandes Pereira; Dias, Alberto Carlos Pires

2017-03-01

Curcumin is a natural polyphenolic compound isolated from turmeric ( Curcuma longa ) with well-demonstrated neuroprotective and anticancer activities. Although curcumin is safe even at high doses in humans, it exhibits poor bioavailability, mainly due to poor absorption, fast metabolism, and rapid systemic elimination. To overcome these issues, several approaches, such as nanoparticle-mediated targeted delivery, have been undertaken with different degrees of success. The present study was conducted to compare the neuroprotective effect of curcumin encapsulated in poly( ε -caprolactone) and methoxy poly(ethylene glycol) poly( ε -caprolactone) nanoparticles in U251 glioblastoma cells. Prepared nanoparticles were physically characterized by laser doppler anemometry, transmission electron microscopy, and X-ray diffraction. The results from laser doppler anemometry confirmed that the size of poly( ε -caprolactone) and poly(ethylene glycol) poly( ε -caprolactone) nanoparticles ranged between 200-240 nm for poly( ε -caprolactone) nanoparticles and 30-70 nm for poly(ethylene glycol) poly( ε -caprolactone) nanoparticles, and transmission electron microscopy images revealed their spherical shape. Treatment of U251 glioma cells and zebrafish embryos with poly( ε -caprolactone) and poly(ethylene glycol) poly( ε -caprolactone) nanoparticles loaded with curcumin revealed efficient cellular uptake. The cellular uptake of poly(ethylene glycol) poly( ε -caprolactone) nanoparticles was higher in comparison to poly( ε -caprolactone) nanoparticles. Moreover, poly(ethylene glycol) poly( ε -caprolactone) di-block copolymer-loaded curcumin nanoparticles were able to protect the glioma cells against tBHP induced-oxidative damage better than free curcumin. Together, our results show that curcumin-loaded poly(ethylene glycol) poly( ε -caprolactone) di-block copolymer nanoparticles possess significantly stronger neuroprotective effect in U251 human glioma cells compared to free curcumin and curcumin-loaded poly( ε -caprolactone) nanoparticles. Georg Thieme Verlag KG Stuttgart · New York.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Middleton, L. Robert; Tarver, Jacob D.; Cordaro, Joseph

Melt state dynamics for a series of strictly linear polyethylenes with precisely spaced associating functional groups were investigated. The periodic pendant acrylic acid groups form hydrogen-bonded acid aggregates within the polyethylene (PE) matrix. The dynamics of these nanoscale heterogeneous morphologies were investigated from picosecond to nanosecond timescales by both quasi-elastic neutron scattering (QENS) measurements and fully atomistic molecular dynamics (MD) simulations. Two dynamic processes were observed. The faster dynamic processes which occur at the picosecond timescales are compositionally insensitive and indicative of spatially restricted local motions. The slower dynamic processes are highly composition dependent and indicate the structural relaxation ofmore » the polymer backbone. Higher acid contents, or shorter PE spacers between pendant acid groups, slow the structural relaxation timescale and increase the stretching parameter (β) of the structural relaxation. Additionally, the dynamics of specific hydrogen atom positions along the backbone correlate structural heterogeneity imposed by the associating acid groups with a mobility gradient along the polymer backbone. At time intervals (<2 ns), the mean-squared displacements for the four methylene groups closest to the acid groups are up to 10 times smaller than those of methylene groups further from the acid groups. At longer timescales acid aggregates rearrange and the chain dynamics of the slow, near-aggregate regions and the faster bridge regions converge, implying a characteristic timescale for the passage of chains between aggregates. As a result, the characterization of the nanoscale chain dynamics in these associating polymer systems both provides validation of simulation force fields and provides understanding of heterogeneous chain dynamics in associating polymers.« less

A manifestation of the Ostwald step rule: molecular-dynamics simulations and free-energy landscape of the primary nucleation and melting of single-molecule polyethylene in dilute solution.

PubMed

Larini, L; Leporini, D

2005-10-08

The paper presents numerical results from extensive molecular-dynamics simulations of the crystallization process of a single polyethylene chain with N=500 monomers. The development of the ordered structure is seen to proceed along different routes involving either the global reorganization of the chain or, alternatively, well-separated connected nuclei. No dependence on the thermal history was observed at the late stages of the crystallization. The folding process involves several intermediate ordered metastable states, in strong analogy with the experiments, and ends up in a well-defined long-lived lamella with ten stems of approximately equal length, arranged into a regular, hexagonal pattern. This behavior may be seen as a microscopic manifestation of the Ostwald step rule. Both the metastable states and the long-lived one are evidenced as the local minima and the global one of the free-energy landscape, respectively. The study of the microscopic organization of the lamella evidenced that the two caps are rather flat, i.e., the loops connecting the stems are short. Interestingly, annealing the chain through the different metastable states leaves the average number of monomers per loop nearly unchanged. It is also seen that the chain ends, the so-called cilia, are localized on the surface of the lamella, in agreement with the experiments, and that structural fluctuations take place on the lamella surface, as noted by recent Monte Carlo simulations. The study of the melting process evidences that the degree of hysteresis is small.

Topological analysis of polymeric melts: chain-length effects and fast-converging estimators for entanglement length.

PubMed

Hoy, Robert S; Foteinopoulou, Katerina; Kröger, Martin

2009-09-01

Primitive path analyses of entanglements are performed over a wide range of chain lengths for both bead spring and atomistic polyethylene polymer melts. Estimators for the entanglement length N_{e} which operate on results for a single chain length N are shown to produce systematic O(1/N) errors. The mathematical roots of these errors are identified as (a) treating chain ends as entanglements and (b) neglecting non-Gaussian corrections to chain and primitive path dimensions. The prefactors for the O(1/N) errors may be large; in general their magnitude depends both on the polymer model and the method used to obtain primitive paths. We propose, derive, and test new estimators which eliminate these systematic errors using information obtainable from the variation in entanglement characteristics with chain length. The new estimators produce accurate results for N_{e} from marginally entangled systems. Formulas based on direct enumeration of entanglements appear to converge faster and are simpler to apply.

Polymer blends for use in photoelectrochemical cells for conversion of solar energy to electricity

DOEpatents

Skotheim, Terje

1986-01-01

There is disclosed a polymer blend of a highly conductive polymer and a solid polymer electrolyte that is designed to achieve better charge transfer across the conductive film/polymer electrolyte interface of the electrochemical photovoltaic cell. The highly conductive polymer is preferably polypyrrole or poly-N-p-nitrophenylpyrrole and the solid polymer electrolyte is preferably polyethylene oxide or polypropylene oxide.

Polymer blends for use in photoelectrochemical cells for conversion of solar energy to electricity

DOEpatents

Skotheim, T.

1984-09-28

There is disclosed a polymer blend of a highly conductive polymer and a solid polymer electrolyte that is designed to achieve better charge transfer across the conductive film/polymer electrolyte interface of the electrochemical photovoltaic cell. The highly conductive polymer is preferably polypyrrole or poly-N-p-nitrophenylpyrrole and the solid polymer electrolyte is preferably polyethylene oxide or polypropylene oxide.

Prototyping Energy Storage Components for Hybrid Power Source

DTIC Science & Technology

2009-12-11

from suitable nanoporous ceramic ( anodized aluminum oxide – AAO ) and polymer (polycarbonate - PC, polyethylene terephtalate - PET) membranes . Metal...of NUC technology: a) sketch of structure, b) SEM image of membrane . The alumina membranes can be easily and inexpensively fabricated via anodization ...of aluminum foil. The pores are formed by self-assembly via pitting and reprecipation of metal oxide . Motivation The work is motivated by the

Preparation of liquid-core nanocapsules from poly[(ethylene oxide)-co-glycidol] with multiple hydrophobic linoleates at an oil-water interface and its encapsulation of pyrene.

PubMed

Ren, Yong; Wang, Guowei; Huang, Junlian

2007-06-01

A convenient approach is provided to prepare liquid-core nanocapsules by cross-linking an amphiphilic copolymer at an oil-water interface. The hydrophilic copolymer poly[(ethylene oxide)-co-glycidol] was prepared by anionic polymerization of ethylene oxide and ethoxyethyl glycidyl ether first, then the hydroxyl groups on the backbone were recovered after hydrolysis and partly modified by hydrophobic conjugated linoleic acid. The copolymer with multiple linoleate pendants was absorbed at an oil-water interface and then cross-linked to form stable nanocapsules. The mean diameter of the nanocapsule was below 350 nm, and the size distribution was relatively narrow (<0.2) at low concentrations of oil in acetone (<10 mg/mL). The particle size could be tuned easily by variation of the emulsification conditions. The nanocapsule was stable in water for at least 5 months, and the shell maintained its integrity after removal of the oily core by solvent. Pyrene was encapsulated in these nanocapsules, and a loading efficiency as high as 94% was measured by UV spectroscopy.

Polyethylene glycol (PEG) assisted size-controlled SnO{sub 2} nanoparticles by sol-gel process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tripathi, P., E-mail: ptrip71@yahoo.com; Ahmed, Ateeq; Ali, Tinku

2016-05-23

Tetragonal phase tin oxide (SnO{sub 2}) nanoparticles have been synthesized by sol–gel method using SnCl{sub 4}.5H{sub 2}O and polyethylene glycol (PEG) of different concentration. The phase, size and purity of the final products are characterized by X-ray diffraction (XRD). The morphology is confirmed by scanning electron microscopy (SEM) analysis. There exists relationship between the concentration of PEG and particle size of SnO{sub 2} nanoparticles. Increase in concentration of PEG caused the reduction of particle size of tin oxide nanoparticles. The results suggest that the concentration of PEG plays a significant role in determining the size of SnO{sub 2} nanoparticles synthesizedmore » via this method. The optical property of the product has been explored by Ultraviolet (UV-visible) and Fourier Transform Infrared (FTIR) spectroscopic techniques.« less

Structural Evolution of Low-Molecular-Weight Poly(ethylene oxide)-block-polystyrene Diblock Copolymer Thin Film

PubMed Central

Huang, Xiaohua

2013-01-01

The structural evolution of low-molecular-weight poly(ethylene oxide)-block-polystyrene (PEO-b-PS) diblock copolymer thin film with various initial film thicknesses on silicon substrate under thermal annealing was investigated by atomic force microscopy, optical microscopy, and contact angle measurement. At film thickness below half of the interlamellar spacing of the diblock copolymer (6.2 nm), the entire silicon is covered by a polymer brush with PEO blocks anchored on the Si substrate due to the substrate-induced effect. When the film is thicker than 6.2 nm, a dense polymer brush which is equal to half of an interlamellar layer was formed on the silicon, while the excess material dewet this layer to form droplets. The droplet surface was rich with PS block and the PEO block crystallized inside the bigger droplet to form spherulite. PMID:24302862

Nanosized amorphous calcium carbonate stabilized by poly(ethylene oxide)-b-poly(acrylic acid) block copolymers.

PubMed

Guillemet, Baptiste; Faatz, Michael; Gröhn, Franziska; Wegner, Gerhard; Gnanou, Yves

2006-02-14

Particles of amorphous calcium carbonate (ACC), formed in situ from calcium chloride by the slow release of carbon dioxide by alkaline hydrolysis of dimethyl carbonate in water, are stabilized against coalescence in the presence of very small amounts of double hydrophilic block copolymers (DHBCs) composed of poly(ethylene oxide) (PEO) and poly(acrylic acid) (PAA) blocks. Under optimized conditions, spherical particles of ACC with diameters less than 100 nm and narrow size distribution are obtained at a concentration of only 3 ppm of PEO-b-PAA as additive. Equivalent triblock or star DHBCs are compared to diblock copolymers. The results are interpreted assuming an interaction of the PAA blocks with the surface of the liquid droplets of the concentrated CaCO3 phase, formed by phase separation from the initially homogeneous reaction mixture. The adsorption layer of the block copolymer protects the liquid precursor of ACC from coalescence and/or coagulation.

Fibrin-polyethylene oxide interpenetrating polymer networks: new self-supported biomaterials combining the properties of both protein gel and synthetic polymer.

PubMed

Akpalo, E; Bidault, L; Boissière, M; Vancaeyzeele, C; Fichet, O; Larreta-Garde, V

2011-06-01

Interpenetrating polymer network (IPN) architectures were conceived to improve the mechanical properties of a fibrin gel. Conditions allowing an enzymatic reaction to create one of the two networks in IPN architecture were included in the synthesis pathway. Two IPN series were carried out, starting from two polyethylene oxide (PEO) network precursors leading to different cross-linking densities of the PEO phase. The fibrin concentration varied from 5 to 20 wt.% in each series. The behavior of these materials during dehydration/hydration cycles was also studied. The mechanical properties of the resulting IPN were characterized in the wet and dry states. These self-supported biomaterials combine the properties of both a protein gel and a synthetic polymer. Finally, cells were grown on PEO/fibrin IPN, indicating that they are non-cytotoxic. Copyright © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

A dendrite-suppressing composite ion conductor from aramid nanofibres.

PubMed

Tung, Siu-On; Ho, Szushen; Yang, Ming; Zhang, Ruilin; Kotov, Nicholas A

2015-01-27

Dendrite growth threatens the safety of batteries by piercing the ion-transporting separators between the cathode and anode. Finding a dendrite-suppressing material that combines high modulus and high ionic conductance has long been considered a major technological and materials science challenge. Here we demonstrate that these properties can be attained in a composite made from Kevlar-derived aramid nanofibres assembled in a layer-by-layer manner with poly(ethylene oxide). Importantly, the porosity of the membranes is smaller than the growth area of the dendrites so that aramid nanofibres eliminate 'weak links' where the dendrites pierce the membranes. The aramid nanofibre network suppresses poly(ethylene oxide) crystallization detrimental for ion transport, giving a composite that exhibits high modulus, ionic conductivity, flexibility, ion flux rates and thermal stability. Successful suppression of hard copper dendrites by the composite ion conductor at extreme discharge conditions is demonstrated, thereby providing a new approach for the materials engineering of solid ion conductors.

Improved electrical conductivity of poly(ethylene oxide) nanofibers using multi-walled carbon nanotubes

NASA Astrophysics Data System (ADS)

Lee, J. Y.; Kang, T.-H.; Choi, J. H.; Choi, I.-S.; Yu, W.-R.

2018-03-01

Highly conductive nanofibers with 1570 S/m were obtained from an electrospun solution of polymer containing multiwalled carbon nanotubes (MWCNTs). Homogeneous dispersion of high concentrations of MWCNTs was achieved by attaching poly(styrenesulfonic acid graft aniline) (PSS-g-ANI), an amphiphilic surfactant, to the MWCNT surface. The hydrophilic sulfonic acid group facilitated the dissolution of PSS-g-ANI-grafted MWCNTs in a polyethylene oxide (PEO) solution up to 6.7 wt% MWCNT. To our knowledge, this is the highest level of MWCNT doping attained in a solution designed for electrospinning. With the incorporation of PSS-g-ANI, the concentration of MWCNTs embedded in the electrospun nanofibers increased. More importantly, the alignment of MWCNTs along the nanofiber axis increased significantly, as confirmed by observed birefringence under crossed polarizers. The combination of higher doping levels and better alignment afforded highly conductive nanofibers suitable for electronic nanodevices.

Effects of Silica Nanostructures in Poly(ethylene oxide)-Based Composite Polymer Electrolytes.

PubMed

Mohanta, Jagdeep; Anwar, Shahid; Si, Satyabrata

2016-06-01

The present work describes the synthesis of some poly(ethylene oxide)-based nanocomposite polymer electrolyte films using various silica nanostructures as the inorganic filler by simple solution mixing technique, in which the nature of the silica nanostructures play a vital role in modulating their electrochemical performances at room temperature. The silica nanostructures are prepared by ammonical hydrolysis of tetraethyl orthosilicate following the modified St6ber method. The resulting films are characterized by X-ray diffraction and differential scanning calorimeter to study their crystallinity. Room temperature AC impedance spectroscopy is utilized to determine the Li+ ion conductivity of the resulting films. The observed conductivity values of various NCPE films depend on the nature of silica filling as well as on their surface characteristics and also on the varying PEO-Li+ ratio, which is observed to be in the order of 10(-7)-10(-6) S cm(-1).

Fabricating metal-oxide-semiconductor field-effect transistors on a polyethylene terephthalate substrate by applying low-temperature layer transfer of a single-crystalline silicon layer by meniscus force

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sakaike, Kohei; Akazawa, Muneki; Nakamura, Shogo

2013-12-02

A low-temperature local-layer technique for transferring a single-crystalline silicon (c-Si) film by using a meniscus force was proposed, and an n-channel metal-oxide-semiconductor field-effect transistor (MOSFET) was fabricated on polyethylene terephthalate (PET) substrate. It was demonstrated that it is possible to transfer and form c-Si films in the required shape at the required position on PET substrates at extremely low temperatures by utilizing a meniscus force. The proposed technique for layer transfer was applied for fabricating high-performance c-Si MOSFETs on a PET substrate. The fabricated MOSFET showed a high on/off ratio of more than 10{sup 8} and a high field-effect mobilitymore » of 609 cm{sup 2} V{sup −1} s{sup −1}.« less

A Multicenter Approach Evaluating the Impact of Vitamin E-Blended Polyethylene in Cementless Total Hip Replacement

PubMed Central

Jäger, Marcus; van Wasen, Andrea; Warwas, Sebastian; Landgraeber, Stefan; Haversath, Marcel; Group, VITAS

2014-01-01

Since polyethylene is one of the most frequently used biomaterials as a liner in total hip arthroplasty, strong efforts have been made to improve design and material properties over the last 50 years. Antioxidants seems to be a promising alternative to further increase durability and reduce polyethylene wear in long term. As of yet, only in vitro results are available. While they are promising, there is yet no clinical evidence that the new material shows these advantages in vivo. To answer the question if vitamin-E enhanced ultra-high molecular weight polyethylene (UHMWPE) is able to improve long-term survivorship of cementless total hip arthroplasty we initiated a randomized long-term multicenter trial. Designed as a superiority study, the oxidation index assessed in retrieval analyses of explanted liners was chosen as primary parameter. Radiographic results (wear rate, osteolysis, radiolucency) and functional outcome (Harris Hip Scores, University of California-Los Angeles, Hip Disability and Osteoarthritis Outcome Score, Visual Analogue Scale) will serve as secondary parameters. Patients with the indication for a cementless total hip arthroplasty will be asked to participate in the study and will be randomized to either receive a standard hip replacement with a highly cross-linked UHMWPE-X liner or a highly cross-linked vitamin-E supplemented UHMWPE-XE liner. The follow-up will be 15 years, with evaluation after 5, 10 and 15 years. The controlled randomized study has been designed to determine if Vitamin-E supplemented highly cross-linked polyethylene liners are superior to standard XLPE liners in cementless total hip arthroplasty. While several studies have been started to evaluate the influence of vitamin-E, most of them evaluate wear rates and functional results. The approach used for this multicenter study, to analyze the oxidation status of retrieved implants, should make it possible to directly evaluate the ageing process and development of the implant material itself over a time period of 15 years. PMID:25002933

Does cyclic stress and accelerated ageing influence the wear behavior of highly crosslinked polyethylene?

PubMed

Affatato, Saverio; De Mattia, Jonathan Salvatore; Bracco, Pierangiola; Pavoni, Eleonora; Taddei, Paola

2016-06-01

First-generation (irradiated and remelted or annealed) and second-generation (irradiated and vitamin E blended or doped) highly crosslinked polyethylenes were introduced in the last decade to solve the problems of wear and osteolysis. In this study, the influence of the Vitamin-E addition on crosslinked polyethylene (XLPE_VE) was evaluated by comparing the in vitro wear behavior of crosslinked polyethylene (XLPE) versus Vitamin-E blended polyethylene XLPE and conventional ultra-high molecular weight polyethylene (STD_PE) acetabular cups, after accelerated ageing according to ASTM F2003-02 (70.0±0.1°C, pure oxygen at 5bar for 14 days). The test was performed using a hip joint simulator run for two millions cycles, under bovine calf serum as lubricant. Mass loss was found to decrease along the series XLPE_VE>STD_PE>XLPE, although no statistically significant differences were found between the mass losses of the three sets of cups. Micro-Raman spectroscopy was used to investigate at a molecular level the morphology changes induced by wear. The spectroscopic analyses showed that the accelerated ageing determined different wear mechanisms and molecular rearrangements during testing with regards to the changes in both the chain orientation and the distribution of the all-trans sequences within the orthorhombic, amorphous and third phases. The results of the present study showed that the addition of vitamin E was not effective to improve the gravimetric wear of PE after accelerated ageing. However, from a molecular point of view, the XLPE_VE acetabular cups tested after accelerated ageing appeared definitely less damaged than the STD_PE ones and comparable to XLPE samples. Copyright © 2016 Elsevier Ltd. All rights reserved.

Synthesis, Crystal Structure, and Magnetic Properties of the Linear-Chain Cobalt Oxide Sr 5Pb 3CoO 12

NASA Astrophysics Data System (ADS)

Yamaura, K.; Huang, Q.; Takayama-Muromachi, E.

2002-02-01

The novel spin-chain cobalt oxide Sr5Pb3CoO12 [Poverline6×2m, a=10.1093(2) Å and c=3.562 51(9) Å at 295 K] is reported. A polycrystalline sample of the compound was studied by neutron diffraction (at 6 and 295 K) and magnetic susceptibility measurements (5 to 390 K). The cobalt oxide was found to be analogous to the copper oxide Sr5Pb3CuO12, which is comprised of magnetic-linear chains at an interchain distance of 10 Å. Although the cobalt oxide chains (μeff of 3.64 μB per Co) are substantially antiferromagnetic (θW=-38.8 K), neither low-dimensional magnetism nor long-range ordering has been found; a local-structure disorder in the chains might have an impact on the magnetism. This compound is highly electrically insulating.

Deformation sensor based on polymer-supported discontinuous graphene multi-layer coatings

NASA Astrophysics Data System (ADS)

Carotenuto, G.; Schiavo, L.; Romeo, V.; Nicolais, L.

2014-05-01

Graphene can be conveniently used in the modification of polymer surfaces. Graphene macromolecules are perfectly transparent to the visible light and electrically conductive, consequently these two properties can be simultaneously provided to polymeric substrates by surface coating with thin graphene layers. In addition, such coating process provides the substrates of: water-repellence, higher surface hardness, low-friction, self-lubrication, gas-barrier properties, and many other functionalities. Polyolefins have a non-polar nature and therefore graphene strongly sticks on their surface. Nano-crystalline graphite can be used as graphene precursor in some chemical processes (e.g., graphite oxide synthesis by the Hummer method), in addition it can be directly applied to the surface of a polyolefin substrate (e.g., polyethylene) to cover it by a thin graphene multilayer. In particular, the nano-crystalline graphite perfectly exfoliate under the application of a combination of shear and friction forces and the produced graphene single-layers perfectly spread and adhere on the polyethylene substrate surface. Such polymeric materials can be used as ITO (indium-tin oxide) substitute and in the fabrication of different electronic devices. Here the fabrication of transparent resistive deformation sensors based on low-density polyethylene films coated by graphene multilayers is described. Such devices are very sensible and show a high reversible and reproducible behavior.

Rapid assessment of oxidation via middle-down LCMS correlates with methionine side-chain solvent-accessible surface area for 121 clinical stage monoclonal antibodies.

PubMed

Yang, Rong; Jain, Tushar; Lynaugh, Heather; Nobrega, R Paul; Lu, Xiaojun; Boland, Todd; Burnina, Irina; Sun, Tingwan; Caffry, Isabelle; Brown, Michael; Zhi, Xiaoyong; Lilov, Asparouh; Xu, Yingda

Susceptibility of methionine to oxidation is an important concern for chemical stability during the development of a monoclonal antibody (mAb) therapeutic. To minimize downstream risks, leading candidates are usually screened under forced oxidation conditions to identify oxidation-labile molecules. Here we report results of forced oxidation on a large set of in-house expressed and purified mAbs with variable region sequences corresponding to 121 clinical stage mAbs. These mAb samples were treated with 0.1% H 2 O 2 for 24 hours before enzymatic cleavage below the hinge, followed by reduction of inter-chain disulfide bonds for the detection of the light chain, Fab portion of heavy chain (Fd) and Fc by liquid chromatography-mass spectrometry. This high-throughput, middle-down approach allows detection of oxidation site(s) at the resolution of 3 distinct segments. The experimental oxidation data correlates well with theoretical predictions based on the solvent-accessible surface area of the methionine side-chains within these segments. These results validate the use of upstream computational modeling to predict mAb oxidation susceptibility at the sequence level.

Preparation of Hybrid Nanoparticle Nucleating Agents and Their Effects on the Crystallization Behavior of Poly(ethylene terephthalate)

PubMed Central

Han, Zhenzhen; Wang, Yao; Wang, Jiuxing; Wang, Shichao; Zhuang, Hongwei; Liu, Jixian; Huang, Linjun; Wang, Yanxin; Wang, Wei; Belfiore, Laurence A.; Tang, Jianguo

2018-01-01

In this research contribution, the primary objective was to enhance the crystallization behavior of poly(ethylene terephthalate) (PET). To accomplish this tack, three kinds of new nucleating agents SiO2-diethylene glycol-LMPET (PET-3), SiO2-triethylene glycol–LMPET(PET-4) and SiO2-tetraethylene glycol-LMPET (PET-5) nucleating agents were prepared via grafting different oligomers (diethylene glycol; triethylene glycol and tetraethylene glycol) to the surface of nano-SiO2 and then linking to the low molecular weight poly(ethylene terephthalate) (LMPET). These nano-particle nucleating agents facilitated the crystallization of PET. Differential scanning calorimetry (DSC) studies of the composites that pure PET blended with PET-3, PET-4 and PET-5 indicated that the longer ethoxy segment in the nucleating agents exhibited (i) higher degrees of crystallinity; (ii) faster rates of crystallization; and (iii) higher crystallization temperatures. The Jeziorny method was employed to analyze the non-isothermal crystallization kinetics of the composites. These works demonstrated that the PET-3, PET-4 and PET-5 were attractive nucleating agents for poly(ethylene terephthalate), and the longer the chain length of the ethoxy segment in the nucleating agents, the more efficient the nucleation effect. PMID:29641456

Structural and optical properties of Ag-doped copper oxide thin films on polyethylene napthalate substrate prepared by low temperature microwave annealing

NASA Astrophysics Data System (ADS)

Das, Sayantan; Alford, T. L.

2013-06-01

Silver doped cupric oxide thin films are prepared on polyethylene naphthalate (flexible polymer) substrates. Thin films Ag-doped CuO are deposited on the substrate by co-sputtering followed by microwave assisted oxidation of the metal films. The low temperature tolerance of the polymer substrates led to the search for innovative low temperature processing techniques. Cupric oxide is a p-type semiconductor with an indirect band gap and is used as selective absorption layer solar cells. X-ray diffraction identifies the CuO phases. Rutherford backscattering spectrometry measurements confirm the stoichiometry of each copper oxide formed. The surface morphology is determined by atomic force microscopy. The microstructural properties such as crystallite size and the microstrain for (-111) and (111) planes are calculated and discussed. Incorporation of Ag led to the lowering of band gap in CuO. Consequently, it is determined that Ag addition has a strong effect on the structural, morphological, surface, and optical properties of CuO grown on flexible substrates by microwave annealing. Tauc's plot is used to determine the optical band gap of CuO and Ag doped CuO films. The values of the indirect and direct band gap for CuO are found to be 2.02 eV and 3.19 eV, respectively.

The in vitro kinetics of the interactions between PEG-ylated magnetic-fluid-loaded liposomes and macrophages.

PubMed

Martina, Marie-Sophie; Nicolas, Valerie; Wilhelm, Claire; Ménager, Christine; Barratt, Gillian; Lesieur, Sylviane

2007-10-01

Binding and uptake kinetics of magnetic-fluid-loaded liposomes (MFL) by endocytotic cells were investigated in vitro on the model cell-line J774. MFL consisted of unilamellar phosphatidylcholine vesicles (mean hydrodynamic diameter close to 200nm) encapsulating 8-nm nanocrystals of maghemite (gamma-Fe(2)O(3)) and sterically stabilized by introducing 5mol% of distearylphosphatidylcholine poly(ethylene glycol)(2,000) (DSPE-PEG(2,000)) in the vesicle bilayer. The association processes with living macrophages were followed at two levels. On one hand, the lipid vesicles were imaged by confocal fluorescence microscopy. For this purpose 1mol% of rhodamine-marked phosphatidylethanolamine was added to the liposome composition. On the other hand, the iron oxide particles associated with cells were independently quantified by magnetophoresis. All the experiments were similarly performed with PEG-ylated or conventional MFL to point out the role of polymer coating. The results showed cell association with both types of liposomes resulting from binding followed by endocytosis. Steric stabilization by PEG chains reduced binding efficiency limiting the amount of MFL internalized by the macrophages. In contrast, PEG coating did not change the kinetics of endocytosis which exhibited the same first-order rate constant for both conventional and PEG-ylated liposomes. Moreover, lipids and iron oxide particle uptakes were perfectly correlated, indicating that MFL vesicle structure and encapsulation rate were preserved upon cell penetration.

Polymer dynamics under nanoscopic constraints: the "corset effect" as revealed by NMR relaxometry and diffusometry.

PubMed

Fatkullin, Nail; Fischer, Elmar; Mattea, Carlos; Beginn, Uwe; Kimmich, Rainer

2004-06-21

A spinodal demixing technique was employed for the preparation of linear poly(ethylene oxide) (PEO) confined in nanoscopic strands, which in turn are embedded in a quasi-solid methacrylate matrix impenetrable to PEO. Both the molecular weight of the PEO and the mean diameter of the strands are variable to a certain degree. Chain dynamics of the PEO in the molten state were examined with the aid of field-gradient NMR diffusometry and field-cycling NMR relaxometry. The dominating mechanism for translational displacements in the nanoscopic strands is shown to be reptation. A formalism for the evaluation of NMR diffusometry is presented, which permits the estimation of the mean PEO strand diameter. Samples of different composition revealed diameters in the range 9-58 nm, in reasonable agreement with electron micrographs. The time scale of the diffusion measurements was 10-300 ms. On the much shorter time scale of field-cycling NMR relaxometry, 10(-9)-10(-4)s, a frequency dispersion of the spin-lattice relaxation time characteristic for reptation clearly showed up in all samples. An effective tube diameter of only 0.6 nm was found even when the strand diameter was larger than the radius of gyration of the PEO chain random coils. The finding that the tube diameter effective on the short time scale of field-cycling NMR relaxometry is much smaller than the diameter of the confining structure is termed the "corset effect", and is traced back to the lack of local free-volume fluctuation capacity under nanoscale confinements. The order of magnitude of the 'pore' diameter, at which the cross-over from confined to bulk chain dynamics is expected, is estimated.

Simulation study of the lithium ion transport mechanism in ternary polymer electrolytes: the critical role of the segmental mobility.

PubMed

Diddens, Diddo; Heuer, Andreas

2014-01-30

We present an extensive molecular dynamics (MD) simulation study of the lithium ion transport in ternary polymer electrolytes consisting of poly(ethylene oxide) (PEO), lithium-bis(trifluoromethane)sulfonimide (LiTFSI), and the ionic liquid N-methyl-N-propylpyrrolidinium bis(trifluoromethane)sulfonimide (PYR13TFSI). In particular, we focus on two different strategies by which the ternary electrolytes can be devised, namely by (a) adding the ionic liquid to PEO20LiTFSI and (b) substituting the PEO chains in PEO20LiTFSI by the ionic liquid. To grasp the changes of the overall lithium transport mechanism, we employ an analytical, Rouse-based cation transport model (Maitra et al. Phys. Rev. Lett. 2007, 98, 227802), which has originally been devised for binary PEO-based electrolytes. This model distinguishes three different microscopic transport mechanisms, each quantified by an individual time scale. In the course of our analysis, we extend this mathematical description to account for an entirely new transport mechanism, namely, the TFSI-supported diffusion of lithium ions decoupled from the PEO chains, which emerges for certain stoichiometries. We find that the segmental mobility plays a decisive role in PEO-based polymer electrolytes. That is, whereas the addition of the ionic liquid to PEO20LiTFSI plasticizes the polymer network and thus also increases the lithium diffusion, the amount of free, mobile ether oxygens reduces when substituting the PEO chains by the ionic liquid, which compensates the plasticizing effect. In total, our observations allow us to formulate some general principles about the lithium ion transport mechanism in ternary polymer electrolytes. Moreover, our insights also shed light on recent experimental observations (Joost et al. Electrochim. Acta 2012, 86, 330).

Physical properties of aqueous solutions of a thermo-responsive neutral copolymer and an anionic surfactant: turbidity and small-angle neutron scattering studies.

PubMed

Galant, Céline; Kjøniksen, Anna-Lena; Knudsen, Kenneth D; Helgesen, Geir; Lund, Reidar; Laukkanen, Antti; Tenhu, Heikki; Nyström, Bo

2005-08-16

Aqueous mixtures of the anionic sodium dodecyl sulfate (SDS) surfactant and thermo-responsive poly(N-vinylcaprolactam) chains grafted with omega-methoxy poly(ethylene oxide) undecyl alpha-methacrylate (PVCL-g-C11EO42) have been characterized using turbidimetry and small-angle neutron scattering (SANS). Turbidity measurements show that the addition of SDS to a dilute aqueous copolymer solution (1.0 wt %) induces an increase of the cloud point (CP) value and a decrease of the turbidity at high temperatures. In parallel, SANS results show a decrease of both the average distance between chains and the global size of the objects in solution at high temperatures as the SDS concentration is increased. Combination of these findings reveals that the presence of SDS in the PVCL-g-C11EO42 solutions (1.0 wt %) promotes the formation of smaller aggregates and, consequently, leads to a more homogeneous distribution of the chains in solution upon heating of the mixtures. Moreover, the SANS data results show that the internal structure of the formed aggregates becomes more swollen as the SDS concentration increases. On the other hand, the addition of moderate amounts of SDS (up to 4 mm) to a semidilute copolymer solution (5.0 wt %) gives rise to a more pronounced aggregation as the temperature rises; turbidity and SANS studies reveal in this case a decrease of the CP value and an increase of the scattered intensity at low q. The overall picture that emerges from this study is that the degree of aggregation can be accurately tuned by varying parameters such as the temperature, level of surfactant addition, and polymer concentration.

Structure and dynamics of water in nonionic reverse micelles: a combined time-resolved infrared and small angle x-ray scattering study.

PubMed

van der Loop, Tibert H; Panman, Matthijs R; Lotze, Stephan; Zhang, Jing; Vad, Thomas; Bakker, Huib J; Sager, Wiebke F C; Woutersen, Sander

2012-07-28

We study the structure and reorientation dynamics of nanometer-sized water droplets inside nonionic reverse micelles (water/Igepal-CO-520/cyclohexane) with time-resolved mid-infrared pump-probe spectroscopy and small angle x-ray scattering. In the time-resolved experiments, we probe the vibrational and orientational dynamics of the O-D bonds of dilute HDO:H(2)O mixtures in Igepal reverse micelles as a function of temperature and micelle size. We find that even small micelles contain a large fraction of water that reorients at the same rate as water in the bulk, which indicates that the polyethylene oxide chains of the surfactant do not penetrate into the water volume. We also observe that the confinement affects the reorientation dynamics of only the first hydration layer. From the temperature dependent surface-water dynamics, we estimate an activation enthalpy for reorientation of 45 ± 9 kJ mol(-1) (11 ± 2 kcal mol(-1)), which is close to the activation energy of the reorientation of water molecules in ice.

Structure of block copolymer micelles in the presence of co-solvents

NASA Astrophysics Data System (ADS)

Robertson, Megan; Wang, Shu; Le, Kim Mai; Piemonte, Rachele; Madsen, Louis

2015-03-01

Amphiphilic block copolymer micelles in water are under broad exploration for drug delivery applications due to their high loading capacity and targeted drug delivery. We aim to understand the kinetic and thermodynamic processes that underlie the self-assembly of diblock copolymer micelle systems. The present work focuses on diblock copolymers containing poly(ethylene oxide) (a hydrophilic polymer) and polycaprolactone (a hydrophobic polymer), which spontaneously self-assemble into spherical micelles in water. Addition of a common good solvent (a co-solvent) for both of the constituting blocks, such as tetrahydrofuran (THF), reduces the interfacial tension at the core-corona interface. We are currently investigating the effect of this phenomenon on the micelle structural properties, using scattering experiments and nuclear magnetic resonance. We have characterized the hydrodynamic radius, core radius, corona thickness, aggregation number, degree of swelling of the micelle core with the co-solvent, and unimer (free chain) concentration, as a function of the co-solvent concentration. Fundamental knowledge from these studies will inform design of drug delivery systems by allowing us to tailor micelle properties for optimal cargo loading.

Generation of Well-Relaxed All-Atom Models of Large Molecular Weight Polymer Melts: A Hybrid Particle-Continuum Approach Based on Particle-Field Molecular Dynamics Simulations.

PubMed

De Nicola, Antonio; Kawakatsu, Toshihiro; Milano, Giuseppe

2014-12-09

A procedure based on Molecular Dynamics (MD) simulations employing soft potentials derived from self-consistent field (SCF) theory (named MD-SCF) able to generate well-relaxed all-atom structures of polymer melts is proposed. All-atom structures having structural correlations indistinguishable from ones obtained by long MD relaxations have been obtained for poly(methyl methacrylate) (PMMA) and poly(ethylene oxide) (PEO) melts. The proposed procedure leads to computational costs mainly related on system size rather than to the chain length. Several advantages of the proposed procedure over current coarse-graining/reverse mapping strategies are apparent. No parametrization is needed to generate relaxed structures of different polymers at different scales or resolutions. There is no need for special algorithms or back-mapping schemes to change the resolution of the models. This characteristic makes the procedure general and its extension to other polymer architectures straightforward. A similar procedure can be easily extended to the generation of all-atom structures of block copolymer melts and polymer nanocomposites.

Force fields for describing the solution-phase synthesis of shape-selective metal nanoparticles

NASA Astrophysics Data System (ADS)

Zhou, Ya; Al-Saidi, Wissam; Fichthorn, Kristen

2013-03-01

Polyvinylpyrrolidone (PVP) and polyethylene oxide (PEO) are structure-directing agents that exhibit different performance in the polyol synthesis of Ag nanostructures. The success of these structure-directing agents in selective nanostructure synthesis is often attributed to their selective binding to Ag(100) facets. We use first-principles, density-functional theory (DFT) calculations in a vacuum environment to show that PVP has a stronger preference to bind to Ag(100) than to Ag(111), whereas PEO exhibits much weaker selectivity. To understand the role of solvent in the surface-sensitive binding, we develop classical force fields to describe the interactions of the structure-directing (PVP and PEO) and solvent (ethylene glycol) molecules with various Ag substrates. We parameterize the force fields through force-and-energy matching to DFT results using simulated annealing. We validate the force fields by comparisons to DFT and experimental binding energies. Our force fields reproduce the surface-sensitive binding predicted by DFT calculations. Molecular dynamics simulations based on these force fields can be used to reveal the role of solvent, polymer chain length, and polymer concentration in the selective synthesis of Ag nanostructures.

Nanoporous Films with Sub-10 nm in Pore Size from Acid-Cleavable Block Copolymers.

PubMed

Li, Yayuan; Xu, Yawei; Cao, Shubo; Zhao, Yongbin; Qu, Ting; Iyoda, Tomokazu; Chen, Aihua

2017-03-01

Nanoporous thin films with pore size of sub-10 nm are fabricated using an acid-cleavable block copolymer (BCP), a benzoic imine junction between poly(ethylene oxide) (PEO) and poly(methacrylate) (PMAAz) bearing an azobenzene side chain (denoted as PEO-bei-PMAAz) as the precursor. After a thermal annealing, the block copolymers are self-assembled to form highly ordered PEO cylinders within a PMAAz matrix normal to the film, even in the case of low BCP molecular weight due to the existing of the liquid crystalline (LC) azobenzene rigid segment. Thus, PMAAz thin films with pore size of ≈7 nm and density of ≈10 12 cm -2 are obtained after removal of the PEO minor phase by breaking the benzoic imine junction under mild acidic conditions. This work enriches the nanoporous polymer films from BCP precursors and introduces the LC property as a functionality which can further enhance the mechanical properties of the films and broaden their applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of organic silicon compounds as additives on charge-discharge cycling efficiencies of lithium in nonaqueous electrolytes for rechargeable lithium cells

NASA Astrophysics Data System (ADS)

Yanagisawa, Ryota; Endo, Hisayuki; Unno, Masafumi; Morimoto, Hideyuki; Tobishima, Shin-ichi

2014-11-01

Influence of mixing organic silicon compounds into 1 M (M: mol L-1) LiPF6-ethylene carbonate (EC)/ethylmethyl carbonate (EMC) (mixing volume ratio = 3:7) mixed solvent electrolytes on charge-discharge cycling efficiencies of lithium metal negative electrodes is examined. As organic silicon compounds, polyether-modified siloxanes with polyethylene oxide chains, chlorotrimethylsilane, tetraethoxysilane, cis-tetra [isobutyl (dimethylsiloxy)] cyclotetrasiloxane and cage-type silsesquioxane are investigated. Charge-discharge cycling tests of lithium are galvanostatically carried out using stainless steel working electrodes. Charge-discharge cycling efficiencies of lithium tend to improve by mixing organic silicon compounds. A cage-type silsesquioxane, octaphenyloctasilsesquioxane (Ph8T8) exhibits the highest cycling efficiency of approximately 80% with small mixing amount of 0.02 M Ph8T8. Mechanism of enhancement of lithium cycling efficiencies by mixing organic silicon compounds is considered to be due to the suppression of excess reduction of LiPF6-EC/EMC by lithium and the growth of surface film on lithium.

From the N-Heterocyclic Carbene-Catalyzed Conjugate Addition of Alcohols to the Controlled Polymerization of (Meth)acrylates.

PubMed

Ottou, Winnie Nzahou; Bourichon, Damien; Vignolle, Joan; Wirotius, Anne-Laure; Robert, Fredéric; Landais, Yannick; Sotiropoulos, Jean-Marc; Miqueu, Karinne; Taton, Daniel

2015-06-22

Among various N-heterocyclic carbenes (NHCs) tested, only 1,3-bis(tert-butyl)imidazol-2-ylidene (NHC(tBu) ) proved to selectively promote the catalytic conjugate addition of alcohols onto (meth)acrylate substrates. This rather rare example of NHC-catalyzed 1,4-addition of alcohols was investigated as a simple means to trigger the polymerization of both methyl methacrylate and methyl acrylate (MMA and MA, respectively). Well-defined α-alkoxy poly(methyl (meth)acrylate) (PM(M)A) chains, the molar masses of which could be controlled by the initial [(meth)acrylate]0/[ROH]0 molar ratio, were ultimately obtained in N,N-dimethylformamide at 25 °C. A hydroxyl-terminated poly(ethylene oxide) (PEO-OH) macro-initiator was also employed to directly access PEO-b-PMMA amphiphilic block copolymers. Investigations into the reaction mechanism by DFT calculations revealed the occurrence of two competitive concerted pathways, involving either the activation of the alcohol or that of the monomer by NHC(tBu) . © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influencing the structure of block copolymer micelles with small molecule additives

NASA Astrophysics Data System (ADS)

Robertson, Megan; Singh, Avantika; Cooksey, Tyler; Kidd, Bryce; Piemonte, Rachele; Wang, Shu; Mai Le, Kim; Madsen, Louis

Amphiphilic block copolymer micelles in water are under broad exploration for drug delivery applications due to their high loading capacity and targeted drug delivery. We aim to understand the kinetic and thermodynamic processes that underlie the self-assembly of diblock copolymer micelle systems. The present work focuses on diblock copolymers containing poly(ethylene oxide) (a hydrophilic polymer) and polycaprolactone (a hydrophobic polymer), which spontaneously self-assemble into spherical micelles in water. Addition of a common good solvent (a co-solvent) for both of the constituting blocks, such as tetrahydrofuran (THF), reduces the interfacial tension at the core-corona interface. We are currently investigating the effect of this phenomenon on the micelle structural properties, using small-angle scattering and nuclear magnetic resonance. We have characterized the hydrodynamic radius, core radius, corona thickness, aggregation number, degree of swelling of the micelle core with the co-solvent, and unimer (free chain) concentration, as a function of the co-solvent concentration. Fundamental knowledge from these studies will inform design of drug delivery systems by allowing us to tailor micelle properties for optimal cargo loading.

Highly stable multi-anchored magnetic nanoparticles for optical imaging within biofilms

DOE PAGES

Stone, R. C.; Fellows, B. D.; Qi, B.; ...

2015-08-05

Magnetic nanoparticles are the next tool in medical diagnoses and treatment in many different biomedical applications, including magnetic hyperthermia as alternative treatment for cancer and bacterial infections, as well as the disruption of biofilms. The colloidal stability of the magnetic nanoparticles in a biological environment is crucial for efficient delivery. A surface that can be easily modifiable can also improve the delivery and imaging properties of the magnetic nanoparticle by adding targeting and imaging moieties, providing a platform for additional modification. The strategy presented in this paper includes multiple nitroDOPA anchors for robust binding to the surface tied to themore » same polymer backbone as multiple poly(ethylene oxide) chains for steric stability. This approach provides biocompatibility and enhanced stability in fetal bovine serum (FBS) and phosphate buffer saline (PBS). As a proof of concept, these polymer-particles complexes were then modified with a near infrared dye and utilized in characterizing the integration of magnetic nanoparticles in biofilms. Finally, the work presented in this manuscript describes the synthesis and characterization of a nontoxic platform for the labeling of near IR-dyes for bioimaging.« less

Controlling domain orientation of liquid crystalline block copolymer in thin films through tuning mesogenic chemical structures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xie, He-Lou; Li, Xiao; Ren, Jiaxing

Controlling the macroscopic orientation of nanoscale periodic structures of amphiphilic liquid crystalline block copolymers (LC BCPs) is important to a variety of technical applications (e.g., lithium conducting polymer electrolytes). To study LC BCP domain orientation, a series of LC BCPs containing a poly(ethylene oxide) (PEO) block as a conventional hydrophilic coil block and LC blocks containing azobenzene mesogens is designed and synthesized. LC ordering in thin films of the BCP leads to the formation of highly ordered, microphase-separated nanostructures, with hexagonally arranged PEO cylinders. Substitution on the tail of the azobenzene mesogen is shown to control the orientation of themore » PEO cylinders. When the substitution on the mesogenic tails is an alkyl chain, the PEO cylinders have a perpendicular orientation to the substrate surface, provided the thin film is above a critical thickness value. In contrast, when the substitution on the mesogenic tails has an ether group the PEO cylinders assemble parallel to the substrate surface regardless of the film thickness value.« less

Soft and flexible poly(ethylene glycol) nanotubes for local drug delivery.

PubMed

Newland, B; Taplan, C; Pette, D; Friedrichs, J; Steinhart, M; Wang, W; Voit, B; Seib, F P; Werner, C

2018-05-10

Nanotubes are emerging as promising materials for healthcare applications but the selection of clinically relevant starting materials for their synthesis remains largely unexplored. Here we present, for the first time, the synthesis of poly(ethylene glycol) (PEG) based nanotubes via the photopolymerization of poly(ethylene glycol) diacrylate and other diacrylate derivatives within the pores of anodized aluminum oxide templates. Template-assisted synthesis allowed the manufacture of a diverse set of polymeric nanotubes with tunable physical characteristics including diameter (∼200-400 nm) and stiffness (405-902 kPa). PEG nanotubes were subjected to cytotoxicty assessment in cell lines and primary stem cells and showed excellent cytocompatability (IC50 > 120 μg ml-1). Nanotubes were readily drug loaded but released the majority of the drug over 5 days. Direct administration of drug loaded nanotubes to human orthotopic breast tumors substantially reduced tumor growth and metastasis and outperformed i.v. administration at the equivalent dose. Overall, this nanotube templating platform is emerging as a facile route for the manufacture of poly(ethylene glycol) nanotubes.

Unique plasma metabolomic signatures of individuals with inherited disorders of long-chain fatty acid oxidation

USDA-ARS?s Scientific Manuscript database

Blood and urine acylcarnitine profiles are commonly used to diagnose long-chain fatty acid oxidation disorders (FAOD: i.e., long-chain hydroxy-acyl-CoA dehydrogenase [LCHAD] and carnitine palmitoyltransferase 2 [CPT2] deficiency), but the global metabolic impact of long-chain FAOD has not been repor...

Aspirin increases mitochondrial fatty acid oxidation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Uppala, Radha; Dudiak, Brianne; Beck, Megan E.

The metabolic effects of salicylates are poorly understood. This study investigated the effects of aspirin on fatty acid oxidation. Aspirin increased mitochondrial long-chain fatty acid oxidation, but inhibited peroxisomal fatty acid oxidation, in two different cell lines. Aspirin increased mitochondrial protein acetylation and was found to be a stronger acetylating agent in vitro than acetyl-CoA. However, aspirin-induced acetylation did not alter the activity of fatty acid oxidation proteins, and knocking out the mitochondrial deacetylase SIRT3 did not affect the induction of long-chain fatty acid oxidation by aspirin. Aspirin did not change oxidation of medium-chain fatty acids, which can freely traverse themore » mitochondrial membrane. Together, these data indicate that aspirin does not directly alter mitochondrial matrix fatty acid oxidation enzymes, but most likely exerts its effects at the level of long-chain fatty acid transport into mitochondria. The drive on mitochondrial fatty acid oxidation may be a compensatory response to altered mitochondrial morphology and inhibited electron transport chain function, both of which were observed after 24 h incubation of cells with aspirin. These studies provide insight into the pathophysiology of Reye Syndrome, which is known to be triggered by aspirin ingestion in patients with fatty acid oxidation disorders. - Highlights: • Aspirin increases mitochondrial—but inhibits peroxisomal—fatty acid oxidation. • Aspirin acetylates mitochondrial proteins including fatty acid oxidation enzymes. • SIRT3 does not influence the effect of aspirin on fatty acid oxidation. • Increased fatty acid oxidation is likely due to altered mitochondrial morphology and respiration.« less

Polymer blends for use in photoelectrochemical cells for conversion of solar energy to electricity and methods for manufacturing such blends

DOEpatents

Skotheim, T.

A polymer blend is disclosed of a highly conductive polymer and a solid polymer electrolyte that is designed to achieve better charge transfer across the conductive film/polymer electrolyte interface of the electrochemical photovoltaic cell. The highly conductive polymer is preferably polypyrrole or poly-N-p-nitrophenylpyrrole and the solid polymer electrolyte is preferably polyethylene oxide or polypropylene oxide.

A Combination Tissue Engineering Strategy for Schwann Cell-Induced Spinal Cord Repair

DTIC Science & Technology

2016-10-01

block copolymer consisting of polyethylene oxide (PEO) and polypropylene oxide (PPO). It has thermoreversible gelation properties when used at...high; Zeus Inc., Orangeburg, SC) were placed on top of the aligned and random fibrous PVDF-TrFE disks in 96-well polypropylene plates to prevent them...2011. Preparation of spinal cord injured tissue for light and electron microscopy including preparation for immunostaining. In: Lane LE , Dunnett BS

In vivo degradation in modern orthopaedic UHMWPE bearings and structural characterization of a novel alternative UHMWPE material

NASA Astrophysics Data System (ADS)

Reinitz, Steven D.

Ultra-high molecular weight polyethylene (UHMWPE) remains the most common bearing material for total joint arthroplasty. Advances in radiation cross-linking and other post-consolidation treatments have led to a rapid differentiation of polyethylene products on the market, with more than twenty unique materials currently being sold by the five largest orthopaedic manufacturers alone. Through oxidation, cross-link density, and free radical measurements, this work demonstrates for the first time that in vivo material degradation is occurring in cross-linked UHMWPE materials. Based on the rate of the reaction in certain materials, it is concluded that oxidative degradation may compromise the mechanical properties of the bearings in as few as ten years, potentially leading to early clinical failure of the devices. Using the knowledge gained from this work as well as previously published observations about UHMWPE oxidation, a two-mechanism model of oxidation is proposed that offers an explanation for the observed in vivo changes. From this model it is concluded that oxidative degradation is in part the result of in vivo chemical species. The two-mechanism model of oxidation suggests that different processing techniques for UHMWPE may reduce the risk of oxidative degradation. It is concluded that by avoiding any radiation cross-linking step, Equal Channel Angular Processing (ECAP) can produce UHMWPE materials with a reduced risk for in vivo oxidation while at the same time offering superior mechanical properties compared to commercially available UHMWPE materials, as well as similar wear behavior. Using dynamic mechanical analysis, the entanglement density in ECAP materials is quantified, and is related back to the ECAP processing parameters. The relationship between entanglement density and resultant material properties is established. The results will allow informed processing parameter selection for producing optimized materials for orthopaedics and other applications.

Synthesis of high molecular weight PEO using non-metal initiators

DOEpatents

Yang, Jin; Sivanandan, Kulandaivelu; Pistorino, Jonathan; Eitouni, Hany Basam

2015-05-19

A new synthetic method to prepare high molecular weight poly(ethylene oxide) with a very narrow molecular weight distribution (PDI<1.5) is described. The method involves a metal free initiator system, thus avoiding dangerous, flammable organometallic compounds.

Polymer/graphite oxide composites as high-performance materials for electric double layer capacitors

NASA Astrophysics Data System (ADS)

Tien, Chien-Pin; Teng, Hsisheng

A single graphene sheet represents a carbon material with the highest surface area available to accommodating molecules or ions for physical and chemical interactions. Here we demonstrate in an electric double layer capacitor the outstanding performance of graphite oxide for providing a platform for double layer formation. Graphite oxide is generally the intermediate compound for obtaining separated graphene sheets. Instead of reduction with hydrazine, we incorporate graphite oxide with a poly(ethylene oxide)-based polymer and anchor the graphene oxide sheets with poly(propylene oxide) diamines. This polymer/graphite oxide composite shows in a "dry" gel-electrolyte system a double layer capacitance as high as 130 F g -1. The polymer incorporation developed here can significantly diversify the application of graphene-based materials in energy storage devices.

Modelling of photodegradation in solar cell modules of substrate and superstrate design made with ethylene-vinyl acetate as pottant material

NASA Technical Reports Server (NTRS)

Somersall, A. C.; Guillet, J. E.

1983-01-01

A computer model was developed which can generate realistic concentration versus time profiles of the chemical species formed during photooxidation of hydrocarbon polymers using as input data a set of elementary reactions with corresponding rate constants and initial conditions. The results of computer simulation have been shown to be consistent with the general experimental observations of the photooxidation of polyethylene exposed to sunlight at ambient temperatures. The useful lifetime (5% oxidation) of the unstabilized polyethylene is predicted to vary from a few months in hot weather (100 F) to almost two years in cool weather (45 F) with an apparent net activation energy of 10 kcal/mol. Modelling studies of alternate mechanisms for stabilization of clear, amorphous, linear polyethylene suggest that the optimum stabilizer would be a molecularly dispensed additive in very low concentration which can trap peroxy radicals and also decompose hydroperoxides.

Synthesis and self-assembly of four-armed star copolymer based on poly(ethylene brassylate) hydrophobic block as potential drug carries

NASA Astrophysics Data System (ADS)

Chen, Jiucun; Li, Junzhi; Liu, Jianhua; Weng, Bo; Xu, Liqun

2016-05-01

A novel well-defined four-armed star poly(ethylene brassylate)- b-poly(poly(ethylene glycol)methyl ether methacrylate) (s-PEB- b-P(PEGMA)) was synthesized and self-assembled via the combination of ring-opening polymerization and reversible addition-fragmentation chain transfer polymerization (RAFT) in this work. It proceeded firstly with the synthesis of hydrophobic four-armed star homopolymer of ethylene brassylate (EB) via ROP with organic catalyst, followed by the esterification reaction of s-PEB with chain transfer agent. Afterward, RAFT polymerization of PEGMA monomer was initialed using PEB-based macro-RAFT agent, resulting in the target amphiphilic four-armed star copolymer. The obtained s-PEB- b-P(PEGMA) can assemble into micelles with PEB segments as core and P(PEGMA) segments as shell in aqueous solution. The self-assembly behavior was studied by dynamic light scattering and transmission electron microscope. The micelles of s-PEB- b-P(PEGMA) exhibited higher loading capacity of the anticancer drug doxorubicin (DOX). The investigation of DOX release from the micelles demonstrated that the release rate of the hydrophobic drug could be effectively controlled.

Multiscale approach for the construction of equilibrated all-atom models of a poly(ethylene glycol)-based hydrogel

PubMed Central

Li, Xianfeng; Murthy, N. Sanjeeva; Becker, Matthew L.; Latour, Robert A.

2016-01-01

A multiscale modeling approach is presented for the efficient construction of an equilibrated all-atom model of a cross-linked poly(ethylene glycol) (PEG)-based hydrogel using the all-atom polymer consistent force field (PCFF). The final equilibrated all-atom model was built with a systematic simulation toolset consisting of three consecutive parts: (1) building a global cross-linked PEG-chain network at experimentally determined cross-link density using an on-lattice Monte Carlo method based on the bond fluctuation model, (2) recovering the local molecular structure of the network by transitioning from the lattice model to an off-lattice coarse-grained (CG) model parameterized from PCFF, followed by equilibration using high performance molecular dynamics methods, and (3) recovering the atomistic structure of the network by reverse mapping from the equilibrated CG structure, hydrating the structure with explicitly represented water, followed by final equilibration using PCFF parameterization. The developed three-stage modeling approach has application to a wide range of other complex macromolecular hydrogel systems, including the integration of peptide, protein, and/or drug molecules as side-chains within the hydrogel network for the incorporation of bioactivity for tissue engineering, regenerative medicine, and drug delivery applications. PMID:27013229

Poly(ethylene glycol)s in Semidilute Regime: Radius of Gyration in the Bulk and Partitioning into a Nanopore

DOE PAGES

Gurnev, Philip A.; Stanley, Christopher B.; Aksoyoglu, M. Alphan; ...

2017-03-09

In this work, using two approaches, small-angle neutron scattering (SANS) from bulk solutions and nanopore conductance-fluctuation analysis, we studied structural and dynamic features of poly(ethylene glycol) (PEG) water/salt solutions in the dilute and semidilute regimes. SANS measurements on PEG 3400 at the zero-average contrast yielded the single chain radius of gyration (R g) over 1–30 wt %. We observed a small but statistically reliable decrease in R g with increasing PEG concentration: at 30 wt % the chain contracts by a factor of 0.94. Analyzing conductance fluctuations of the α-hemolysin nanopore in the mixtures of PEG 200 with PEG 3400,more » we demonstrated that polymer partitioning into the nanopore is mostly due to PEG 200. Specifically, for a 1:1 wt/wt mixture the smaller polymer dominates to the extent that only about 1/25 of the nanopore volume is taken by the larger polymer. In conclusion, these findings advance our conceptual and quantitative understanding of nanopore polymer partitioning; they also support the main assumptions of the recent “polymers-pushing-polymers” model.« less

Concentrations and congener profiles of chlorinated paraffins in domestic polymeric products in China.

PubMed

Wang, Chu; Gao, Wei; Liang, Yong; Wang, Yawei; Jiang, Guibin

2018-03-21

Chlorinated paraffins (CPs) are widely used in domestic polymeric products as plasticizers and fire retardants. In this study, concentrations and congener profiles of short-chain and medium-chain chlorinated paraffins (SCCPs and MCCPs) were investigated in domestic polymeric products, including plastics, rubber and food packaging in China. The average concentrations of SCCPs in polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE) and food packaging were 234, 3968, 150 and 188 ng/g, respectively and the corresponding average concentrations of MCCPs in these samples were 37.4, 2537, 208 and 644 ng/g, respectively. The concentrations of CPs in rubber and polyvinylchloride (PVC) were significantly higher than in other matrices. The highest concentrations of SCCPs and MCCPs were found in a PVC cable sheath with 191 mg/g and 145 mg/g, respectively. Congener group profiles analysis indicated C 11 - and C 13 -congener groups were predominant in carbon homologues of SCCPs, and C 14 -congener groups were predominant in MCCPs. High levels of SCCPs and MCCPs in domestic polymeric products implied that they might be a significant source to the environment and human exposure. Copyright © 2018. Published by Elsevier Ltd.

Structure and self-assembly properties of a new chitosan-based amphiphile.

PubMed

Huang, Yuping; Yu, Hailong; Guo, Liang; Huang, Qingrong

2010-06-17

A new chitosan-based amphiphile, octanoyl-chitosan-polyethylene glycol monomethyl ether (acylChitoMPEG), has been prepared using both hydrophobic octanoyl and hydrophilic polyethylene glycol monomethyl ether (MPEG) substitutions. The success of synthesis was confirmed by Fourier transform infrared (FT-IR) and (1)H NMR spectroscopy. The synthesized acylChitoMPEG exhibited good solubility in either aqueous solution or common organic solvents such as ethanol, acetone, and CHCl(3). The self-aggregation behavior of acylChitoMPEG in solutions was studied by a combination of pyrene fluorescence technique, dynamic light scattering, atomic force microscopy, and small-angle X-ray scattering (SAXS). The critical aggregation concentration (CAC) and hydrodynamic diameter were found to be 0.066 mg/mL and 24.4 nm, respectively. SAXS results suggested a coiled structure of the triple helical acylChitoMPEG backbone with the hydrophobic moieties hiding in the center of the backbone, and the hydrophilic MPEG chains surrounding the acylChitoMPEG backbone in a random Gaussian chain conformation. Cytotoxicity results showed that acylChitoMPEG exhibited negligible cytotoxicity even at concentrations as high as 1.0 mg/mL. All results implied that acylChitoMPEG has the potential to be used for biological or medical applications.

Comparison of the MBBR denitrification carriers for advanced nitrogen removal of wastewater treatment plant effluent.

PubMed

Yuan, Quan; Wang, Haiyan; Hang, Qianyu; Deng, Yangfan; Liu, Kai; Li, Chunmei; Zheng, Shengzhi

2015-09-01

The moving bed biofilm reactors (MBBRs) were used to remove the residual NO3(-)-N of wastewater treatment plant (WWTP) effluent, and the MBBR carriers for denitrification were compared. The results showed that high denitrification efficiency can be achieved with polyethylene, polypropylene, polyurethane foam, and haydite carriers under following conditions: 7.2 to 8.0 pH, 24 to 26 °C temperature, 12 h hydraulic retention time (HRT), and 25.5 mg L(-1) external methanol dosage, while the WWTP effluent total nitrogen (TN) was between 2.6 and 15.4 mg L(-1) and NO3(-)-N was between 0.2 and 12.6 mg L(-1). The MBBR filled with polyethylene carriers had higher TN and NO3(-)-N removal rate (44.9 ± 19.1 and 83.4 ± 13.0%, respectively) than those with other carriers. The minimum effluent TN and NO3(-)-N of polyethylene MBBR were 1.6 and 0.1 mg L(-1), respectively, and the maximum denitrification rate reached 23.0 g m(-2) day(-1). When chemical oxygen demand (COD)/TN ratio dropped from 6 to 4, the NO3(-)- N and TN removal efficiency decreased significantly in all reactors except for that filled with polyethylene, which indicated that the polyethylene MBBR can resist influent fluctuation much better. The three-dimensional excitation-emission matrix analysis showed that all the influent and effluent of MBBRs contain soluble microbial products (SMPs)-like organics and biochemical oxygen demand (BOD), which can be removed better by MBBRs filled with haydite and polyethylene carriers. The nitrous oxide reductase (nosZ)-based terminal restriction fragment length polymorphism (T-RFLP) analysis suggested that the dominant bacteria in polyethylene MBBR are the key denitrificans.

Compartmentalization Technologies via Self-Assembly and Cross-Linking of Amphiphilic Random Block Copolymers in Water.

PubMed

Matsumoto, Mayuko; Terashima, Takaya; Matsumoto, Kazuma; Takenaka, Mikihito; Sawamoto, Mitsuo

2017-05-31

Orthogonal self-assembly and intramolecular cross-linking of amphiphilic random block copolymers in water afforded an approach to tailor-make well-defined compartments and domains in single polymer chains and nanoaggregates. For a double compartment single-chain polymer, an amphiphilic random block copolymer bearing hydrophilic poly(ethylene glycol) (PEG) and hydrophobic dodecyl, benzyl, and olefin pendants was synthesized by living radical polymerization (LRP) and postfunctionalization; the dodecyl and benzyl units were incorporated into the different block segments, whereas PEG pendants were statistically attached along a chain. The copolymer self-folded via the orthogonal self-assembly of hydrophobic dodecyl and benzyl pendants in water, followed by intramolecular cross-linking, to form a single-chain polymer carrying double yet distinct hydrophobic nanocompartments. A single-chain cross-linked polymer with a chlorine terminal served as a globular macroinitiator for LRP to provide an amphiphilic tadpole macromolecule comprising a hydrophilic nanoparticle and a hydrophobic polymer tail; the tadpole thus self-assembled into multicompartment aggregates in water.

Specific targeting and noninvasive magnetic resonance imaging of an asthma biomarker in the lung using polyethylene glycol functionalized magnetic nanocarriers.

PubMed

Al Faraj, Achraf; Shaik, Asma Sultana; Afzal, Sibtain; Al-Muhsen, Saleh; Halwani, Rabih

2016-05-01

Simultaneous inhibition of IL4 and IL13 via the common receptor chain IL4Rα to block adequately their biologic effects presents a promising therapeutic approach to give the additional relief required for asthma patients. In this study, superparamagnetic iron oxide nanoparticles were conjugated with anti-IL4Rα blocking antibodies via polyethylene glycol (PEG) polymers. The delivery of these blocking antibodies to the inflammatory sites in the lung via the developed nanocarriers was assessed using noninvasive free-breathing pulmonary MRI. Biocompatibility assays confirmed the safety of the developed nanocarriers for pre-clinical investigations. For all the investigated formulations, nanocarriers were found to be very stable at neutral pH. However, the stability noticeably decreased with the PEG length in acidic environment and thus the loaded antibodies were preferentially released. Immunofluorescence and fluorimetry assays confirmed the binding of the nanocarriers to the IL4Rα asthma biomarker. Pulmonary MRI performed using an ultra-short echo time sequence allowed simultaneous noninvasive monitoring of inflammatory responses induced by ovalbumin challenge and tracking of the developed nanocarriers, which were found to colocalize with the inflammatory sites in the lung. Targeting of the developed nanocarriers to areas rich in IL4Rα positive inflammatory cells was confirmed using histological and flow cytometry analyses. The anti-IL4Rα-conjugated nanocarriers developed here have been confirmed to be efficient in targeting key inflammatory cells during chronic lung inflammation following intrapulmonary administration. Targeting efficiency was monitored using noninvasive MRI, allowing detection of the nanocarriers' colocalizations with the inflammatory sites in the lung of ovalbumin-challenged asthmatic mice. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.

Effect of molecular weight of polyethylene glycol on the rheological properties of fumed silica-polyethylene glycol shear thickening fluid

NASA Astrophysics Data System (ADS)

Singh, Mansi; Verma, Sanjeev K.; Biswas, Ipsita; Mehta, Rajeev

2018-05-01

The steady-shear viscosity and dynamic visco-elastic behavior of suspensions of 20 wt% fumed silica-polyethylene glycol (PEG200) shear thickening fluid (STF) with different concentrations of various molecular weight PEG (4600, 6000 and 10000) has been studied. The results demonstrate that with an increase in the molecular weight of dispersing medium, the shear thickening parameters are significantly enhanced. In steady-state rheology, addition of PEG6000 as an additive results in high shear thickening at both low and high temperatures whereas in dynamic state, PEG4600 gives high values of all dynamic parameters. Additionally, long polymer can interconnect several particles, acting as cross-links which explain the mechanism of the enhancement in viscosity. Interestingly, compositions having PEG10000 as additive exhibits shear thinning rheology. Long polymer chains increases hydrodynamic forces thus aggregation of particles increases. Also, the results demonstrate the effect of high molecular weight PEGs on the elasticity and stability of the STF, which is important with regard to high impact resisting applications.

To what extent are microplastics from the open ocean weathered?

PubMed

Ter Halle, Alexandra; Ladirat, Lucie; Martignac, Marion; Mingotaud, Anne Françoise; Boyron, Olivier; Perez, Emile

2017-08-01

It is necessary to better characterize plastic marine debris in order to understand its fate in the environment and interaction with organisms, the most common type of debris being made of polyethylene (PE) and polypropylene (PP). In this work, plastic debris was collected in the North Atlantic sub-tropical gyre during the Expedition 7th Continent sea campaign and consisted mainly in PE. While the mechanisms of PE photodegradation and biodegradation in controlled laboratory conditions are well known, plastic weathering in the environment is not well understood. This is a difficult task to examine because debris comes from a variety of manufactured objects, the original compositions and properties of which vary considerably. A statistical approach was therefore used to compare four sample sets: reference PE, manufactured objects, mesoplastics (5-20 mm) and microplastics (0.3-5 mm). Infrared spectroscopy showed that the surface of all debris presented a higher oxidation state than the reference samples. Differential scanning calorimetry analysis revealed that the microplastics were more crystalline contrarily to the mesoplastics which were similar to references samples. Size exclusion chromatography showed that the molar mass decreased from the references to meso- and microplastics, revealing a clear degradation of the polymer chains. It was thus concluded that the morphology of marine microplastic was much altered and that an unambiguous shortening of the polymer chains took place even for this supposedly robust and inert polymer. Copyright © 2017 Elsevier Ltd. All rights reserved.

Biodegradable copolymers carrying cell-adhesion peptide sequences.

PubMed

Proks, Vladimír; Machová, Lud'ka; Popelka, Stepán; Rypácek, Frantisek

2003-01-01

Amphiphilic block copolymers are used to create bioactive surfaces on biodegradable polymer scaffolds for tissue engineering. Cell-selective biomaterials can be prepared using copolymers containing peptide sequences derived from extracellular-matrix proteins (ECM). Here we discuss alternative ways for preparation of amphiphilic block copolymers composed of hydrophobic polylactide (PLA) and hydrophilic poly(ethylene oxide) (PEO) blocks with cell-adhesion peptide sequences. Copolymers PLA-b-PEO were prepared by a living polymerisation of lactide in dioxane with tin(II)2-ethylhexanoate as a catalyst. The following approaches for incorporation of peptides into copolymers were elaborated. (a) First, a side-chain protected Gly-Arg-Gly-Asp-Ser-Gly (GRGDSG) peptide was prepared by solid-phase peptide synthesis (SPPS) and then coupled with delta-hydroxy-Z-amino-PEO in solution. In the second step, the PLA block was grafted to it via a controlled polymerisation of lactide initiated by the hydroxy end-groups of PEO in the side-chain-protected GRGDSG-PEO. Deprotection of the peptide yielded a GRGDSG-b-PEO-b-PLA copolymer, with the peptide attached through its C-end. (b) A protected GRGDSG peptide was built up on a polymer resin and coupled with Z-carboxy-PEO using a solid-phase approach. After cleavage of the delta-hydroxy-PEO-GRGDSG copolymer from the resin, polymerisation of lactide followed by deprotection of the peptide yielded a PLA-b-PEO-b-GRGDSG block copolymer, in which the peptide is linked through its N-terminus.

Relationship between complement activation, cellular uptake and surface physicochemical aspects of novel PEG-modified nanocapsules.

PubMed

Mosqueira, V C; Legrand, P; Gulik, A; Bourdon, O; Gref, R; Labarre, D; Barratt, G

2001-11-01

The aim of our work was to examine the relationship between modifications of the surface of nanocapsules (NC) by adsorption or covalent grafting of poly(ethylene oxide) (PEG), and changes in their phospholipid (PL) content on complement activation (C3 cleavage) and on uptake by macrophages. The physicochemical characterization of the NC included an investigation of their properties, such as surface charge, size, hydrophilicity, morphology and homogeneity. This is the first time that such properties have been correlated with biological interactions for NC, a novel carrier system with a structure more complex than nanospheres. C3 crossed immunoelectrophoresis revealed the reduced activation for NC with longer PEG chain and higher density, although all formulations induced C3 cleavage to a lesser or greater extent. NC bearing PEG covalently bound to the surface were weaker activators of complement than plain PLA [poly(D,L-lactide)] NC or nanospheres (NS). Furthermore, the fluorescent/confocal microscopy of J774A1 cells in contact with NC reveal a dramatically reduced interaction with PEG-bearing NC. However, the way in which PEG was attached (covalent or adsorbed) seemed to affect the mechanism of uptake. Taken together, these results suggest that the low level of protein binding to NC covered with a high density of 20kDa PEG chains is likely to be due to the steric barriers surrounding these particles, which prevents protein adsorption and reduces their interaction with macrophages.

Photodegradable neutral-cationic brush block copolymers for nonviral gene delivery.

PubMed

Hu, Xianglong; Li, Yang; Liu, Tao; Zhang, Guoying; Liu, Shiyong

2014-08-01

We report on the fabrication of a photodegradable gene-delivery vector based on PEO-b-P(GMA-g-PDMAEMA) neutral-cationic brush block copolymers that possess cationic poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) brushes for DNA compaction, poly(ethylene oxide) (PEO) as a hydrophilic block, and poly(glycidyl methacrylate) (PGMA) as the backbone. The PEO-b-P(GMA-g-PDMAEMA) copolymers were synthesized through the combination of reversible addition-fragmentation transfer (RAFT) polymerization and postmodification. A photocleavable PEO-based macroRAFT agent was first synthesized; next, the PEO-b-PGMA block copolymer was prepared by RAFT polymerization of GMA; this was followed by a click reaction to introduce the RAFT initiators on the side chains of the PGMA block; then, RAFT polymerization of DMAEMA afforded the PEO-b-P(GMA-g-PDMAEMA) copolymer. The obtained neutral-cationic brush block copolymer could effectively complex plasmid DNA (pDNA) into nanoparticles at an N/P ratio (i.e., the number of nitrogen residues per DNA phosphate) of 4. Upon UV irradiation, pDNA could be released owing to cleavage of the pDNA-binding cationic PDMAEMA side chains as well as the nitrobenzyl ester linkages at the diblock junction point. In addition, in vitro gene transfection results demonstrated that the polyplexes could be effectively internalized by cells with good transfection efficiency, and the UV irradiation protocol could considerably enhance the efficiency of gene transfection. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Micelles of enzymatically synthesized PEG-poly(amine-co-ester) block copolymers as pH-responsive nanocarriers for docetaxel delivery.

PubMed

Zhang, Xiaofang; Liu, Bo; Yang, Zhe; Zhang, Chao; Li, Hao; Luo, Xingen; Luo, Huiyan; Gao, Di; Jiang, Qing; Liu, Jie; Jiang, Zhaozhong

2014-03-01

A series of PEGylated poly(amine-co-ester) terpolymers were successfully synthesized in one step via lipase-catalyzed copolymerization of ω-pentadecalactone (PDL), diethyl sebacate (DES), and N-methyldiethanolamine (MDEA) comonomers in the presence of poly(ethylene glycol) methyl ether as a chain-terminating agent. The resultant amphiphilic poly(ethylene glycol)-poly(PDL-co-MDEA-co-sebacate) (PEG-PPMS) block copolymers consisted of hydrophilic PEG chain segments and hydrophobic random PPMS chain segments, which self-assembled in aqueous medium to form stable, nanosized micelles at physiological pH of 7.4. Upon decreasing the medium pH from 7.4 to 5.0, the copolymer micelles swell significantly due to protonation of the amino groups in the micelle PPMS cores. Correspondingly, docetaxel (DTX)-encapsulated PEG2K-PPMS copolymer micelles showed gradual sustained drug release at pH of 7.4, but remarkably accelerated DTX release at acidic pH of 5.0. The drug-loaded micelle particles were readily internalized by SK-BR-3 cancer cells and, compared to free DTX drug, DTX-loaded micelles of the copolymers with optimal compositions exhibited enhanced potency against the cells. Biodegradable PEG-PPMS copolymer micelles represent a new type of promising, pH-responsive nanocarriers for anticancer drug delivery, and the drug release rate from the micelles can be systematically controlled by both pH and the copolymer composition. Copyright © 2013 Elsevier B.V. All rights reserved.

Amphiphilic graft polymer with reduction breakable main chain prepared via click polymerization and grafting onto

NASA Astrophysics Data System (ADS)

Zhang, Xiaojin; Dai, Yu

2018-06-01

Amphiphilic graft polymer PSS- g-Pal/PEG with reduction breakable main chain was synthesized via click polymerization of dialkynyl (containing disulfide bond) and diazide (containing pendant diol) and one-pot grafting onto of hydrophobic palmitate (Pal) and hydrophilic methoxy poly(ethylene glycol) (PEG). PSS- g-Pal/PEG is able to form polymeric micelles by self-assembly in water via dialysis. Polymeric micelles are nano-sized spheres and the particle size is approximately 70 nm. Of note, polymeric micelles are reduction-responsive owing to the disulfide bonds in main chain of PSS- g-Pal/PEG. Therefore, polymeric micelles prepared from amphiphilic graft polymer PSS- g-Pal/PEG are able to fast release the drugs in the presence of the reducing agents such as DL-dithiothreitol (DTT).

Polymer blends for use in photoelectrochemical cells for conversion of solar energy to electricity and methods for manufacturing such blends

DOEpatents

Skotheim, Terje

1984-01-01

There is disclosed a polymer blend of a highly conductive polymer and a solid polymer electrolyte that is designed to achieve better charge transfer across the conductive film/polymer electrolyte interface of the electrochemical photovoltaic cell. The highly conductive polymer is preferably polypyrrole or poly-N-p-nitrophenylpyrrole and the solid polymer electrolyte is preferably polyethylene oxide or polypropylene oxide.

A catalyst-free, temperature controlled gelation system for in-mold fabrication of microgels.

PubMed

Krüger, Andreas J D; Köhler, Jens; Cichosz, Stefan; Rose, Jonas C; Gehlen, David B; Haraszti, Tamás; Möller, Martin; De Laporte, Laura

2018-06-19

Anisometric microgels are prepared via thermal crosslinking using an in-mold polymerization technique. Star-shaped poly(ethylene oxide-stat-propylene oxide) polymers, end-modified with amine and epoxy groups, form hydrogels, of which the mechanical properties and gelation rate can be adjusted by the temperature, duration of heating, and polymer concentration. Depending on the microgel stiffness, the rod-shaped microgels self-assemble into ordered or disordered structures.

Study of crosslinking onset and hydrogen annealing of ultra-high molecular weight polyethylene irradiated with high-energy protons

NASA Astrophysics Data System (ADS)

Wilson, John Ford

1997-09-01

Ultra high molecular weight polyethylene (UHMW-PE) is used extensively in hip and knee endoprostheses. Radiation damage from the sterilization of these endoprostheses prior to surgical insertion results in polymer crosslinking and decreased oxidative stability. The motivation for this study was to determine if UHMW-PE could be crosslinked by low dose proton irradiation with minimal radiation damage and its subsequent deleterious effects. I found that low dose proton irradiation and post irradiation hydrogen annealing did crosslink UHMW-PE and limit post irradiation oxidation. Crosslinking onset was investigated for UHMW-PE irradiated with 2.6 and 30 MeV H+ ions at low doses from 5.7 × 1011-2.3 × 1014 ions/cm2. Crosslinking was determined from gel permeation chromatography (GPC) of 1,2,4 trichlorobenzene sol fractions and increased with dose. Fourier transform infrared spectroscopy (FTIR) showed irradiation resulted in increased free radicals confirmed from increased carbonyl groups. Radiation damage, especially at the highest doses observed, also showed up in carbon double bonds and increased methyl end groups. Hydrogen annealing after ion irradiation resulted in 40- 50% decrease in FTIR absorption associated with carbonyl. The hydrogen annealing prevented further oxidation after aging for 1024 hours at 80oC. Hydrogen annealing was successful in healing radiation damage through reacting with the free radicals generated during proton irradiation. Polyethylenes, polyesters, and polyamides are used in diverse applications by the medical profession in the treatment of orthopedic impairments and cardiovascular disease and for neural implants. These artificial implants are sterilized with gamma irradiation prior to surgery and the resulting radiation damage can lead to accelerated deterioration of the implant properties. The findings in this study will greatly impact the continued use of these materials through the elimination of many problems associated with radiation damage from sterilization. The higher energy transfer for proton compared to gamma irradiation greatly accelerated the radiation damage. Radiation damage increased linearly with dose over the range of doses examined. These results were consistent with findings from earlier researchers of gamma irradiation of polyethylene.

Influence of Pro-Oxidant on Photodegradation of a Low-Density Polyethylene-Nanosilica Composite

EPA Science Inventory

Use of polymer nanocomposites is burgeoning and they represent one of the fastest growing components of the manufactured nanomaterials market. Incorporation of nanoscale fillers in these plastics significantly improves their stiffness and other key mechanical properties. Although...

Hole hopping through tyrosine/tryptophan chains protects proteins from oxidative damage

PubMed Central

Gray, Harry B.; Winkler, Jay R.

2015-01-01

Living organisms have adapted to atmospheric dioxygen by exploiting its oxidizing power while protecting themselves against toxic side effects. Reactive oxygen and nitrogen species formed during oxidative stress, as well as high-potential reactive intermediates formed during enzymatic catalysis, could rapidly and irreversibly damage polypeptides were protective mechanisms not available. Chains of redox-active tyrosine and tryptophan residues can transport potentially damaging oxidizing equivalents (holes) away from fragile active sites and toward protein surfaces where they can be scavenged by cellular reductants. Precise positioning of these chains is required to provide effective protection without inhibiting normal function. A search of the structural database reveals that about one third of all proteins contain Tyr/Trp chains composed of three or more residues. Although these chains are distributed among all enzyme classes, they appear with greatest frequency in the oxidoreductases and hydrolases. Consistent with a redox-protective role, approximately half of the dioxygen-using oxidoreductases have Tyr/Trp chain lengths ≥3 residues. Among the hydrolases, long Tyr/Trp chains appear almost exclusively in the glycoside hydrolases. These chains likely are important for substrate binding and positioning, but a secondary redox role also is a possibility. PMID:26195784

Competitive adsorption of surfactants and polymers at the free water surface. A computer simulation study of the sodium dodecyl sulfate-poly(ethylene oxide) system.

PubMed

Darvas, Mária; Gilányi, Tibor; Jedlovszky, Pál

2011-02-10

Competitive adsorption of a neutral amphiphilic polymer, namely poly(ethylene oxide) (PEO) and an ionic surfactant, i.e., sodium dodecyl sulfate (SDS), is investigated at the free water surface by computer simulation methods at 298 K. The sampled equilibrium configurations are analyzed in terms of the novel identification of the truly interfacial molecules (ITIM) method, by which the intrinsic surface of the aqueous phase (i.e., its real surface corrugated by the capillary waves) instead of an ideally flat surface approximating its macroscopic surface plane, can be taken into account. In the simulations, the surface density of SDS is gradually increased from zero up to saturation, and the structural, dynamical, and energetic aspects of the gradual squeezing out of the PEO chains from the surface are analyzed in detail. The obtained results reveal that this squeezing out occurs in a rather intricate way. Thus, in the presence of a moderate amount of SDS the majority of the PEO monomer units, forming long bulk phase loops in the absence of SDS, are attracted to the surface of the solution. This synergistic effect of SDS of moderate surface density on the adsorption of PEO is explained by two factors, namely by the electrostatic attraction between the ionic groups of the surfactant and the moderately polar monomer units of the polymer, and by the increase of the conformational entropy of the polymer chain in the presence of the surfactant. This latter effect, thought to be the dominant one among the above two factors, also implies the formation of similar polymer/surfactant complexes at the interface than what are known to exist in the bulk phase of the solution. Finally, in the presence of a large amount of SDS the more surface active surfactant molecules gradually replace the PEO monomer units at the interfacial positions, and squeezing out the PEO molecules from the surface in a monomer unit by monomer unit manner.

Molecular dynamics study of the diffusivity of a hydrophobic drug Cucurbitacin B in pseudo-poly(ethylene oxide-b-caprolactone) micelle environments.

PubMed

Razavilar, Negin; Choi, Phillip

2014-07-08

Isobaric-isothermal molecular dynamics simulation was used to study the diffusion of a hydrophobic drug Cucurbitacin B (CuB) in pseudomicelle environments consisting of poly(ethylene oxide-b-caprolactone) (PEO-b-PCL) swollen by various amounts of water. Two PEO-b-PCL configurations, linear and branched, with the same total molecular weight were used. For the branched configuration, the block copolymer contained one linear block of PEO with the same molecular weight as that of the PEO block used in the linear configuration but with one end connecting to three PCL blocks with the same chain length, hereafter denoted PEO-b-3PCL. Regardless of the configuration, the simulation results showed that the diffusivity of CuB was insensitive to the water concentration up to ∼8 wt % while that of water decreased with an increasing water concentration. The diffusivity of CuB (10(-8) cm(2)/s) was 3 orders of magnitude lower than that of water (10(-5) cm(2)/s). This is attributed to the fact that CuB relied on the wiggling motion of the block copolymers to diffuse while water molecules diffused via a hopping mechanism. The rates at which CuB and water diffused into PEO-b-PCL were twice those in PEO-b-3PCL because the chain mobility and the degree of swelling are higher and there are fewer intermolecular hydrogen bonds in the case of PEO-b-PCL. The velocity autocorrelation functions of CuB show that the free volume holes formed by PEO-b-3PCL are more rigid than those formed by PEO-b-PCL, making CuB exhibit higher-frequency collision motion in PEO-b-3PCL than in PEO-b-PCL, and the difference in frequency is insensitive to water concentration.

Breakdown of the Stokes-Einstein Relation for the Rotational Diffusivity of Polymer Grafted Nanoparticles in Polymer Melts.

PubMed

Maldonado-Camargo, Lorena; Rinaldi, Carlos

2016-11-09

We report observations of breakdown of the Stokes-Einstein relation for the rotational diffusivity of polymer-grafted spherical nanoparticles in polymer melts. The rotational diffusivity of magnetic nanoparticles coated with poly(ethylene glycol) dispersed in poly(ethylene glycol) melts was determined through dynamic magnetic susceptibility measurements of the collective rotation of the magnetic nanoparticles due to imposed time-varying magnetic torques. These measurements clearly demonstrate the existence of a critical molecular weight for the melt polymer, below which the Stokes-Einstein relation accurately describes the rotational diffusivity of the polymer-grafted nanoparticles and above which the Stokes-Einstein relation ceases to apply. This critical molecular weight was found to correspond to a chain contour length that approximates the hydrodynamic diameter of the nanoparticles.

The structural characteristics of inflatable beams

NASA Astrophysics Data System (ADS)

Wicker, William J.

1992-08-01

Two inflatable beams are designed and fabricated from polyethylene of ultrahigh molecular weight, and the structures are tested against similar composite and metal-alloy tubes. Specific attention is given to the choice of material that insures material stiffness, good strength-to-weight ratio, creep resistance, and durability. A cloth beam is built from a commercial extended-chain polyethylene fiber, and the inflated beams are tested by means of three- and four-point loading to measure bending and shear deformation. Comparing geometrically similar structures shows that the fabric beams can be about 35 percent as stiff as aluminum for small deflections. The inflatable beams have elastic stiffness coefficients five and two times higher than those for nylon and polyester tubes, respectively. Inflatable structures are concluded to hold promise for lightweight aerospace applications which demand small storage areas.

Simulation of polyethylene glycol and calcium-mediated membrane fusion

NASA Astrophysics Data System (ADS)

Pannuzzo, Martina; De Jong, Djurre H.; Raudino, Antonio; Marrink, Siewert J.

2014-03-01

We report on the mechanism of membrane fusion mediated by polyethylene glycol (PEG) and Ca2+ by means of a coarse-grained molecular dynamics simulation approach. Our data provide a detailed view on the role of cations and polymer in modulating the interaction between negatively charged apposed membranes. The PEG chains cause a reduction of the inter-lamellar distance and cause an increase in concentration of divalent cations. When thermally driven fluctuations bring the membranes at close contact, a switch from cis to trans Ca2+-lipid complexes stabilizes a focal contact acting as a nucleation site for further expansion of the adhesion region. Flipping of lipid tails induces subsequent stalk formation. Together, our results provide a molecular explanation for the synergistic effect of Ca2+ and PEG on membrane fusion.

Disparate effects of oxidation on plasma acyltransferase activities: inhibition of cholesterol esterification but stimulation of transesterification of oxidized phospholipids.

PubMed

Subbaiah, P V; Liu, M

1996-05-31

Oxidation of lipoproteins results in the formation of several polar phospholipids with pro-inflammatory and pro-atherogenic properties. To examine the possible role of lecithin/cholesterol acyltransferase (LCAT) in the metabolism of these oxidized phospholipids, we oxidized whole plasma with either Cu(2+) or a free-radical generator, and determined the various activities of LCAT. Oxidation caused a reduction in plasma phosphatidylcholine (PC), an increase in a short-chain polar PC (SCP-PC), and an inhibition of the transfer of long-chain acyl groups to cholesterol (LCAT activity) or to lyso PC (lysolecithin acyltransferase (LAT) I activity). However, the transfer of short-chain acyl groups from SCP-PC to lyso PCLAT II activity) was stimulated several fold, in direct correlation with the degree of oxidation. LAT II activity was not stimulated by oxidation in LCAT-deficient plasma, showing that it is carried out by LCAT. Oxidized normal plasma exhibited low LCAT activity even in the presence of exogenous proteoliposome substrate, indicating that the depletion of substrate PC was not responsible for the loss of activity. Oxidation of isolated LDL or HDL abolished their ability to support LCAT and LAT I activities of exogenous enzyme, but promoted the LAT II activity. Purified LCAT lost its LCAT and LAT I functions, but not its LAT II function, when oxidized in vitro. These results show that while oxidation of plasma causes a loss of LCAT's ability to transfer long-chain acyl groups, its ability to transfer short-chain acyl groups, from SCP-PC is retained, and even stimulated, suggesting that LCAT may have a physiological role in the metabolism of oxidized PC in plasma.

The Role of Interfaces in Polyethylene/Metal-Oxide Nanocomposites for Ultrahigh-Voltage Insulating Materials.

PubMed

Pourrahimi, Amir Masoud; Olsson, Richard T; Hedenqvist, Mikael S

2018-01-01

Recent progress in the development of polyethylene/metal-oxide nanocomposites for extruded high-voltage direct-current (HVDC) cables with ultrahigh electric insulation properties is presented. This is a promising technology with the potential of raising the upper voltage limit in today's underground/submarine cables, based on pristine polyethylene, to levels where the loss of energy during electric power transmission becomes low enough to ensure intercontinental electric power transmission. The development of HVDC insulating materials together with the impact of the interface between the particles and the polymer on the nanocomposites electric properties are shown. Important parameters from the atomic to the microlevel, such as interfacial chemistry, interfacial area, and degree of particle dispersion/aggregation, are discussed. This work is placed in perspective with important work by others, and suggested mechanisms for improved insulation using nanoparticles, such as increased charge trap density, adsorption of impurities/ions, and induced particle dipole moments are considered. The effects of the nanoparticles and of their interfacial structures on the mechanical properties and the implications of cavitation on the electric properties are also discussed. Although the main interest in improving the properties of insulating polymers has been on the use of nanoparticles, leading to nanodielectrics, it is pointed out here that larger microscopic hierarchical metal-oxide particles with high surface porosity also impart good insulation properties. The impact of the type of particle and its inherent properties (purity and conductivity) on the nanocomposite dielectric and insulating properties are also discussed based on data obtained by a newly developed technique to directly observe the charge distribution on a nanometer scale in the nanocomposite. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evidence of formation of site-selective inclusion complexation between beta-cyclodextrin and poly(ethylene oxide)-block-poly(propylene oxide)- block-poly(ethylene oxide) copolymers.

PubMed

Tsai, Chi-Chun; Zhang, Wen-Bin; Wang, Chien-Lung; Van Horn, Ryan M; Graham, Matthew J; Huang, Jing; Chen, Yongming; Guo, Mingming; Cheng, Stephen Z D

2010-05-28

A series of inclusion complexes of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (PEO-b-PPO-b-PEO) with beta-cyclodextrin (beta-CD) was prepared. Their formation, structure, and dynamics were investigated by solution two-dimensional rotating-frame Overhauser effect spectroscopy (2D ROESY) and one-dimensional (1D) and 2D solid-state (13)C NMR. The inclusion complexes between the PEO-b-PPO-b-PEO copolymers and the beta-CDs were formed in aqueous solution and detected by 2D ROESY. The high efficiency of cross polarization and spin diffusion experiments in (13)C solid-state NMR showed that the mobility of the PPO blocks dramatically decreases after beta-CD complexation, indicating that they are selectively incorporated onto the PPO blocks. The hydrophobic cavities of beta-CD restrict the PPO block mobility, which is evidence of the formation of inclusion complexes in the solid state. The 2D wide-line separation NMR experiments suggested that beta-CDs only thread onto the PPO blocks while forming the inclusion complexes. The stoichiometry of inclusion complexes was studied using (1)H NMR, and a 3:1 (PO unit to beta-CD) was found for all inclusion complexes, which indicated that the number of threaded beta-CDs was only dependent on the molecular weight of the PPO blocks. 1D wide angle x-ray diffraction studies demonstrated that the beta-CD in the inclusion complex formed a channel-like structure that is different from the pure beta-CD crystal structure.

Evidence of formation of site-selective inclusion complexation between β-cyclodextrin and poly(ethylene oxide)-block-poly(propylene oxide)- block-poly(ethylene oxide) copolymers

NASA Astrophysics Data System (ADS)

Tsai, Chi-Chun; Zhang, Wen-Bin; Wang, Chien-Lung; Van Horn, Ryan M.; Graham, Matthew J.; Huang, Jing; Chen, Yongming; Guo, Mingming; Cheng, Stephen Z. D.

2010-05-01

A series of inclusion complexes of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (PEO-b-PPO-b-PEO) with β-cyclodextrin (β-CD) was prepared. Their formation, structure, and dynamics were investigated by solution two-dimensional rotating-frame Overhauser effect spectroscopy (2D ROESY) and one-dimensional (1D) and 2D solid-state C13 NMR. The inclusion complexes between the PEO-b-PPO-b-PEO copolymers and the β-CDs were formed in aqueous solution and detected by 2D ROESY. The high efficiency of cross polarization and spin diffusion experiments in C13 solid-state NMR showed that the mobility of the PPO blocks dramatically decreases after β-CD complexation, indicating that they are selectively incorporated onto the PPO blocks. The hydrophobic cavities of β-CD restrict the PPO block mobility, which is evidence of the formation of inclusion complexes in the solid state. The 2D wide-line separation NMR experiments suggested that β-CDs only thread onto the PPO blocks while forming the inclusion complexes. The stoichiometry of inclusion complexes was studied using H1 NMR, and a 3:1 (PO unit to β-CD) was found for all inclusion complexes, which indicated that the number of threaded β-CDs was only dependent on the molecular weight of the PPO blocks. 1D wide angle x-ray diffraction studies demonstrated that the β-CD in the inclusion complex formed a channel-like structure that is different from the pure β-CD crystal structure.

The "New Polyethylene Glycol Dilemma": Polyethylene Glycol Impurities and Their Paradox Role in mAb Crystallization.

PubMed

Hildebrandt, Christian; Joos, Lea; Saedler, Rainer; Winter, Gerhard

2015-06-01

Polyethylene glycols (PEG) represent the most successful and frequently applied class of excipients used for protein crystallization. PEG auto-oxidation and formation of impurities such as peroxides and formaldehydes that foster protein drug degradation is known. However, their effect on mAb crystallization has not been studied in detail before. During the present study, a model IgG1 antibody (mAb1) was crystallized in PEG solutions. Aggregate formation was observed during crystallization and storage that was ascribed to PEG degradation products. Reduction of peroxide and formaldehyde levels prior to crystallization by vacuum and freeze-drying was investigated for its effect on protein degradation. Vacuum drying was superior in removal of peroxides but inferior in reducing formaldehyde residues. Consequently, double purification allowed extensive removal of both impurities. Applying of purified PEG led to 50% lower aggregate fractions. Surprisingly, PEG double purification or addition of methionine prior to crystallization prevented crystal formation. With increased PEG concentration or spiking with peroxides and formaldehydes, crystal formation could be recovered again. With these results, we demonstrate that minimum amounts of oxidizing impurities and thus in consequence chemically altered proteins are vital to initiate mAb1 crystallization. The present study calls PEG as good precipitant for therapeutic biopharmaceuticals into question. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

Polyethylene Nanocomposites for the Next Generation of Ultralow-Transmission-Loss HVDC Cables: Insulation Containing Moisture-Resistant MgO Nanoparticles.

PubMed

Pourrahimi, Amir Masoud; Pallon, Love K H; Liu, Dongming; Hoang, Tuan Anh; Gubanski, Stanislaw; Hedenqvist, Mikael S; Olsson, Richard T; Gedde, Ulf W

2016-06-15

The use of MgO nanoparticles in polyethylene for cable insulation has attracted considerable interest, although in humid media the surface regions of the nanoparticles undergo a conversion to a hydroxide phase. A facile method to obtain MgO nanoparticles with a large surface area and remarkable inertness to humidity is presented. The method involves (a) low temperature (400 °C) thermal decomposition of Mg(OH)2, (b) a silicone oxide coating to conceal the nanoparticles and prevent interparticle sintering upon exposure to high temperatures, and (c) heat treatment at 1000 °C. The formation of the hydroxide phase on these silicone oxide-coated MgO nanoparticles after extended exposure to humid air was assessed by thermogravimetry, infrared spectroscopy, and X-ray diffraction. The nanoparticles showed essentially no sign of any hydroxide phase compared to particles prepared by the conventional single-step thermal decomposition of Mg(OH)2. The moisture-resistant MgO nanoparticles showed improved dispersion and interfacial adhesion in the LDPE matrix with smaller nanosized particle clusters compared with conventionally prepared MgO. The addition of 1 wt % moisture-resistant MgO nanoparticles was sufficient to decrease the conductivity of polyethylene 30 times. The reduction in conductivity is discussed in terms of defect concentration on the surface of the moisture-resistant MgO nanoparticles at the polymer/nanoparticle interface.

Dynamics in entangled polyethylene melts [Multi time scale dynamics in entangled polyethylene melts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Salerno, K. Michael; Agrawal, Anupriya; Peters, Brandon L.

Polymer dynamics creates distinctive viscoelastic behavior as a result of a coupled interplay of motion at the atomic length scale and motion of the entire macromolecule. Capturing the broad time and length scales of polymeric motion however, remains a challenge. Using linear polyethylene as a model system, we probe the effects of the degree of coarse graining on polymer dynamics. Coarse-grained (CG) potentials are derived using iterative Boltzmann inversion with λ methylene groups per CG bead (denoted CGλ) with λ = 2,3,4 and 6 from a fully-atomistic polyethylene melt simulation. By rescaling time in the CG models by a factormore » α, the chain mobility for the atomistic and CG models match. We show that independent of the degree of coarse graining, all measured static and dynamic properties are essentially the same once the dynamic scaling factor α and a non-crossing constraint for the CG6 model are included. The speedup of the CG4 model is about 3 times that of the CG3 model and is comparable to that of the CG6 model. Furthermore, using these CG models we were able to reach times of over 500 μs, allowing us to measure a number of quantities, including the stress relaxation function, plateau modulus and shear viscosity, and compare directly to experiment.« less

Dynamics in entangled polyethylene melts [Multi time scale dynamics in entangled polyethylene melts

DOE PAGES

Salerno, K. Michael; Agrawal, Anupriya; Peters, Brandon L.; ...

2016-10-10

Polymer dynamics creates distinctive viscoelastic behavior as a result of a coupled interplay of motion at the atomic length scale and motion of the entire macromolecule. Capturing the broad time and length scales of polymeric motion however, remains a challenge. Using linear polyethylene as a model system, we probe the effects of the degree of coarse graining on polymer dynamics. Coarse-grained (CG) potentials are derived using iterative Boltzmann inversion with λ methylene groups per CG bead (denoted CGλ) with λ = 2,3,4 and 6 from a fully-atomistic polyethylene melt simulation. By rescaling time in the CG models by a factormore » α, the chain mobility for the atomistic and CG models match. We show that independent of the degree of coarse graining, all measured static and dynamic properties are essentially the same once the dynamic scaling factor α and a non-crossing constraint for the CG6 model are included. The speedup of the CG4 model is about 3 times that of the CG3 model and is comparable to that of the CG6 model. Furthermore, using these CG models we were able to reach times of over 500 μs, allowing us to measure a number of quantities, including the stress relaxation function, plateau modulus and shear viscosity, and compare directly to experiment.« less

Chemical modification of protein a chromatography ligands with polyethylene glycol. II: Effects on resin robustness and process selectivity.

PubMed

Weinberg, Justin; Zhang, Shaojie; Kirkby, Allison; Shachar, Enosh; Carta, Giorgio; Przybycien, Todd

2018-04-20

We have proposed chemical modification of Protein A (ProA) chromatography ligands with polyethylene glycol (PEGylation) as a strategy to increase the resin selectivity and robustness by providing the ligand with a steric repulsion barrier against non-specific binding. Here, we report on robustness and selectivity benefits for Repligen CaptivA PriMAB resin with ligands modified with 5.2 kDa and 21.5 kDa PEG chains, respectively. PEGylation of ProA ligands allowed the resin to retain a higher percentage of static binding capacity relative to the unmodified resin upon digestion with chymotrypsin, a representative serine protease. The level of protection against digestion was independent of the PEG molecular weight or modification extent for the PEGylation chemistry used. Additionally, PEGylation of the ligands was found to decrease the level of non-specific binding of fluorescently labeled bovine serum albumin (BSA) aggregates to the surface of the resin particles as visualized via confocal laser scanning microscopy (CLSM). The level of aggregate binding decreased as the PEG molecular weight increased, but increasing the extent of modification with 5.2 kDa PEG chains had no effect. Further examination of resin particles via CLSM confirmed that the PEG chains on the modified ligands were capable of blocking the "hitchhiking" association of BSA, a mock contaminant, to an adsorbed mAb that is prone to BSA binding. Ligands modified with 21.5 kDa PEG chains were effective at blocking the association, while ligands modified with 5.2 kDa PEG chains were not. Finally, ligands with 21.5 kDa PEG chains increased the selectivity of the resin against host cell proteins (HCPs) produced by Chinese Hamster Ovary (CHO) cells by up to 37% during purification of a monoclonal antibody (mAb) from harvested cell culture fluid (HCCF) using a standard ProA chromatography protocol. The combined work suggests that PEGylating ProA chromatography media is a viable pathway for increasing both resin lifetime and host cell impurity clearance in downstream bioprocessing. Copyright © 2018 Elsevier B.V. All rights reserved.

7Li NMR spectroscopy and ion conduction mechanism in mesoporous silica (SBA-15) composite poly(ethylene oxide) electrolyte

NASA Astrophysics Data System (ADS)

Reddy, M. Jaipal; Chu, Peter P.

A composite of mesoporous silica (SBA-15) with a polyethylene oxide (PEO) polymer electrolyte is examined for use in various electrochemical devices. Incorporation of SBA-15 in a PEO:LiClO 4 polymer electrolyte facilitates salt dissociation, enhances ion conductivity, and improves miscibility between organic and inorganic moieties. Optimized conductivity is found at 10 wt.% SBA-15 composition, above this concentration the conductivity is reduced due to aggregation of a SBA-15:Li rich phase. Heating above melt temperature of PEO allows more of the polymer segments to interact with SBA-15. This results in a greater degree of disorder upon cooling, and the ion conductivity is enhanced. A 7Li MAS NMR study reveals three types of lithium-ion coordination. Two major types of conduction mechanism can be identified: one through conventional amorphous PEO; a second via hopping in a sequential manner by replacing the nearby vacancies ('holes') on the surface (both interior and exterior) of the SBA-15 channels.

Flexible Epoxy Resin Formed Upon Blending with a Triblock Copolymer through Reaction-Induced Microphase Separation

PubMed Central

Chu, Wei-Cheng; Lin, Wei-Sheng; Kuo, Shiao-Wei

2016-01-01

In this study, we used diglycidyl ether bisphenol A (DGEBA) as a matrix, the ABA block copolymer poly(ethylene oxide–b–propylene oxide–b–ethylene oxide) (Pluronic F127) as an additive, and diphenyl diaminosulfone (DDS) as a curing agent to prepare flexible epoxy resins through reaction-induced microphase separation (RIMPS). Fourier transform infrared spectroscopy confirmed the existence of hydrogen bonding between the poly(ethylene oxide) segment of F127 and the OH groups of the DGEBA resin. Small-angle X-ray scattering, atomic force microscopy, and transmission electron microscopy all revealed evidence for the microphase separation of F127 within the epoxy resin. Glass transition temperature (Tg) phenomena and mechanical properties (modulus) were determined through differential scanning calorimetry and dynamic mechanical analysis, respectively, of samples at various blend compositions. The modulus data provided evidence for the formation of wormlike micelle structures, through a RIMPS mechanism, in the flexible epoxy resin upon blending with the F127 triblock copolymer. PMID:28773571