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Sample records for polymer degradation probed

  1. Coating flexible probes with an ultra fast degrading polymer to aid in tissue insertion

    PubMed Central

    Wang, Shuwu; Singh, Sagar; Damodaran, Vinod B.; Kaplan, Hilton M.; Kohn, Joachim; Shreiber, David I.; Zahn, Jeffrey D.

    2016-01-01

    We report a fabrication process for coating neural probes with an ultrafast degrading polymer to create consistent and reproducible devices for neural tissue insertion. The rigid polymer coating acts as a probe insertion aid, but resorbs within hours post-implantation. Despite the feasibility for short term neural recordings from currently available neural prosthetic devices, most of these devices suffer from long term gliosis, which isolates the probes from adjacent neurons, increasing the recording impedance and stimulation threshold. The size and stiffness of implanted probes have been identified as critical factors that lead to this long term gliosis. Smaller, more flexible probes that match the mechanical properties of brain tissue could allow better long term integration by limiting the mechanical disruption of the surrounding tissue during and after probe insertion, while being flexible enough to deform with the tissue during brain movement. However, these small flexible probes inherently lack the mechanical strength to penetrate the brain on their own. In this work, we have developed a micromolding method for coating a non-functional miniaturized SU-8 probe with an ultrafast degrading tyrosine-derived polycarbonate (E5005(2K)). Coated, non-functionalized probes of varying dimensions were reproducibly fabricated with high yields. The polymer erosion/degradation profiles of the probes were characterized in vitro. The probes were also mechanically characterized in ex vivo brain tissue models by measuring buckling and insertion forces during probe insertion. The results demonstrate the ability to produce polymer coated probes of consistent quality for future in vivo use, for example to study the effects of different design parameters that may affect tissue response during long term chronic intra-cortical microelectrode neural recordings. PMID:25681971

  2. Coating flexible probes with an ultra fast degrading polymer to aid in tissue insertion.

    PubMed

    Lo, Meng-chen; Wang, Shuwu; Singh, Sagar; Damodaran, Vinod B; Kaplan, Hilton M; Kohn, Joachim; Shreiber, David I; Zahn, Jeffrey D

    2015-04-01

    We report a fabrication process for coating neural probes with an ultrafast degrading polymer to create consistent and reproducible devices for neural tissue insertion. The rigid polymer coating acts as a probe insertion aid, but resorbs within hours post-implantation. Despite the feasibility for short term neural recordings from currently available neural prosthetic devices, most of these devices suffer from long term gliosis, which isolates the probes from adjacent neurons, increasing the recording impedance and stimulation threshold. The size and stiffness of implanted probes have been identified as critical factors that lead to this long term gliosis. Smaller, more flexible probes that match the mechanical properties of brain tissue could allow better long term integration by limiting the mechanical disruption of the surrounding tissue during and after probe insertion, while being flexible enough to deform with the tissue during brain movement. However, these small flexible probes inherently lack the mechanical strength to penetrate the brain on their own. In this work, we have developed a micromolding method for coating a non-functional miniaturized SU-8 probe with an ultrafast degrading tyrosine-derived polycarbonate (E5005(2K)). Coated, non-functionalized probes of varying dimensions were reproducibly fabricated with high yields. The polymer erosion/degradation profiles of the probes were characterized in vitro. The probes were also mechanically characterized in ex vivo brain tissue models by measuring buckling and insertion forces during probe insertion. The results demonstrate the ability to produce polymer coated probes of consistent quality for future in vivo use, for example to study the effects of different design parameters that may affect tissue response during long term chronic intra-cortical microelectrode neural recordings.

  3. Synchrotron powered FT-IR microspectroscopic incremental probing of photochemically degraded polymer films

    NASA Astrophysics Data System (ADS)

    Wetzel, David L.; Carter, Roscoe O.

    1998-06-01

    An acrylic polymer automotive coating that had been subjected to Florida sun for 3 years was subsequently exposed to accelerated photochemical attack with Xenon lamps. Microtomed 6 μm-thick sections of the photochemically degraded polymer films were mounted between two 13 mm diameter×2 mm thick barium fluoride disks in a compression cell. With dual apertures 6 μm wide and 36 μm long, a line mapping procedure was performed by stepping the motorized stage in 5 μm increments. The chemical composition was mapped from the outermost edge through the degraded and washed out area into the pristine part of the clear coat, the base coat, and finally the primer. The results of incremental probing of the exposed acrylic polymer coating was compared to a retained specimen of the same material that had been protected from exposure to ultraviolet radiation. Previous attempts with photoacoustic infrared spectroscopy had established the destruction of some absorption bands and the appearance of new broad bands of oxidation products. The depth of the photochemical action was revealed by transmission probing as described here including 1 μm increment line mapping across the clear coat. Interdiffusion of adjacent clear and base coats was also evident. Other polymers subjected to impingement of O+4 at different levels of flux showed oxidation by ATR microspectroscopy of the exposed surface in comparison to spectra obtained by the same means from the unexposed back side of the 0.25 in-thick specimen of polypropylene.

  4. Carbon-13 Labeling Used to Probe Cure and Degradation Reactions of High- Temperature Polymers

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B.; Johnston, J. Christopher

    1998-01-01

    High-temperature, crosslinked polyimides are typically insoluble, intractible materials. Consequently, in these systems it has been difficult to follow high-temperature curing or long-term degradation reactions on a molecular level. Selective labeling of the polymers with carbon-13, coupled with solid nuclear magnetic resonance spectrometry (NMR), enables these reactions to be followed. We successfully employed this technique to provide insight into both curing and degradation reactions of PMR-15, a polymer matrix resin used extensively in aircraft engine applications.

  5. Remote inhibition of polymer degradation.

    SciTech Connect

    Clough, Roger Lee; Celina, Mathias Christopher

    2005-08-01

    Polymer degradation has been explored on the basis of synergistic infectious and inhibitive interaction between separate materials. A dual stage chemiluminescence detection system with individually controlled hot stages was applied to probe for interaction effects during polymer degradation in an oxidizing environment. Experimental confirmation was obtained that volatile antioxidants can be transferred over a relatively large distance. The thermal degradation of a polypropylene (PP) sample receiving traces of inhibitive antioxidants from a remote source is delayed. Similarly, volatiles from two stabilized elastomers were also capable of retarding a degradation process remotely. This observation demonstrates inhibitive cross-talk as a novel interactive phenomenon between different polymers and is consequential for understanding general polymer interactions, fundamental degradation processes and long-term aging effects of multiple materials in a single environment.

  6. An overview of degradable polymers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Many degradable polymers are being investigated for research purpose or for possible commercial use. This overview provides a listing of the more important degradable polymers and their mechanisms of action. Some application areas, particularly in packaging, housewares, personal care, biomaterials, ...

  7. An overview of degradable polymers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Many degradable polymers are being investigated for research purpose or for possible commercial use. This overview provides a listing of the more important degradable polymers and their mechanisms of action. Some application areas, particularly in packaging, housewares, personal care, biomaterials...

  8. Foldable polymers as probes

    DOEpatents

    Li, Alexander D. Q.; Wang, Wei

    2007-07-03

    Disclosed herein are novel probes, which can be used to detect and identify target molecules of interest in a sample. The disclosed probes can be used to monitor conformational changes induced by molecular recognition events in addition to providing signaling the presence and/or identity of a target molecule. Methods, including solid phase synthesis techniques, for making probe molecules that exhibit changes in their optical properties upon target molecule binding are described in the disclosure. Also disclosed herein are novel chromophore moieties, which have tailored fluorescent emission spectra.

  9. Foldable polymers as probes

    DOEpatents

    Li, Alexander D. Q.; Wang, Wei

    2009-07-07

    Disclosed herein are novel probes, which can be used to detect and identify target molecules of interest in a sample. The disclosed probes can be used to monitor conformational changes induced by molecular recognition events in addition to providing signaling the presence and/or identity of a target molecule. Methods, including solid phase synthesis techniques, for making probe molecules that exhibit changes in their optical properties upon target molecule binding are described in the disclosure. Also disclosed herein are novel chromophore moieties, which have tailored fluorescent emission spectra.

  10. Polymer Coatings Degradation Properties

    DTIC Science & Technology

    1985-02-01

    release; distribution unlimited. 17. DISTRIBUTION STATEMENT (of 1*. 460060 00md ( Ag 8106k 2.It 4011--t - RepiI) Is. SUPPLEMENTARY NOTES IS. KEY WORDS...two radicals interact The photodegradation mechanism of poly(urethanes) is not known in detail, however, much has been added to our understanding. The...red PAS is also consistent with the probable degradation mechanism, i.e. disappearance of the urethane link- ages . This is another sensitive technique

  11. Degradable vinyl polymers for biomedical applications.

    PubMed

    Delplace, Vianney; Nicolas, Julien

    2015-10-01

    Vinyl polymers have been the focus of intensive research over the past few decades and are attractive materials owing to their ease of synthesis and their broad diversity of architectures, compositions and functionalities. Their carbon-carbon backbones are extremely resistant to degradation, however, and this property limits their uses. Degradable polymers are an important field of research in polymer science and have been used in a wide range of applications spanning from (nano)medicine to microelectronics and environmental protection. The development of synthetic strategies to enable complete or partial degradation of vinyl polymers is, therefore, of great importance because it will offer new opportunities for the application of these materials. This Review captures the most recent and promising approaches to the design of degradable vinyl polymers and discusses the potential of these materials for biomedical applications.

  12. Evolution of the nanostructure of Pt and Pt-Co polymer electrolyte membrane fuel cell electrocatalysts at successive degradation stages probed by X-ray photoemission

    NASA Astrophysics Data System (ADS)

    Ali, Mushtaq; Witkowska, Agnieszka; Abbas, Mamatimin; Gunnella, Roberto; Di Cicco, Andrea

    2014-12-01

    We present a set of XPS (X-ray photoemission spectroscopy) measurements and detailed data-analysis of electrodes for polymer electrolyte membrane fuel cell (PEMFC) based on carbon supported catalysts (Pt and Pt-Co) subjected to a step-like potential cycling (accelerated degradation test). The results of the measurements complete and corroborate parallel TEM (transmission electron microscopy), XRD (X-ray diffraction) and XAS (X-ray absorption spectroscopy) results pointing at a modification of the nanostructure of the catalyst grains. The surface sensitivity of the XPS measurements is used to study the modification of the reactive surface structure of the nanoparticles and the interplay of reactivity and dissolution/precipitation/agglomeration of metal clusters during the catalyst work. The combination of XPS results with XRD, XAS and TEM ones allowed us to obtain a model for the structural changes in Pt-Co nanoparticles occurring during operation. The main structural modifications, in which predominantly Co atoms are involved, occur during the first hours of catalyst operation changing the stoichiometry and degree of disorder in external particles shell. In the last stages of the degradation process, core-shell particles structure, with ordered Pt4Co core and Pt-rich shell (and finally Pt-skin), is formed possibly explaining higher Pt-Co catalyst stability (structural and electrochemical) than pure Pt catalyst.

  13. Coating of fertilizers by degradable polymers.

    PubMed

    Devassine, M; Henry, F; Guerin, P; Briand, X

    2002-08-21

    The conventional agriculture leads to some important pollution of ground water (particularly, by nitrates). The solution is the coating of fertilizers by degradable polymers. In this work, we have studied the water vapour and liquid diffusion through polymer films detached from their support. Therefore, we may classify polymers as a function of their properties like water vapour and liquid barrier. We may choose the best polymer(s) for coating.coated fertilizers by chosen polymer(s) with mechanical techniques such as fluidised bed and pan coating. Moreover, the electron microscopy used to see the quality of the wall has showed the presence of pores due to the rapid evaporation of solvent. A drying in air current and an annealing could be done to avoid this problem.followed the ions release of fertilizers immersed in distilled water by conductimetry. The more interesting result was obtained with fertilizers coated by polylactic acid. In effect, the total release reached three weeks.

  14. Polymer scaffold degradation control via chemical control

    SciTech Connect

    Hedberg-Dirk, Elizabeth L.; Dirk, Shawn; Cicotte, Kirsten

    2016-01-05

    A variety of polymers and copolymers suitable for use as biologically compatible constructs and, as a non-limiting specific example, in the formation of degradable tissue scaffolds as well methods for synthesizing these polymers and copolymers are described. The polymers and copolymers have degradation rates that are substantially faster than those of previously described polymers suitable for the same uses. Copolymers having a synthesis route which enables one to fine tune the degradation rate by selecting the specific stoichiometry of the monomers in the resulting copolymer are also described. The disclosure also provides a novel synthesis route for maleoyl chloride which yields monomers suitable for use in the copolymer synthesis methods described herein.

  15. Polymer Composites Corrosive Degradation: A Computational Simulation

    NASA Technical Reports Server (NTRS)

    Chamis, Christos C.; Minnetyan, Levon

    2007-01-01

    A computational simulation of polymer composites corrosive durability is presented. The corrosive environment is assumed to manage the polymer composite degradation on a ply-by-ply basis. The degradation is correlated with a measured pH factor and is represented by voids, temperature and moisture which vary parabolically for voids and linearly for temperature and moisture through the laminate thickness. The simulation is performed by a computational composite mechanics computer code which includes micro, macro, combined stress failure and laminate theories. This accounts for starting the simulation from constitutive material properties and up to the laminate scale which exposes the laminate to the corrosive environment. Results obtained for one laminate indicate that the ply-by-ply degradation degrades the laminate to the last one or the last several plies. Results also demonstrate that the simulation is applicable to other polymer composite systems as well.

  16. High pressure luminescence probes in polymers

    SciTech Connect

    Drickamer, H.G.

    1980-01-01

    High pressure luminescence has proved to be a very powerful tool for characterizing crystalline solids and liquids. Two problems involving glassy polymers are analyzed. In the first problem the excited states of azulene and its derivatives are used to probe intermolecular interactions in PMMA and PS. In the second problem the change in emission intensity with pressure from two excimer states of polyvinylcarbazole as a pure polymer and in dilute solution in polystyrene (PS), polymethylmethacrylate (PMMA) and polyisoliutylene (PIB) is studied. The relative emission from the two states depends strongly on the possibility for motion of polymer segments. The observations are related to the proximity to the glass transition.

  17. Controlling the Degradation of Bioresorbable Polymers

    NASA Astrophysics Data System (ADS)

    Moritz, Istvan; Crowley, Brian; Brundage, Elizabeth; Rende, Deniz; Ozisik, Rahmi

    Bioresorbable polymers play a vital role in the development of implantable materials that are used in surgical procedures, controlled drug delivery systems; and tissue engineering scaffolds. The half-life of common bioresorbable polymers ranges from 3 to over 12 months and slow bioresorption rates of these polymers restrict their use to a limited set of applications. The use of embedded enzymes was previously proposed to control the degradation rate of bioresorbable polymers, and was shown to decrease average degradation time to about 0.5 months. In this study, electromagnetic actuation of iron oxide magnetic nanoparticles embedded in an encapsulant polymer, poly(ethyleneoxide), PEO, was employed to initiate enzyme assisted degradation of bioresorbable polymer poly(caprolactone), PCL. Results indicate that the internal temperature of iron oxide magnetic nanoparticle doped PEO samples can be increased via an alternating magnetic field, and temperature increase depends strongly on nanoparticle concentration and magnetic field parameters. The temperature achieved is sufficient to relax the PEO matrix and to enable the diffusion of enzymes from PEO to a surrounding PCL matrix. Current studies are directed at measuring the degradation rate of PCL due to the diffused enzyme. This material is based upon work supported by the National Science Foundation under Grant No. CMMI-1538730.

  18. Accelerated Testing Of Photothermal Degradation Of Polymers

    NASA Technical Reports Server (NTRS)

    Kim, Soon Sam; Liang, Ranty Hing; Tsay, Fun-Dow

    1989-01-01

    Electron-spin-resonance (ESR) spectroscopy and Arrhenius plots used to determine maximum safe temperature for accelerated testing of photothermal degradation of polymers. Aging accelerated by increasing illumination, temperature, or both. Results of aging tests at temperatures higher than those encountered in normal use valid as long as mechanism of degradation same throughout range of temperatures. Transition between different mechanisms at some temperature identified via transition between activation energies, manifesting itself as change in slope of Arrhenius plot at that temperature.

  19. Degradability of Polymers for Implantable Biomedical Devices

    PubMed Central

    Lyu, SuPing; Untereker, Darrel

    2009-01-01

    Many key components of implantable medical devices are made from polymeric materials. The functions of these materials include structural support, electrical insulation, protection of other materials from the environment of the body, and biocompatibility, as well as other things such as delivery of a therapeutic drug. In such roles, the stability and integrity of the polymer, over what can be a very long period of time, is very important. For most of these functions, stability over time is desired, but in other cases, the opposite–the degradation and disappearance of the polymer over time is required. In either case, it is important to understand both the chemistry that can lead to the degradation of polymers as well as the kinetics that controls these reactions. Hydrolysis and oxidation are the two classes of reactions that lead to the breaking down of polymers. Both are discussed in detail in the context of the environmental factors that impact the utility of various polymers for medical device applications. Understanding the chemistry and kinetics allows prediction of stability as well as explanations for observations such as porosity and the unexpected behavior of polymeric composite materials in some situations. In the last part, physical degradation such interfacial delamination in composites is discussed. PMID:19865531

  20. Investigation of polymer electrolyte membrane chemical degradation and degradation mitigation using in situ fluorescence spectroscopy

    PubMed Central

    Prabhakaran, Venkateshkumar; Arges, Christopher G.; Ramani, Vijay

    2012-01-01

    A fluorescent molecular probe, 6-carboxy fluorescein, was used in conjunction with in situ fluorescence spectroscopy to facilitate real-time monitoring of degradation inducing reactive oxygen species within the polymer electrolyte membrane (PEM) of an operating PEM fuel cell. The key requirements of suitable molecular probes for in situ monitoring of ROS are presented. The utility of using free radical scavengers such as CeO2 nanoparticles to mitigate reactive oxygen species induced PEM degradation was demonstrated. The addition of CeO2 to uncatalyzed membranes resulted in close to 100% capture of ROS generated in situ within the PEM for a period of about 7 h and the incorporation of CeO2 into the catalyzed membrane provided an eightfold reduction in ROS generation rate. PMID:22219367

  1. Degradation of amine-based water treatment polymers during chloramination as N-nitrosodimethylamine (NDMA) precursors.

    PubMed

    Park, Sang-Hyuck; Wei, Shuting; Mizaikoff, Boris; Taylor, Amelia E; Favero, Cedrick; Huang, Ching-Hua

    2009-03-01

    Recent studies indicated that water treatment polymers such as poly(epichlorohydrin dimethylamine) (polyamine) and poly(diallyldimethylammonium chloride) (polyDADMAC) may form N-nitrosodimethylamine (NDMA) when in contact with chloramine water disinfectants. To minimize such potential risk and improve the polymer products, the mechanisms of how the polymers behave as NDMA precursors need to be elucidated. Direct chloramination of polymers and intermediate monomers in reagent water was conducted to probe the predominant mechanisms. The impact of polymer properties including polymer purity, polymer molecular weight and structure, residual dimethylamine (DMA), and other intermediate compounds involved in polymer synthesis, and reaction conditions such as pH, oxidant dose, and contact time on the NDMA formation potential (NDMA-FP) was investigated. Polymer degradation after reaction with chloramines was monitored at the molecular level using FT-IR and Raman spectroscopy. Overall, polyamines have greater NDMA-FP than polyDADMAC, and the NDMA formation from both polymers is strongly related to polymer degradation and DMA release during chloramination. Polyamines' tertiary amine chain ends play a major role in their NDMA-FP, while polyDADMACs' NDMA-FP is related to degradation of the quaternary ammonium ring group.

  2. Characterization and characteristics of degradable polymer sacks

    SciTech Connect

    Davis, Georgina

    2003-10-15

    This paper reviews the categories and characteristics of degradable polymers used to manufacture sacks for the collection and subsequent treatment of organic wastes from householders. The characteristics of polyethylene (PE) and starch-based sacks were examined using a number of different methods, including scanning electron microscopy (SEM), chemical analysis and mechanical strength testing of the sacks during their use. The analyses revealed that the characteristics of the PE and starch-based sacks were very different. Photomicrographs indicated that the surface of the PE sack was much smoother than the surface of the starch-based sacks. Polyethylene sacks exhibited a greater mechanical strength, both in the unused state and over time during householder use. The severe loss of mechanical strength during use of the starch-based sacks indicated that only thicker gauge sacks were suitable for the fortnightly kerbside collection of biodegradable municipal waste (BMW). Chemical analysis of two different PE sacks indicated that transition metals and other elements were commonly incorporated into the PE structure in order to facilitate increased polymer degradation.

  3. Development and investigation of flexible polymer neural probe for chronic neural recording

    NASA Astrophysics Data System (ADS)

    Smith, Courtney; Song, Kyo D.; Yoon, Hargsoon; Kim, Woong-Ki; Zeng, Tao; Sanford, Larry D.

    2012-04-01

    Neural recording through microelectrodes requires biocompatibility and long term chronic usage. With a potential for various applications and effort to improve the performance of neural recording probes, consideration is taken to the tissue and cellular effects in these device designs. The degeneration of neurons due to brain tissue motion is an issue along with brain tissue inflammation in the insertion of the probes. To account for motion and irritation the material structure of the probes must be improved upon. This research presents the fabrication of neural probes on the microscale utilizing flexible polymers. Polyimide neural probes have been considered possibly to reduce degradation in their variability caused by brain motion. The microfabrication of the polyimide neural probe has an increased flexibility while accounting for biocompatibility and the needs for chronic use. Through microfabrication processes a needle probe is produced and tested for neural recording.

  4. Polymeric photoresist nanoparticles: light-induced degradation of hydrophobic polymers in aqueous dispersion.

    PubMed

    Klinger, Daniel; Landfester, Katharina

    2011-12-15

    Nanoparticles consisting of a photoreactive polymer able to radically switch its hydrophobicity are successfully prepared by miniemulsion polymerization. Irradiation with UV light causes degradation of the particles where at complete dissolution is achieved by changing the initial hydrophobic photoresist polymer into hydrophilic poly(methacrylic acid). Incorporation of the fluorescence-sensitive Nile red serves as a solvatochromic probe to study the particle degradation. Diffusion of either Nile red out from or water into the former hard spherical nanoparticles is studied and not only renders the described material an ideal system for applications, where in situ dissolution of nanoparticles may be needed, but also bears the additional advantage of performing controlled burst release.

  5. FOREWORD: Focus on the Degradation and Stability of Polymers

    NASA Astrophysics Data System (ADS)

    Terano, Minoru

    2008-06-01

    Modern society is so reliant on polymers that products incorporating these macromolecules are almost 'invisible'. Polymers are indispensable materials used for manufacturing compact disks, clothes, lightweight airplanes, automobiles, footware and even the humble polystyrene boxes for packing our favorite hamburgers and fries. But, like many other materials, polymers degrade and become unstable, so a deeper understanding of the physical mechanisms responsible for degradation is necessary to address issues such as potential applications, recycling and the impact of polymer-products on the environment. In particular, polymers are highly vulnerable to oxidative degradation at elevated temperatures and in sunlight. Unfortunately, in spite of extensive research on polymer degradation, our knowledge is still incomplete. The analysis of polymer degradation and stability has recently become harder and more complicated because of the wider range of polymer applications, including blends and composites. Notably, composites with nanofillers are being studied for automotive, electrical and other industrial applications. With this background, the 1st International Symposium on Ultimate Stability of NanoStructured Polymers and Composites (NT2007) was held in October at the Japan Advanced Institute of Science and Technology in Ishikawa Prefecture. The meeting provided a forum to discuss advanced research achievements to resolve problems in this field of research. The papers selected for this focus issue describe recent discoveries on the stability, weatherability and flame retardancy of polymers, as well as providing an insight into degradation mechanisms of nanostructured polymers and composites. We hope that this focus issue will serve as a timely source of information about one of the most important topics in polymer science and related technologies.

  6. Thermal Degradation of Lead Monoxide Filled Polymer Composite Radiation Shields

    NASA Astrophysics Data System (ADS)

    Harish, V.; Nagaiah, N.

    2011-07-01

    Lead monoxide filled Isophthalate resin particulate polymer composites were prepared with different filler concentrations and investigated for physical, thermal, mechanical and gamma radiation shielding characteristics. This paper discusses about the thermo gravimetric analysis of the composites done to understand their thermal properties especially the effect of filler concentration on the thermal stability & degradation rate of composites. Pristine polymer exhibits single stage degradation whereas filled composites exhibit two stage degradation processes. Further, the IDT values as well as degradation rates decrease with the increased filler content in the composite.

  7. Thermal Degradation of Lead Monoxide Filled Polymer Composite Radiation Shields

    SciTech Connect

    Harish, V.; Nagaiah, N.

    2011-07-15

    Lead monoxide filled Isophthalate resin particulate polymer composites were prepared with different filler concentrations and investigated for physical, thermal, mechanical and gamma radiation shielding characteristics. This paper discusses about the thermo gravimetric analysis of the composites done to understand their thermal properties especially the effect of filler concentration on the thermal stability and degradation rate of composites. Pristine polymer exhibits single stage degradation whereas filled composites exhibit two stage degradation processes. Further, the IDT values as well as degradation rates decrease with the increased filler content in the composite.

  8. REGULATION OF COAL POLYMER DEGRADATION BY FUNGI

    SciTech Connect

    John A. Bumpus

    1998-11-30

    A variety of lignin degrading fungi mediate solubilization and subsequent biodegradation of coal macromolecules (a.k.a. coal polymer) from highly oxidized low rank coals such as leonardites. It appears that oxalate or possibly other metal chelators (i.e., certain Krebs Cycle intermediates) mediate solubilization of low rank coals while extracellular oxidases have a role in subsequent oxidation of solubilized coal macromolecule. These processes are under nutritional control. For example, in the case of P. chrysosporium, solubilization of leonardite occurred when the fungi were cultured on most but not all nutrient agars tested and subsequent biodegradation occurred only in nutrient nitrogen limited cultures. Lignin peroxidases mediate oxidation of coal macromolecule in a reaction that is dependent on the presence of veratryl alcohol and hydrogen peroxide. Kinetic evidence suggests that veratryl alcohol is oxidized to the veratryl alcohol cation radical which then mediates oxidation of the coal macromolecule. Results by others suggest that Mn peroxidases mediate formation of reactive Mn{sup 3+} complexes which also mediate oxidation of coal macromolecule. A biomimetic approach was used to study solubilization of a North Dakota leonardite. It was found that a concentration {approximately}75 mM sodium oxalate was optimal for solubilization of this low rank coal. This is important because this is well above the concentration of oxalate produced by fungi in liquid culture. Higher local concentrations probably occur in solid agar cultures and thus may account for the observation that greater solubilization occurs in agar media relative to liquid media. The characteristics of biomimetically solubilized leonardite were similar to those of biologically solubilized leonardite. Perhaps our most interesting observation was that in addition to oxalate, other common Lewis bases (phosphate/hydrogen phosphate/dihydrogen phosphate and bicarbonate/carbonate ions) are able to mediate

  9. Direct probing of a polymer electrolyte/luminescent conjugated polymer mixed ionic/electronic conductor.

    PubMed

    Hu, Yufeng; Gao, Jun

    2009-12-30

    What will happen if one brings two metallic probes into direct contact with a polymer film and apply a voltage bias? We demonstrate that, for a mixed ionic/electronic conductor containing a luminescent conjugated polymer and a polymer electrolyte, it is possible to induce strong in situ electrochemical doping of the luminescent polymer and form a dynamic light-emitting p-n junction. Using time-lapse fluorescence imaging, we have visualized p- and n-doping of various shapes and shades, p-n junction electroluminescence, and the effects of voltage reversal. The direct probing technique offers great simplicity and versatility for studying luminescent mixed ionic/electronic conductors.

  10. Degradable Polymer Composites Fabricated from Starch and Alkyl Cyanoacrylate Monomer

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Degradable polymer composites are fabricated from alkyl cyanoacrylate monomer and starch without special equipment. Alkyl cyanoacrylate, which is a major component of “super glue”, is a monomer that polymerizes at room temperature in the presence of initiators. During the fabrication of polymer com...

  11. Thermal Degradation and Identification of Heat-Sensitive Polymers

    ERIC Educational Resources Information Center

    Clough, Stuart C.; Goldman, Emma W.

    2005-01-01

    A study demonstrates the thermal degradation of two heat-sensitive polymers, namely, polystyrene and poly (methyl methacrylate). The experiment described in the study introduces undergraduate students to polymer structure as well as the application of spectroscopic techniques to the solution of structural problems.

  12. A direct evidence of morphological degradation on a nanometer scale in polymer solar cells.

    PubMed

    Schaffer, Christoph J; Palumbiny, Claudia M; Niedermeier, Martin A; Jendrzejewski, Christian; Santoro, Gonzalo; Roth, Stephan V; Müller-Buschbaum, Peter

    2013-12-10

    In situ measurement of a polymer solar cell using micro grazing incidence small angle X-ray scattering (μGISAXS) and current-voltage tracking is demonstrated. While measuring electric characteristics under illumination, morphological changes are probed by μGISAXS. The X-ray beam (green) impinges on the photo active layer with a shallow angle and scatters on a 2d detector. Degradation is explained by the ongoing nanomorphological changes observed.

  13. Ultrafast resorbing polymers for use as carriers for cortical neural probes.

    PubMed

    Lewitus, Dan; Smith, Karen L; Shain, William; Kohn, Joachim

    2011-06-01

    We have identified a polymeric system based on a novel tyrosine-derived terpolymer that offers desirable insertion capability for flexible neural prosthetic devices. To test this concept, flexible films were coated with this terpolymer and their suitability for peranchyma insertion was visualized. The effect of the polymer on neural recording was evaluated using coated microwire probes. The stiff but readily resorbable polymer rapidly degrades (molecular weight half-life of 170 min) while turning into a soft gel, followed by complete resorption within 240 min. This polymeric platform maintains sufficient stiffness to facilitate pial penetration with a dry elastic modulus of 393±44 MPa but loses its strength within 30 min once immersed in saline. In vitro, the polymer's ability to locally deliver dexamethasone has been confirmed through a first order release profile over a 360 min period. In vitro, coated microwire probes regained their original impedance values of 0.5 KΩ within 20 min of wetting via water absorption and polymer resorption. In vivo, the retention of electrical recording capability was also demonstrated through multiple waveform detection in live animals. The ultrafast resorbing polymer as a platform to facilitate the implantation of micronized flexible probes can be utilized in future designs of chronic neural devices.

  14. Mechanisms of Polymer Curing and Thermal Degradation

    DTIC Science & Technology

    1979-12-01

    polymerization. By analogy with simple conjugated polyenes , the protonated polymers, in particular that of the model compound in Fig. 8b, exhibit weak bands at 960...3.1 ppm, indicative of pendant ethynyl groups. The relative intensities of the ethynyl and aromatic protons are consistent with the polyene structure...reasonable agreement between the observed and estimated chemical shifts supports the polyene structure assumed for each polymer. Changes in 13C spectra

  15. Holographic Grating Relaxation Studies of Probe Diffusion in Amorphous Polymers

    DTIC Science & Technology

    1994-06-15

    Relaxation, Chromophore Diffusion in PS, PMMA, PVAc, Polybutadiene, Polyethylmethacryla ;% PRICE cooE Effects of Glass Transition, chain branching. 17...properties such as molecular weight, glass transition temperature (Tg) and chain conformation on the probe diffusion coefficient, and effects of polymer...crosslinking and plasticising on the same process are also studied. Page 4 Experimental Matels • Camphorquinone (CQ), thymorquinone (TM) and diacetyl (DA

  16. The use of scanning probe microscopy to characterize polymer blends

    SciTech Connect

    Joseph, T.; Yao, L.; Beatty, C.L.

    1996-12-31

    The use of scanning probe microscopy for the examination of atomic scale phenomena in polymers has been well documented, but the use of scanning probe microscopy to examine submicron scale structures has not been well documented. The purpose of this project was to examine the structure of polymer blends on a submicron scale. Two different systems were studied; a blend of recycled thermoplastics and a blend of ground rubber tire particles in a polystyrene matrix. Topographical images, z modulation plots, internal sensor measurements, and lateral force microscopy images were obtained for both systems. The plots were compared to the structures that we were expected to obtain. A second method of mathematical analysis, fractal dimension measurement, was also performed on the topographical images. Fractal dimension measurement has been correlated to fracture toughness in homopolymers, but the correlation has not been established for polymer blends. Comparison of both methods will be shown.

  17. Mechanisms of polymer degradation using an oxygen plasma generator

    NASA Technical Reports Server (NTRS)

    Colony, Joe A.; Sanford, Edward L.

    1987-01-01

    An RF oxygen plasma generator was used to produce polymer degradation which appears to be similar to that which has been observed in low Earth orbit. Mechanisms of this type of degradation were studied by collecting the reaction products in a cryogenic trap and identifying the molecular species using infrared, mass spectral, and X-ray diffraction techniques. No structurally dependent species were found from Kapton, Teflon, or Saran polymers. However, very reactive free radical entities are produced during the polymer degradation, as well as carbon dioxide and water. Reactions of the free radicals with the glass reaction vessel, with copper metal in the cold trap, and with a triphenyl phosphate scavenger in the cold trap, demonstrated the reactivity of the primary products.

  18. Ultrasound-enhanced polymer degradation and release of incorporated substances.

    PubMed Central

    Kost, J; Leong, K; Langer, R

    1989-01-01

    The effect of ultrasound on the degradation of polymers and the release rate of incorporated molecules within those polymers was examined. Up to 5-fold reversible increases in degradation rate and up to 20-fold reversible increases in release rate of incorporated molecules were observed with biodegradable polyanhydrides, polyglycolides, and polylactides. Up to 10-fold reversible increases in release rate of incorporated molecules within nonerodible ethylene/vinyl acetate copolymer were also observed. The release rate increased in proportion to the intensity of ultrasound. Temperature and mixing were relatively unimportant in effecting enhanced polymer degradation, whereas cavitation appeared to play a significant role. Increased release rates were also observed when ultrasound was applied to biodegradable polymers implanted in rats. Histological examination revealed no differences between normal rat skin and rat skin that had been exposed to ultrasonic radiation for 1 hr. With further study, ultrasound may prove useful as a way of externally regulating release rates from polymers in a variety of situations where on-demand release is required. Images PMID:2813349

  19. Degradation Testing of Fluorotelomer-based polymers (FTPs)

    EPA Science Inventory

    Over the last decade, concern about sources of per and polyfluorochemicals (PFCs) have led to an increasing need for information on the microbial and/or abiotic degradation of polymer materials that contain PFC structural fragments that may be released. EPA, OECD, ASTM and other...

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. Water and UV degradable lactic acid polymers

    SciTech Connect

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

    1990-06-26

    A water and UV light degradable copolymer of monomers of lactic acid and a modifying monomer selected from the class consisting of ethylene and polyethylane glycols (PVB 6/22/90), propylene and and polypropylene (PVB 6/22/90) 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.

  5. Spin Transfer in Polymer Degradation of Abnormal Linkage

    NASA Astrophysics Data System (ADS)

    Yu, Tianrong; Tian, Chuanjin; Liu, Xizhe; Wang, Jia; Gao, Yang; Wang, Zhigang

    2016-09-01

    The degradation of polymer materials plays an important role in production and life. In this work, the degradation mechanism of poly-α-methylstyrene (PAMS) tetramers with abnormal linkage was investigated by using density functional theory (DFT). Calculated results indicate that the head-to-head and the tail-to-tail reactions needed to overcome the energy barriers are about 0.15 eV and about 1.26 eV, respectively. The broken C-C bond at the unsaturated end of the chain leads to the dissociation of alpha-methylstyrene (AMS) monomers one by one. Furthermore, the analyses of bond characteristics are in good agreement with the results of energy barriers. In addition, the spin population analysis presents an interesting net spin transfer process in depolymerization reactions. We hope that the current theoretical results provide useful help to understand the degradation mechanism of polymers.

  6. Partial Discharge Degradation of Several Biodegradable Polymers

    NASA Astrophysics Data System (ADS)

    Fuse, Norikazu; Fujita, Shinjiro; Hirai, Naoshi; Tanaka, Toshikatsu; Kozako, Masahiro; Kohtoh, Masanori; Okabe, Shigemitsu; Ohki, Yoshimichi

    Partial discharge (PD) resistance was examined by applying a constant voltage for four kinds of biodegradable polymers, i.e. poly-L-lactic acid (PLLA), polyethylene terephthalate succinate (PETS), poly ε-caprolactone butylene succinate (PCL-BS), and polybutylene succinate (PBS), and the results were compared with those of low density polyethylene (LDPE) and crosslinked low density polyethylene (XLPE). The PD resistance is determined by the erosion depth and the surface roughness caused by PDs, and is ranked as LDPE ≅ XLPE > PLLA ≅ PETS > PBS > PCL-BS. This means that the sample with a lower permittivity has better PD resistance. Furthermore, observations of the sample surface by a polarization microscope and a laser confocal one reveal that crystalline regions with spherulites are more resistant to PDs than amorphous regions. Therefore, good PD resistance can be achieved by the sample with a high crystallinity and a low permittivity.

  7. Branched Macromolecular Architectures for Degradable, Multifunctional Phosphorus-Based Polymers.

    PubMed

    Henke, Helena; Brüggemann, Oliver; Teasdale, Ian

    2017-02-01

    This feature article briefly highlights some of the recent advances in polymers in which phosphorus is an integral part of the backbone, with a focus on the preparation of functional, highly branched, soluble polymers. A comparison is made between the related families of materials polyphosphazenes, phosphazene/phosphorus-based dendrimers and polyphosphoesters. The work described herein shows this to be a rich and burgeoning field, rapidly catching up with organic chemistry in terms of the macromolecular synthetic control and variety of available macromolecular architectures, whilst offering unique property combinations not available with carbon backbones, such as tunable degradation rates, high multi-valency and facile post-polymerization functionalization. As an example of their use in advanced applications, we highlight some investigations into their use as water-soluble drug carriers, whereby in particular the degradability in combination with multivalent nature has made them useful materials, as underlined by some of the recent studies in this area.

  8. Probing nano-rheology in thin polymer films

    NASA Astrophysics Data System (ADS)

    Dalnoki-Veress, Kari

    2013-03-01

    In this talk I will summarize our recent work on using stepped films to uncover some of the physics relevant to polymer rheology on length scales comparable to the size of polymer molecules. The work presented will focus on the efforts of a larger collaboration (Elie Raphael's theory group in Paris and James Forrest's group in Waterloo). The simple geometry of a polymer film on a substrate with a step at the free surface is unfavourable due to the excess interface induced by the step. Laplace pressure will drive flow within the film which can be studied with optical and atomic force microscopies. Because of the excellent agreement between theory and experiment when we probe ``bulk-like'' properties, these studies provide an opportunity to study how such systems transition from the bulk to confined. Starting with some of the results of levelling experiments on simple stepped films as well as the levelling of polymer droplets on thin films, I will finish with a discussion on our more recent efforts to elucidate confinement effects.

  9. Mesoscale Polymer Dissolution Probed by Raman Spectroscopy and Molecular Simulations

    SciTech Connect

    Chang, Tsun-Mei; Xantheas, Sotiris S.; Vasdekis, Andreas E.

    2016-10-13

    The diffusion of various solvents into a polystyrene (PS) matrix was probed experimentally by monitoring the temporal profiles of the Raman spectra and theoretically from molecular dynamics (MD) simulations of the binary system. The simulation results assist in providing a fundamental, molecular level connection between the mixing/dissolution processes and the difference = solvent – PS in the values of the Hildebrand parameter () between the two components of the binary systems: solvents having similar values of with PS (small ) exhibit fast diffusion into the polymer matrix, whereas the diffusion slows down considerably when the ’s are different (large ). To this end, the Hildebrand parameter was identified as a useful descriptor that governs the process of mixing in polymer – solvent binary systems. The experiments also provide insight into further refinements of the models specific to non-Fickian diffusion phenomena that need to be used in the simulations.

  10. Development of degradable renewable polymers and stimuli-responsive nanocomposites

    NASA Astrophysics Data System (ADS)

    Eyiler, Ersan

    The overall goal of this research was to explore new living radical polymerization methods and the blending of renewable polymers. Towards this latter goal, polylactic acid (PLA) was blended with a new renewable polymer, poly(trimethylene-malonate) (PTM), with the aim of improving mechanical properties, imparting faster degradation, and examining the relationship between degradation and mechanical properties. Blend films of PLA and PTM with various ratios (5, 10, and 20 wt %) were cast from chloroform. Partially miscible blends exhibited Young's modulus and elongation-to-break values that significantly extend PLA's usefulness. Atomic force microscopy (AFM) data showed that incorporation of 10 wt% PTM into PLA matrix exhibited a Young's modulus of 4.61 GPa, which is significantly higher than that of neat PLA (1.69 GPa). The second part of the bioplastics study involved a one-week hydrolytic degradation study of PTM and another new bioplastic, poly(trimethylene itaconate) (PTI) using DI water (pH 5.4) at room temperature, and the effects of degradation on crystallinity and mechanical properties of these films were examined by differential scanning calorimetry (DSC) and AFM. PTI showed an increase in crystallinity with degradation, which was attributed to predominately degradation of free amorphous regions. Depending on the crystallinity, the elastic modulus increased at first, and decreased slightly. Both bulk and surface-tethered stimuli-responsive polymers were studied on amine functionalized magnetite (Fe3O4) nanoparticles. Stimuli-responsive polymers studied, including poly(N-isopropylacrylamide) (PNIPAM), poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA), and poly(itaconic acid) (PIA), were grafted via surface-initiated aqueous atom transfer radical polymerization (SI-ATRP). Both Fourier transform infrared spectroscopy (FTIR) and x-ray photoelectron spectroscopy (XPS) spectroscopies showed the progression of the grafting. The change in particle size as a

  11. Stable Isotope Probing Approaches to Study Anaerobic Hydrocarbon Degradation and Degraders.

    PubMed

    Vogt, Carsten; Lueders, Tillmann; Richnow, Hans H; Krüger, Martin; von Bergen, Martin; Seifert, Jana

    2016-01-01

    Stable isotope probing (SIP) techniques have become state-of-the-art in microbial ecology over the last 10 years, allowing for the targeted detection and identification of organisms, metabolic pathways and elemental fluxes active in specific processes within complex microbial communities. For studying anaerobic hydrocarbon-degrading microbial communities, four stable isotope techniques have been used so far: DNA/RNA-SIP, PLFA (phospholipid-derived fatty acids)-SIP, protein-SIP, and single-cell-SIP by nanoSIMS (nanoscale secondary ion mass spectrometry) or confocal Raman microscopy. DNA/RNA-SIP techniques are most frequently applied due to their most meaningful phylogenetic resolution. Especially using 13C-labeled benzene and toluene as model substrates, many new hydrocarbon degraders have been identified by SIP under various electron acceptor conditions. This has extended the current perspective of the true diversity of anaerobic hydrocarbon degraders relevant in the environment. Syntrophic hydrocarbon degradation was found to be a common mechanism for various electron acceptors. Fundamental concepts and recent advances in SIP are reflected here. A discussion is presented concerning how these techniques generate direct insights into intrinsic hydrocarbon degrader populations in environmental systems and how useful they are for more integrated approaches in the monitoring of contaminated sites and for bioremediation.

  12. Quantitation of buried contamination by use of solvents. [degradation of silicone polymers by amine solvents

    NASA Technical Reports Server (NTRS)

    Pappas, S. P.; Hsiao, Y. C.; Hill, L. W.

    1973-01-01

    Spore recovery form cured silicone potting compounds using amine solvents to degrade the cured polymers was investigated. A complete list of solvents and a description of the effect of each on two different silicone polymers is provided.

  13. Aliphatic polyester block polymers: renewable, degradable, and sustainable.

    PubMed

    Hillmyer, Marc A; Tolman, William B

    2014-08-19

    Nearly all polymers are derived from nonrenewable fossil resources, and their disposal at their end of use presents significant environmental problems. Nonetheless, polymers are ubiquitous, key components in myriad technologies and are simply indispensible for modern society. An important overarching goal in contemporary polymer research is to develop sustainable alternatives to "petro-polymers" that have competitive performance properties and price, are derived from renewable resources, and may be easily and safely recycled or degraded. Aliphatic polyesters are particularly attractive targets that may be prepared in highly controlled fashion by ring-opening polymerization of bioderived lactones. However, property profiles of polyesters derived from single monomers (homopolymers) can limit their applications, thus demanding alternative strategies. One such strategy is to link distinct polymeric segments in an A-B-A fashion, with A and B chosen to be thermodynamically incompatible so that they can self-organize on a nanometer-length scale and adopt morphologies that endow them with tunable properties. For example, such triblock copolymers can be useful as thermoplastic elastomers, in pressure sensitive adhesive formulations, and as toughening modifiers. Inspired by the tremendous utility of petroleum-derived styrenic triblock copolymers, we aimed to develop syntheses and understand the structure-property profiles of sustainable alternatives, focusing on all renewable and all readily degradable aliphatic polyester triblocks as targets. Building upon oxidation chemistry reported more than a century ago, a constituent of the peppermint plant, (-)-menthol, was converted to the ε-caprolactone derivative menthide. Using a diol initiator and controlled catalysis, menthide was polymerized to yield a low glass transition temperature telechelic polymer (PM) that was then further functionalized using the biomass-derived monomer lactide (LA) to yield fully renewable PLA

  14. Modeling the Insertion Mechanics of Flexible Neural Probes Coated with Sacrificial Polymers for Optimizing Probe Design

    PubMed Central

    Singh, Sagar; Lo, Meng-Chen; Damodaran, Vinod B.; Kaplan, Hilton M.; Kohn, Joachim; Zahn, Jeffrey D.; Shreiber, David I.

    2016-01-01

    Single-unit recording neural probes have significant advantages towards improving signal-to-noise ratio and specificity for signal acquisition in brain-to-computer interface devices. Long-term effectiveness is unfortunately limited by the chronic injury response, which has been linked to the mechanical mismatch between rigid probes and compliant brain tissue. Small, flexible microelectrodes may overcome this limitation, but insertion of these probes without buckling requires supporting elements such as a stiff coating with a biodegradable polymer. For these coated probes, there is a design trade-off between the potential for successful insertion into brain tissue and the degree of trauma generated by the insertion. The objective of this study was to develop and validate a finite element model (FEM) to simulate insertion of coated neural probes of varying dimensions and material properties into brain tissue. Simulations were performed to predict the buckling and insertion forces during insertion of coated probes into a tissue phantom with material properties of brain. The simulations were validated with parallel experimental studies where probes were inserted into agarose tissue phantom, ex vivo chick embryonic brain tissue, and ex vivo rat brain tissue. Experiments were performed with uncoated copper wire and both uncoated and coated SU-8 photoresist and Parylene C probes. Model predictions were found to strongly agree with experimental results (<10% error). The ratio of the predicted buckling force-to-predicted insertion force, where a value greater than one would ideally be expected to result in successful insertion, was plotted against the actual success rate from experiments. A sigmoidal relationship was observed, with a ratio of 1.35 corresponding to equal probability of insertion and failure, and a ratio of 3.5 corresponding to a 100% success rate. This ratio was dubbed the “safety factor”, as it indicated the degree to which the coating should be over

  15. Modeling the Insertion Mechanics of Flexible Neural Probes Coated with Sacrificial Polymers for Optimizing Probe Design.

    PubMed

    Singh, Sagar; Lo, Meng-Chen; Damodaran, Vinod B; Kaplan, Hilton M; Kohn, Joachim; Zahn, Jeffrey D; Shreiber, David I

    2016-03-04

    Single-unit recording neural probes have significant advantages towards improving signal-to-noise ratio and specificity for signal acquisition in brain-to-computer interface devices. Long-term effectiveness is unfortunately limited by the chronic injury response, which has been linked to the mechanical mismatch between rigid probes and compliant brain tissue. Small, flexible microelectrodes may overcome this limitation, but insertion of these probes without buckling requires supporting elements such as a stiff coating with a biodegradable polymer. For these coated probes, there is a design trade-off between the potential for successful insertion into brain tissue and the degree of trauma generated by the insertion. The objective of this study was to develop and validate a finite element model (FEM) to simulate insertion of coated neural probes of varying dimensions and material properties into brain tissue. Simulations were performed to predict the buckling and insertion forces during insertion of coated probes into a tissue phantom with material properties of brain. The simulations were validated with parallel experimental studies where probes were inserted into agarose tissue phantom, ex vivo chick embryonic brain tissue, and ex vivo rat brain tissue. Experiments were performed with uncoated copper wire and both uncoated and coated SU-8 photoresist and Parylene C probes. Model predictions were found to strongly agree with experimental results (<10% error). The ratio of the predicted buckling force-to-predicted insertion force, where a value greater than one would ideally be expected to result in successful insertion, was plotted against the actual success rate from experiments. A sigmoidal relationship was observed, with a ratio of 1.35 corresponding to equal probability of insertion and failure, and a ratio of 3.5 corresponding to a 100% success rate. This ratio was dubbed the "safety factor", as it indicated the degree to which the coating should be over

  16. Probing the Contact and Sliding of Elastomer/Polymer Interfaces

    NASA Astrophysics Data System (ADS)

    Yurdumakan, Betul; Nanjundiah, Kumar; Dhinojwala, Ali

    2006-03-01

    In this study, we have designed a novel approach to couple interface sensitive infrared-visible sum frequency generation (SFG) spectroscopy with adhesion and friction experiments. This provides a direct probe of the interfacial structure in terms of orientation and density of molecules during contact and sliding which is important in understanding the molecular origin of adhesion and friction. Here, we show that the friction forces between poly(dimethyl siloxane) (PDMS) lens and glassy poly(styrene) (PS) are 4 times higher than PDMS sliding on surfaces of crystalline alkyl side chain comb polymers. This cannot be explained by the differences in adhesion energy or hysteresis. The in-situ SFG measurements indicate local interdigitation during contact, which is evident from the decrease in the number of oriented phenyl groups at the interface. The local penetration is unexpected at room temperature (TR) that is much below the Tg of PS. For comparison, we have also studied poly(n-butyl methacrylate) and poly(n-propyl methacrylate) having Tg above and below TR, respectively. Both of these polymers show similar adhesion and friction forces as PS. The SFG results indicate that local changes in interfacial structure affect friction, regardless of the bulk Tg. These results also show that the adhesion energy and hysteresis are not sufficient to predict friction, which makes the characterization of the molecular structure during contact and sliding essential.

  17. Cellulose acetate polymer film modified microstructured polymer optical fiber towards a nitrite optical probe

    NASA Astrophysics Data System (ADS)

    Li, Dongdong; Wang, Lili

    2010-07-01

    A novel microstructured polymer optical fiber (MPOF) probe for nitrites (NO 2-) detection was made by forming rhodamine 6G (Rh 6G)-doped cellulose acetate (CA) on the side wall of array holes in a MPOF. It was found that the MPOF probe only have a response to nitrites in a certain concentration of sulfuric acid solution. The calibration graph of fluorescence intensity versus nitrites concentration was linear in the range of 2.0 × 10 - 4 g/ml-5.0 × 10 - 3 g/ml. The method possesses ease of chemical modification, low cost design, and potential for direct integration with existing instrumentation, and has been applied to the determination of nitrites in real samples with satisfactory results.

  18. A model for calculating polymer injectivity including the effects of shear degradation

    SciTech Connect

    Sorbie, K.S.; Roberts, L.J.

    1984-04-01

    Polymers are frequently injected into oil reservoirs in order to improve recovery. As they reduce the in-situ mobility of the aqueous phase (either by viscosity increase or permeability reduction), the fluid injectivity generally drops. It is very useful to be able to estimate in advance from a few laboratory measured quantities the injectivity of the polymer and whether the polymer is likely to be seriously degraded by the high shear experienced in the near-wellbore region. It is difficult to calculate the injectivity of the polymer solutions due to their complex rheological behaviour within porous media, especially when the polymer mechanically degrades. In this paper, the authors investigate one approach to calculating the injectivity of polymers in the general case where mechanical degradation occurs. A kinetic model for polymer degradation is proposed which is used to obtain the radial viscosity profile of the degrading polymer. This may in turn be used to calculate the steady-state pressure drops associated with the degrading polymer. The model is based on a discrete multicomponent representation of the polymer molecular weight distribution (MWD). During mechanical degradation, the MWD changes as higher components degrade into lower molecular weight fragments. The degradation rate of a given component of the MWD is related to the local shear/elongational stress within the porous medium and the concentration of the component (C /SUB i/ ). The model is used to match the results of experiments studying the shear degradation of polyacrylamide (PAM) in radial sandstone cores. The quantitative predictions of the model are very satisfactory. In addition, the model gives insight into the mechanism of shear degradation of polymers in porous media.

  19. Characterization and degradation studies on synthetic polymers for aerospace application

    NASA Technical Reports Server (NTRS)

    Hsu, M. T. S.

    1982-01-01

    The anti-misting additive for jet fuels known as FM-9 (proprietary polymer) was characterized by elemental analysis, solubility studies and molecular weight determination. Physical properties of surface tension, viscosity, specific gravity and other physical parameters were determined. These results are compared with properties of polyisobutylene and fuels modified with the same; the misting characteristics of polyisobutylene and FM-9 in Jet A fuel are included. Characterization and degradation of phthalocyanine and its derivatives were accomplished by use of a mass spectrometer and a pyroprobe solid pyrolyzer. Metal phthalocyanine tetracarboxylic acids and phthalocyanine-tetraamine cured epoxies were studied. Epoxy/graphite composite panels were exposed to a NASA-Ames radiant panel fire simulator in the flaming and non-flaming modes; toxic gases of HCN and HZS were measured along with oxygen, Co2, Co, and organic gases.

  20. Analytical methods for toxic gases from thermal degradation of polymers

    NASA Technical Reports Server (NTRS)

    Hsu, M.-T. S.

    1977-01-01

    Toxic gases evolved from the thermal oxidative degradation of synthetic or natural polymers in small laboratory chambers or in large scale fire tests are measured by several different analytical methods. Gas detector tubes are used for fast on-site detection of suspect toxic gases. The infrared spectroscopic method is an excellent qualitative and quantitative analysis for some toxic gases. Permanent gases such as carbon monoxide, carbon dioxide, methane and ethylene, can be quantitatively determined by gas chromatography. Highly toxic and corrosive gases such as nitrogen oxides, hydrogen cyanide, hydrogen fluoride, hydrogen chloride and sulfur dioxide should be passed into a scrubbing solution for subsequent analysis by either specific ion electrodes or spectrophotometric methods. Low-concentration toxic organic vapors can be concentrated in a cold trap and then analyzed by gas chromatography and mass spectrometry. The limitations of different methods are discussed.

  1. Molecular degradation, injectivity, and elastic properties of polymer solutions

    SciTech Connect

    Southwick, J.G.; Manke, C.W.

    1986-01-01

    New features of polymer rheology in porous media were observed when hydrolyzed polyacrylamide (HPAM) solutions were flowed through sandstone, gravel packs, and glass bead packs at high rates. Independent measurement of elongational viscosity (eta,/sub e/) with a ductless siphon technique demonstrates that the enhanced resistance seen at high flow rates is not directly proportional to eta/sub e/. Furthermore, permeability trends in resistance factor and mechanical degradation when plotted against strain rate are discussed. When these results are translated to field flow rates and geometries they indicate that HPAM solutions can be injected at reasonable injection pressures with minimal viscosity losses provided that perforated completions are designed with either sufficient perforation density or perforation size.

  2. High Temperature Degradation Mechanisms in Polymer Matrix Composites

    NASA Technical Reports Server (NTRS)

    Cunningham, Ronan A.

    1996-01-01

    Polymer matrix composites are increasingly used in demanding structural applications in which they may be exposed to harsh environments. The durability of such materials is a major concern, potentially limiting both the integrity of the structures and their useful lifetimes. The goal of the current investigation is to develop a mechanism-based model of the chemical degradation which occurs, such that given the external chemical environment and temperatures throughout the laminate, laminate geometry, and ply and/or constituent material properties, we can calculate the concentration of diffusing substances and extent of chemical degradation as functions of time and position throughout the laminate. This objective is met through the development and use of analytical models, coupled to an analysis-driven experimental program which offers both quantitative and qualitative information on the degradation mechanism. Preliminary analyses using a coupled diffusion/reaction model are used to gain insight into the physics of the degradation mechanisms and to identify crucial material parameters. An experimental program is defined based on the results of the preliminary analysis which allows the determination of the necessary material coefficients. Thermogravimetric analyses are carried out in nitrogen, air, and oxygen to provide quantitative information on thermal and oxidative reactions. Powdered samples are used to eliminate diffusion effects. Tests in both inert and oxidative environments allow the separation of thermal and oxidative contributions to specimen mass loss. The concentration dependency of the oxidative reactions is determined from the tests in pure oxygen. Short term isothermal tests at different temperatures are carried out on neat resin and unidirectional macroscopic specimens to identify diffusion effects. Mass loss, specimen shrinkage, the formation of degraded surface layers and surface cracking are recorded as functions of exposure time. Geometry effects

  3. High Temperature Degradation Mechanisms in Polymer Matrix Composites

    NASA Technical Reports Server (NTRS)

    Cunningham, Ronan A.; McManus, Hugh L.

    1997-01-01

    Polymer matrix composites are increasingly used in demanding structural applications in which they may be exposed to harsh environments. The durability of such materials is a major concern, potentially limiting both the integrity of the structures and their useful lifetimes. The goal of the current investigation is to develop a mechanism-based model of the chemical degradation which occurs, such that given the external chemical environment and temperatures throughout the laminate, laminate geometry, and ply and/or constituent material properties, we can calculate the concentration of diffusing substances and extent of chemical degradation as functions of time and position throughout the laminate. This objective is met through the development and use of analytical models, coupled to an analysis-driven experimental program which offers both quantitative and qualitative information on the degradation mechanism. Preliminary analyses using coupled diffusion/reaction model are used to gain insight into the physics of the degradation mechanisms and to identify crucial material parameters. An experimental program is defined based on the results of the preliminary analysis which allows the determination of the necessary material coefficients. Thermogravimetric analyses are carried out in nitrogen, air, and oxygen to provide quantitative information on thermal and oxidative reactions. Powdered samples are used to eliminate diffusion effects. Tests in both inert and oxidative environments allow the separation of thermal and oxidative contributions to specimen mass loss. The concentration dependency of the oxidative reactions is determined from the tests in pure oxygen. Short term isothermal tests at different temperatures are carried out on neat resin and unidirectional macroscopic specimens to identify diffusion effects. Mass loss, specimen shrinkage, the formation of degraded surface layers and surface cracking are recorded as functions of exposure time. Geometry effects in

  4. Degradation of Ultra-High Molar Mass Polymers in Size-Exclusion Chromatography

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The degradation of high molar mass polymers during size-exclusion chromatography (SEC) analysis has been a topic of interest for several decades. Should a polymer degrade during analysis, the accuracy of the molar mass (M) and architectural information obtained will be compromised. To this effect,...

  5. Optical pump terahertz probe studies of semiconducting polymers

    NASA Astrophysics Data System (ADS)

    Cunningham, Paul D.

    Optical-pump terahertz-probe spectroscopy (OPTP) has been applied to study charge generation, transport and the evolution of the photo-induced excited states in thin film organic semiconductors, with emphasis on their relevance to photovoltaic technology. In these experiments the response of the photoexcited material to the AC electric field of a terahertz (THz) pulse was measured. From this response, the evolution of the complex conductivity in the far-infrared was monitored. OPTP presents advantages over other techniques by being an all-optical probe of the complex conductivity over nanometer scale distances with sub-picosecond resolution and exhibits particular sensitivity to carrier scattering rates, which typically lay in the THz range. Conductivity models were applied to the extracted conductivity curves in order to determine technologically relevant quantities like the charge carrier mobility and external quantum yield of charge carrier generation. We observed charge carriers generated on a subpicosecond time scale in thin films of polyhexylthiophene (P3HT). Through application of the Drude-Smith model (DSM) over the 0-2 THz band, we determined a room temperature intrinsic mobility of about 30 cm2/Vs. The temperature dependence of the conductivity dynamics showed signs of thermally activated polaron hopping influenced by torsional disorder. Both above and below gap excitation resulted in similar dynamics, showing that the majority of carriers recombine within 1 ps. We were able to observe charge transfer occurring on a sub-ps timescale to the soluble fullerene, PCBM, for both excited states, demonstrating that narrow gap polymers can be blended with PCBM for photovoltaic applications. We observed charge carrier generated on a sub-ps time scale in thin amorphous films of metalated polymers. The time evolution of the conductivity showed that charge carriers recombine and only excitons persist after 100 ps. This characteristic appears to be common to amorphous

  6. Photocatalytic degradation of methyl orange using polymer-titania microcomposites.

    PubMed

    Coutinho, Cecil A; Gupta, Vinay K

    2009-05-15

    Photodegradation of an organic dye was studied experimentally using novel polymer-titania microcomposites. These microcomposites were prepared from titanium dioxide (TiO(2)) nanoparticles embedded within cross-linked, thermally-responsive microgels of poly(N-isopropylacrylamide) and contained interpenetrating linear chains of poly(acrylic acid) that functionalize the nanoparticles of TiO(2). Because these microcomposites settle more than a hundred times faster than freely suspended TiO(2) nanoparticles, they are extremely useful for simple gravity separation of the photocatalyst in applications that employ titania nanoparticles. Methyl orange (MO) was used as a model contaminant to investigate the degradation kinetics using the microcomposites in aqueous suspensions. Kinetics of the photodegradation were evaluated by monitoring the changes in methyl orange concentration using UV-Vis spectroscopy. The photocatalytic behavior of functional microcomposites containing 65 wt% titania was studied and the influence of the solution pH as well as the total titania concentration in solution was explored. The results indicated that pH of the solution changes the surface interactions between the poly(acrylic acid), titania, and methyl orange and this interplay determined the overall degradation kinetics of the chemical contaminants. Nearly identical reaction rate constants were observed in acidic solutions for the microcomposites when compared to freely suspended titania. The latter showed higher rate constants than the microcomposites at a neutral pH. Release of the titania from the microcomposites was observed under basic conditions. Complete degradation of the microcomposites was observed after prolonged (7-13 h) UV irradiation. However, the microcomposites were easily regenerated by addition of microgels and no loss of photocatalytic activity was observed.

  7. Pathways for degradation of plastic polymers floating in the marine environment.

    PubMed

    Gewert, Berit; Plassmann, Merle M; MacLeod, Matthew

    2015-09-01

    Each year vast amounts of plastic are produced worldwide. When released to the environment, plastics accumulate, and plastic debris in the world's oceans is of particular environmental concern. More than 60% of all floating debris in the oceans is plastic and amounts are increasing each year. Plastic polymers in the marine environment are exposed to sunlight, oxidants and physical stress, and over time they weather and degrade. The degradation processes and products must be understood to detect and evaluate potential environmental hazards. Some attention has been drawn to additives and persistent organic pollutants that sorb to the plastic surface, but so far the chemicals generated by degradation of the plastic polymers themselves have not been well studied from an environmental perspective. In this paper we review available information about the degradation pathways and chemicals that are formed by degradation of the six plastic types that are most widely used in Europe. We extrapolate that information to likely pathways and possible degradation products under environmental conditions found on the oceans' surface. The potential degradation pathways and products depend on the polymer type. UV-radiation and oxygen are the most important factors that initiate degradation of polymers with a carbon-carbon backbone, leading to chain scission. Smaller polymer fragments formed by chain scission are more susceptible to biodegradation and therefore abiotic degradation is expected to precede biodegradation. When heteroatoms are present in the main chain of a polymer, degradation proceeds by photo-oxidation, hydrolysis, and biodegradation. Degradation of plastic polymers can lead to low molecular weight polymer fragments, like monomers and oligomers, and formation of new end groups, especially carboxylic acids.

  8. Insights into the Mechanism and Kinetics of Thermo-Oxidative Degradation of HFPE High Performance Polymer.

    PubMed

    Kunnikuruvan, Sooraj; Parandekar, Priya V; Prakash, Om; Tsotsis, Thomas K; Nair, Nisanth N

    2016-06-02

    The growing requisite for materials having high thermo-oxidative stability makes the design and development of high performance materials an active area of research. Fluorination of the polymer backbone is a widely applied strategy to improve various properties of the polymer, most importantly the thermo-oxidative stability. Many of these fluorinated polymers are known to have thermo-oxidative stability up to 700 K. However, for space and aerospace applications, it is important to improve its thermo-oxidative stability beyond 700 K. Molecular-level details of the thermo-oxidative degradation of such polymers can provide vital information to improve the polymer. In this spirit, we have applied quantum mechanical and microkinetic analysis to scrutinize the mechanism and kinetics of the thermo-oxidative degradation of a fluorinated polymer with phenylethenyl end-cap, HFPE. This study gives an insight into the thermo-oxidative degradation of HFPE and explains most of the experimental observations on the thermo-oxidative degradation of this polymer. Thermolysis of C-CF3 bond in the dianhydride component (6FDA) of HFPE is found to be the rate-determining step of the degradation. Reaction pathways that are responsible for the experimentally observed weight loss of the polymer is also scrutinized. On the basis of these results, we propose a modification of HFPE polymer to improve its thermo-oxidative stability.

  9. Deformation and degradation of polymers in ultra-high-pressure liquid chromatography.

    PubMed

    Uliyanchenko, Elena; van der Wal, Sjoerd; Schoenmakers, Peter J

    2011-09-28

    Ultra-high-pressure liquid chromatography (UHPLC) using columns packed with sub-2 μm particles has great potential for separations of many types of complex samples, including polymers. However, the application of UHPLC for the analysis of polymers meets some fundamental obstacles. Small particles and narrow bore tubing in combination with high pressures generate significant shear and extensional forces in UHPLC systems, which may affect polymer chains. At high stress conditions flexible macromolecules may become extended and eventually the chemical bonds in the molecules can break. Deformation and degradation of macromolecules will affect the peak retention and the peak shape in the chromatogram, which may cause errors in the obtained results (e.g. the calculated molecular-weight distributions). In the present work we explored the limitations of UHPLC for the analysis of polymers. Degradation and deformation of macromolecules were studied by collecting and re-injecting polymer peaks and by off-line two-dimensional liquid chromatography. Polystyrene standards with molecular weight of 4 MDa and larger were found to degrade at UHPLC conditions. However, for most polymers degradation could be avoided by using low linear velocities. No degradation of 3-MDa PS (and smaller) was observed at linear velocities up to 7 mm/s. The column frits were implicated as the main sources of polymer degradation. The extent of degradation was found to depend on the type of the column and on the column history. At high flow rates degradation was observed without a column being installed. We demonstrated that polymer deformation preceded degradation. Stretched polymers eluted from the column in slalom chromatography mode (elution order opposite to that in SEC or HDC). Under certain conditions we observed co-elution of large and small PS molecules though a convolution of slalom chromatography and hydrodynamic chromatography.

  10. Production of degradable polymers from food-waste streams

    SciTech Connect

    Tsai, S.P.: Coleman, R.D.; Bonsignore, P.V.; Moon, S.H.

    1992-01-01

    In the United States, billions of pounds of cheese whey permeate and approximately 10 billion pounds of potatoes processed each year are typically discarded or sold as cattle feed at $3{endash}6/ton; moreover, the transportation required for these means of disposal can be expensive. As a potential solution to this economic and environmental problem, Argonne National Laboratory is developing technology that: Biologically converts existing food-processing waste streams into lactic acid and uses lactic acid for making environmentally safe, degradable polylactic acid (PLA) and modified PLA plastics and coatings. An Argonne process for biologically converting high-carbohydrate food waste will not only help to solve a waste problem for the food industry, but will also save energy and be economically attractive. Although the initial substrate for Argonne's process development is potato by-product, the process can be adapted to convert other food wastes, as well as corn starch, to lactic acid. Proprietary technology for biologically converting greater than 90% of the starch in potato wastes to glucose has been developed. Glucose and other products of starch hydrolysis are subsequently fermented by bacteria that produce lactic acid. The lactic acid is recovered, concentrated, and further purified to a polymer-grade product.

  11. Production of degradable polymers from food-waste streams

    SciTech Connect

    Tsai, S.P.: Coleman, R.D.; Bonsignore, P.V.; Moon, S.H.

    1992-07-01

    In the United States, billions of pounds of cheese whey permeate and approximately 10 billion pounds of potatoes processed each year are typically discarded or sold as cattle feed at $3{endash}6/ton; moreover, the transportation required for these means of disposal can be expensive. As a potential solution to this economic and environmental problem, Argonne National Laboratory is developing technology that: Biologically converts existing food-processing waste streams into lactic acid and uses lactic acid for making environmentally safe, degradable polylactic acid (PLA) and modified PLA plastics and coatings. An Argonne process for biologically converting high-carbohydrate food waste will not only help to solve a waste problem for the food industry, but will also save energy and be economically attractive. Although the initial substrate for Argonne`s process development is potato by-product, the process can be adapted to convert other food wastes, as well as corn starch, to lactic acid. Proprietary technology for biologically converting greater than 90% of the starch in potato wastes to glucose has been developed. Glucose and other products of starch hydrolysis are subsequently fermented by bacteria that produce lactic acid. The lactic acid is recovered, concentrated, and further purified to a polymer-grade product.

  12. The rheology, degradation, processing, and characterization of renewable resource polymers

    NASA Astrophysics Data System (ADS)

    Conrad, Jason David

    Renewable resource polymers have become an increasingly popular alternative to conventional fossil fuel based polymers over the past couple decades. The push by the government as well as both industrial and consumer markets to go "green" has provided the drive for companies to research and develop new materials that are more environmentally friendly and which are derived from renewable materials. Two polymers that are currently being produced commercially are poly-lactic acid (PLA) and polyhydroxyalkanoate (PHA) copolymers, both of which can be derived from renewable feedstocks and have shown to exhibit similar properties to conventional materials such as polypropylene, polyethylene, polystyrene, and PET. PLA and PHA are being used in many applications including food packaging, disposable cups, grocery bags, and biomedical applications. In this work, we report on the rheological properties of blends of PLA and PHA copolymers. The specific materials used in the study include Natureworks RTM 7000D grade PLA and PHA copolymers of poly(3-hydroxybutyrate-co-3-hydroxyvalerate). Blends ranging from 10 to 50 percent PHA by weight are also examined. Shear and extensional experiments are performed to characterize the flow behavior of the materials in different flow fields. Transient experiments are performed to study the shear rheology over time in order to determine how the viscoelastic properties change under typical processing conditions and understand the thermal degradation behavior of the materials. For the blends, it is determined that increasing the PHA concentration in the blend results in a decrease in viscosity and increase in degradation. Models are fit to the viscosity of the blends using the pure material viscosities in order to be able to predict the behavior at a given blend composition. We also investigate the processability of these materials into films and examine the resultant properties of the cast films. The mechanical and thermal properties of the

  13. Metal Evaporation-Induced Degradation of Fullerene Acceptors in Polymer/Fullerene Solar Cells.

    PubMed

    Huang, Wenchao; Gann, Eliot; Thomsen, Lars; Tadich, Anton; Cheng, Yi-Bing; McNeill, Christopher R

    2016-01-27

    Surface-sensitive NEXAFS spectroscopy is used to probe the interaction between low work function metal electrodes and fullerene derivatives in organic solar cells. Evaporation of either Ca or Al electrodes onto films of the fullerene derivatives (6,6)-phenyl-C61-butyric acid methyl ester (PCBM) and indene-C60 bisadduct (ICBA) leads to a dramatic change in the observed NEXAFS spectrum. The observed changes cannot be explained only in terms of interfacial electronic doping or charge transfer, but rather point to the formation of new chemical bonds that destroy the extensive electron delocalization on the C60 cage. A combination of ex situ and in situ ultrahigh vacuum measurements indicates that metal evaporation results in a change in the electronic structure of PCBM that then facilitates chemical degradation and oxidation in the presence of oxygen. To investigate the effect of this chemical interaction on device performance, a unique transfer method to laminate the Al electrode to the top of polymer blend is used, in which case, the chemical degradation of the fullerene is not observed. Device performance of P3HT/PCBM blend solar cells in which the top metal electrode has either been thermally evaporated or transferred is then compared. These results highlight that chemical, as well as electronic, interactions between metals and organic semiconductors must be considered.

  14. Probing degradation in complex engineering silicones by 1H multiple quantum NMR

    SciTech Connect

    Maxwell, R S; Chinn, S C; Giuliani, J; Herberg, J L

    2007-09-05

    Static {sup 1}H Multiple Quantum Nuclear Magnetic Resonance (MQ NMR) has recently been shown to provide detailed insight into the network structure of pristine silicon based polymer systems. The MQ NMR method characterizes the residual dipolar couplings of the silicon chains that depend on the average molecular weight between physical or chemical constraints. Recently, we have employed MQ NMR methods to characterize the changes in network structure in a series of complex silicone materials subject to numerous degradation mechanisms, including thermal, radiative, and desiccative. For thermal degradation, MQ NMR shows that a combination of crosslinking due to post-curing reactions as well as random chain scissioning reactions occurs. For radiative degradation, the primary mechanisms are via crosslinking both in the network and at the interface between the polymer and the inorganic filler. For samples stored in highly desiccating environments, MQ NMR shows that the average segmental dynamics are slowed due to increased interactions between the filler and the network polymer chains.

  15. Polyester-based (bio)degradable polymers as environmentally friendly materials for sustainable development.

    PubMed

    Rydz, Joanna; Sikorska, Wanda; Kyulavska, Mariya; Christova, Darinka

    2014-12-29

    This review focuses on the polyesters such as polylactide and polyhydroxyalkonoates, as well as polyamides produced from renewable resources, which are currently among the most promising (bio)degradable polymers. Synthetic pathways, favourable properties and utilisation (most important applications) of these attractive polymer families are outlined. Environmental impact and in particular (bio)degradation of aliphatic polyesters, polyamides and related copolymer structures are described in view of the potential applications in various fields.

  16. Polyester-Based (Bio)degradable Polymers as Environmentally Friendly Materials for Sustainable Development

    PubMed Central

    Rydz, Joanna; Sikorska, Wanda; Kyulavska, Mariya; Christova, Darinka

    2014-01-01

    This review focuses on the polyesters such as polylactide and polyhydroxyalkonoates, as well as polyamides produced from renewable resources, which are currently among the most promising (bio)degradable polymers. Synthetic pathways, favourable properties and utilisation (most important applications) of these attractive polymer families are outlined. Environmental impact and in particular (bio)degradation of aliphatic polyesters, polyamides and related copolymer structures are described in view of the potential applications in various fields. PMID:25551604

  17. Experimental degradation of polymer shopping bags (standard and degradable plastic, and biodegradable) in the gastrointestinal fluids of sea turtles.

    PubMed

    Müller, Christin; Townsend, Kathy; Matschullat, Jörg

    2012-02-01

    The persistence of marine debris such as discarded polymer bags has become globally an increasing hazard to marine life. To date, over 177 marine species have been recorded to ingest man-made polymers that cause life-threatening complications such as gut impaction and perforation. This study set out to test the decay characteristics of three common types of shopping bag polymers in sea turtle gastrointestinal fluids (GIF): standard and degradable plastic, and biodegradable. Fluids were obtained from the stomachs, small intestines and large intestines of a freshly dead Green turtle (Chelonia mydas) and a Loggerhead turtle (Caretta caretta). Controls were carried out with salt and freshwater. The degradation rate was measured over 49 days, based on mass loss. Degradation rates of the standard and the degradable plastic bags after 49 days across all treatments and controls were negligible. The biodegradable bags showed mass losses between 3 and 9%. This was a much slower rate than reported by the manufacturers in an industrial composting situation (100% in 49 days). The GIF of the herbivorous Green turtle showed an increased capacity to break down the biodegradable polymer relative to the carnivorous Loggerhead, but at a much lower rate than digestion of natural vegetative matter. While the breakdown rate of biodegradable polymers in the intestinal fluids of sea turtles is greater than standard and degradable plastics, it is proposed that this is not rapid enough to prevent morbidity. Further study is recommended to investigate the speed at which biodegradable polymers decompose outside of industrial composting situations, and their durability in marine and freshwater systems.

  18. Formation of microscopic particles during the degradation of different polymers.

    PubMed

    Lambert, Scott; Wagner, Martin

    2016-10-01

    This study investigated the formation and size distribution of microscopic plastic particles during the degradation of different plastic materials. Particle number concentrations in the size range 30 nm-60 μm were measured by nanoparticle tracking analysis (NTA) and Coulter Counter techniques. Each of the plastics used exhibited a measureable increase in the release of particles into the surrounding solution, with polystyrene (PS) and polylactic acid (PLA) generating the highest particle concentrations. After 112 d, particle concentrations ranged from 2147 particles ml(-1) in the control (C) to 92,465 particles ml(-1) for PS in the 2-60 μm size class; 1.2 × 10(5) particles ml(-1) (C) to 11.6 × 10(6) for PLA in the 0.6-18 μm size class; and 0.2 × 10(8) particles ml(-1) (C) to 6.4 × 10(8) particles ml(-1) for PS in the 30-2000 nm size class (84 d). A classification of samples based on principal component analysis showed a separation between the different plastic types, with PLA clustering individually in each of the three size classes. In addition, particle size distribution models were used to examine more closely the size distribution data generated by NTA. Overall, the results indicate that at the beginning of plastic weathering processes chain scission at the polymer surface causes many very small particles to be released into the surrounding solution and those concentrations may vary between plastic types.

  19. BET, thermal degradation, and FTIR spectras of triazine polyamine polymers.

    PubMed

    Can, Mustafa

    2017-04-01

    Here we show effect of the polyamine polymer chain length to BET isotherms. According to IUPAC classification [1], all three polymers are fitting type 1 physical adsorption isotherm with H3 hysteresis (except for EDA having H2 hysteresis). Moreover, TG and TGA analysis of polymers triazine-ethylenediamine (EDA) and triazine-triethylenetetramine (TETA) are provided. Due to the similarities of the structure, main decomposition temperatures are close to each other (between 593 K and 873 K). In order to understand change of FTIR spectra with adsorption and stripping Au(III), fresh, Au(III) adsorbed and recycled spectras of polymers measured. For further discussions about the effect of chain length to adsorption of Au(III) onto triazine polyamine polymer particles "Au (III) Uptake by Triazine Polyamine Polymers: Mechanism, Kinetic and Equilibrium Studies" Can et al. [2] (article in press).

  20. Probing the temperature dependence of the mechanical properties of polymers at the nanoscale with band excitation thermal scanning probe microscopy.

    PubMed

    Nikiforov, M P; Jesse, S; Morozovska, A N; Eliseev, E A; Germinario, L T; Kalinin, S V

    2009-09-30

    Understanding local mechanisms for temperature-induced phase transitions in polymers requires quantitative measurements of the thermomechanical behavior, including glass transition and melting temperatures as well as temperature dependent elastic and loss modulus and thermal expansion coefficients in nanoscale volumes. Here, we demonstrate an approach for probing local thermal phase transitions based on the combination of thermal field confinement by a heated SPM probe and multi-frequency thermomechanical detection. The local measurement of the glass transition temperature is demonstrated and the detection limits are established.

  1. Soluble methane monooxygenase component B gene probe for identification of methanotrophs that rapidly degrade trichloroethylene.

    PubMed Central

    Tsien, H C; Hanson, R S

    1992-01-01

    Restriction fragment length polymorphisms, Western blot (immunoblot) analysis, and fluorescence-labelled signature probes were used for the characterization of methanotrophic bacteria as well as for the identification of methanotrophs which contained the soluble methane monooxygenase (MMO) gene and were able to degrade trichloroethylene (TCE). The gene encoding a soluble MMO component B protein from Methylosinus trichosporium OB3b was cloned. It contained a 2.2-kb EcoRI fragment. With this cloned component B gene as probe, methanotroph types I, II, and X and environmental and bioreactor samples were screened for the presence of the gene encoding soluble MMO. Fragments produced by digestion of DNA with rare cutting restriction endonucleases were separated by pulsed-field gel electrophoresis and transferred to Zeta-Probe membrane (Bio-Rad) for Southern blot analysis. Samples were also analyzed for the presence of soluble MMO by Western blot analysis and the ability to degrade TCE. The physiological groups of methanotrophs in each sample were determined by hybridizing cells with fluorescence-labelled signature probes. Among twelve pure or mixed cultures, DNA fragments of seven methanotrophs hybridized with the soluble MMO B gene probe. When grown in media with limited copper, all of these bacteria degraded TCE. All of them are type II methanotrophs. The soluble MMO component B gene of the type X methanotroph, Methylococcus capsulatus Bath, did not hybridize to the M. trichosporium OB3b soluble MMO component B gene probe, although M. capsulatus Bath also produces a soluble MMO. Images PMID:1349468

  2. Rheological techniques for determining degradation of polylactic acid in bioresorbable medical polymer systems

    NASA Astrophysics Data System (ADS)

    Choong, Gabriel Y. H.; Parsons, Andrew J.; Grant, David M.; De Focatiis, Davide S. A.

    2015-05-01

    A method developed in the 1980s for the conversion of linear rheological data to molar mass distribution is revisited in the context of degradable polymers. The method is first applied using linear rheology for a linear polystyrene, for which all conversion parameters are known. A proof of principle is then carried out on four polycarbonate grades. Finally, preliminary results are shown on degradable polylactides. The application of this method to degrading polymer systems, and to systems containing nanofillers, is also discussed. This work forms part of a wider study of bioresorbable nanocomposites using polylactides, novel hydroxyapatite nanoparticles and tailored dispersants for medical applications.

  3. Kinetics and mechanism of thermal degradation of pentose- and hexose-based carbohydrate polymers.

    PubMed

    Akbar, Jamshed; Iqbal, Mohammad S; Massey, Shazma; Masih, Rashid

    2012-10-15

    This work aims at study of thermal degradation kinetics and mechanism of pentose- and hexose-based carbohydrate polymers isolated from Plantago ovata (PO), Salvia aegyptiaca (SA) and Ocimum basilicum (OB). The analysis was performed by isoconversional method. The materials exhibited mainly two-stage degradation. The weight loss at ambient-115°C characterized by low activation energy corresponds to loss of moisture. The kinetic triplets consisting of E, A and g(α) model of the materials were determined. The major degradation stage represents a loss of high boiling volatile components. This stage is exothermic in nature. Above 340°C complete degradation takes place leaving a residue of 10-15%. The master plots of g(α) function clearly differentiated the degradation mechanism of hexose-based OB and SA polymers and pentose-based PO polymer. The pentose-based carbohydrate polymer showed D(4) type and the hexose-based polymers showed A(4) type degradation mechanism.

  4. Main chain acid-degradable polymers for the delivery of bioactive materials

    DOEpatents

    Frechet, Jean M. J. [Oakland, CA; Standley, Stephany M [Evanston, IL; Jain, Rachna [Milpitas, CA; Lee, Cameron C [Cambridge, MA

    2012-03-20

    Novel main chain acid degradable polymer backbones and drug delivery systems comprised of materials capable of delivering bioactive materials to cells for use as vaccines or other therapeutic agents are described. The polymers are synthesized using monomers that contain acid-degradable linkages cleavable under mild acidic conditions. The main chain of the resulting polymers readily degrade into many small molecules at low pH, but remain relatively stable and intact at physiological pH. The new materials have the common characteristic of being able to degrade by acid hydrolysis under conditions commonly found within the endosomal or lysosomal compartments of cells thereby releasing their payload within the cell. The materials can also be used for the delivery of therapeutics to the acidic regions of tumors and other sites of inflammation.

  5. Probing the degradation and homogeneity of embedded perovskite semiconducting layers in photovoltaic devices by Raman spectroscopy.

    PubMed

    Hooper, K E A; Lee, H K H; Newman, M J; Meroni, S; Baker, J; Watson, T M; Tsoi, W C

    2017-02-15

    The key challenges for perovskite solar cells include their poor stability and film homogeneity. Studying the degradation and homogeneity of perovskite layers within device structures can be challenging but critical to the understanding of stability and effect of processing in real life conditions. We show that Raman spectroscopy (RS) is a unique and powerful method (simple and fast) to probe the degradation of the perovskite film within the device structure and image perovskite formation. We demonstrate that RS can be used to directly probe chemical (PbI2) and physical (dihydrated phase) degradation of a perovskite film, and estimate the relative amount of the degradation species formed, mapping its distribution with ∼1 μm spatial resolution. This has been applied to mapping a large area perovskite module to characterise the efficacy of PbI2 to perovskite conversion. We also use RS to study the degradation species and kinetics under diverse accelerated degradation conditions (temperature and humidity) in situ. These capabilities are difficult to achieve with other methods, presenting RS as an important tool to gain understanding of the degradation and effect of processing on perovskite-based photovoltaic devices.

  6. Quantification of omeprazole degradation by enteric coating polymers: an UV-VIS spectroscopy study.

    PubMed

    Riedel, A; Leopold, C S

    2005-02-01

    The aim of this study was to investigate the degradation of the acid-labile proton-pump-inhibitor omeprazole in organic polymer solutions and aqueous dispersions of enteric coating polymers by UV spectroscopy. Furthermore, data were compared with those obtained in a previous HPLC study. For comparative purposes the cationic Eudragit RS 100 and the monomeric acid acetic acid were included in this study. The discolorations of degraded omeprazole solutions were analysed by VIS spectroscopy. UV-VIS spectra were recorded after preparation of the solutions and after 180 min of storage. The change of absorption was calculated as the difference of the absorption values at 305 nm. Degradation of omeprazole depends on the amount of acidic groups in the polymer structure. This decomposition manifests itself in a shifting of the absorption maximum to lower wavelengths and a decrease of absorption intensity. UV-VIS spectroscopy was used to determine the extent of degradation induced by enteric polymers. A good correlation of these results with previous HPLC data was found when excluding UV absorbing polymers. Nevertheless, values obtained by UV-VIS spectroscopy were always lower than those obtained by HPLC. For evaluation of the discoloration of degraded omeprazole solutions, VIS spectroscopy is a simple and fast method.

  7. Probing anode degradation in automotive Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Kwon, Ou Jung

    The lithium-ion battery is drawing attention as a power source for future clean and fuel-efficient vehicles. Although the Li-ion battery presently shows best performance for energy density and power density compared to other rechargeable batteries, some degradation problems still remain as key challenges for long-term durability in automotive applications. Among those problems, Li deposition is well known for causing permanent capacity loss. Fundamental mechanisms of Li deposition in the carbon anode are, however, not fully understood, especially at subzero temperature and/or under high rate charge. This dissertation introduces comprehensive study of Li deposition using automotive 18650 Li-ion cells. The mechanism and relevant diagnostic methods as well as preventive charging protocol are discussed. In part one, a new diagnostic tool is introduced utilizing 3-electrode cell system, which measures thermodynamic and kinetic parameters of cathode and anode, respectively, as a function of temperature and SOC (state of charge): open circuit potential (OCP); Li diffusion coefficient in active particles; and internal resistance. These data are employed to understand electrochemical reaction and its thermal interaction under charging conditions that result in Li deposition. Part two provides a threshold parameter for the onset of Li deposition, which is not commonly used anode potential but charge capacity, or more specifically the amount of Li+ ions participating in intercalation reaction without Li deposition at given charging circumstances. This is called the critical charge capacity in this thesis, beyond which capacity loss at normal operating condition is observed, which becomes more serious as temperature is lowered and/or charge C-rate increases. Based on these experimental results, the mechanism of Li deposition is proposed as the concept of anode particle surface saturation, meaning that once the anode particle surface is saturated with Li in any charging

  8. Rotational diffusion in polymer nanocomposites as probed by anisotropic particles

    NASA Astrophysics Data System (ADS)

    Clarke, Laura

    2014-03-01

    Metal nanoparticles strongly absorb specific wavelengths of light with no (or only a very weak) radiative relaxation by which to release this energy. As a result, the absorbed energy is efficiently converted to local heat (a photothermal effect). With an effective cross-section of up to 10 times its physical size, each particle acts as a ``super-sized'' absorber even when embedded within a transparent material environment such as a polymer, resulting in dramatic heating originating at the particles. Thus, with spatially-uniform illumination, one can metaphorically reach inside a polymer nanocomposite and apply heat to pre-selected subsets (e.g., causing them to dramatically change properties due to actuation, cross-linking, crystallization, or chemical reaction) without heating the sample surface or strongly affecting the remainder of the material. By utilizing optically-accessible additives including the particles themselves, the thermal gradient from the particle outward can be experimentally determined. In particular, rotational diffusion of anisotropic particles can be used to measure the temperature at the nanoparticle, which is the warmest point in a polymeric film or nanofiber under photothermal heating. Conversely, the same technique can be utilized to measure polymer dynamics in nanocomposites in the immediate vicinity of the particle. Funding: National Science Foundation CMMI-1069108.

  9. Probing the molecular connectivity of water confined in polymer hydrogels

    NASA Astrophysics Data System (ADS)

    Rossi, B.; Venuti, V.; Mele, A.; Punta, C.; Melone, L.; Crupi, V.; Majolino, D.; Trotta, F.; D'Amico, F.; Gessini, A.; Masciovecchio, C.

    2015-01-01

    The molecular connectivity and the extent of hydrogen-bond patterns of water molecules confined in the polymer hydrogels, namely, cyclodextrin nanosponge hydrogels, are here investigated by using vibrational spectroscopy experiments. The proposed spectroscopic method exploits the combined analysis of the vibrational spectra of polymers hydrated with water and deuterated water, which allows us to separate and selectively investigate the temperature-evolution of the HOH bending mode of engaged water molecules and of the vibrational modes assigned to specific chemical groups of the polymer matrix involved in the physical interactions with water. As main results, we find a strong experimental evidence of a liquid-like behaviour of water molecules confined in the nano-cavities of hydrogel and we observe a characteristic destructuring effect on the hydrogen-bonds network of confined water induced by thermal motion. More interestingly, the extent of this temperature-disruptive effect is found to be selectively triggered by the cross-linking degree of the hydrogel matrix. These results give a more clear picture of the molecular mechanism of water confinement in the pores of nanosponge hydrogel and open the possibility to exploit the spectroscopic method here proposed as investigating tools for water-retaining soft materials.

  10. Spectroscopic investigations into degradation of polymer membranes for fuel cells applications

    NASA Astrophysics Data System (ADS)

    Kruczała, Krzysztof; Szczubiałka, Krzysztof; Łańcucki, Łukasz; Zastawny, Izabela; Góra-Marek, Kinga; Dyrek, Krystyna; Sojka, Zbigniew

    2008-05-01

    The research was focused on synthesis of proton conductive, easily degradable polymer membranes, which can be used as a model system to verify the efficiency of transition metal ions (TMI) in prevention of polymer degradation. Two polymers composed of 2-hydroxyethyl methacrylate (HEMA), 2-acrylamido-2-methyl-1-propane sulfonic acid (AMPS), and styrenesulfonic acid (SS) were synthesized. The copolymers were characterized by gel permeation chromatography (GPC), elementary analysis, and FTIR and fluorescence spectroscopies. The results allowed determination of weight-average molecular weight and the copolymer composition. The protons of sulfonic groups were substituted by paramagnetic transition metal ions of various spin states (Cr 3+, S = 3/2 and Mn 2+, S = 5/2) with the loading varying from 0.5 up to 10 mol%. The effectiveness of spin catalysis was checked by EPR. The results obtained indicate enhancement of polymer stability in the presence of Mn 2+.

  11. A Suite of Activity-Based Probes for Cellulose Degrading Enzymes

    PubMed Central

    Chauvigné-Hines, Lacie M.; Anderson, Lindsey N.; Weaver, Holly M.; Brown, Joseph N.; Koech, Phillip K.; Nicora, Carrie D.; Hofstad, Beth A.; Smith, Richard D.; Wilkins, Michael J.; Callister, Stephen J.; Wright, Aaron T.

    2012-01-01

    Microbial glycoside hydrolases play a dominant role in the biochemical conversion of cellulosic biomass to high-value biofuels. Anaerobic cellulolytic bacteria are capable of producing multicomplex catalytic subunits containing cell-adherent cellulases, hemicellulases, xylanases, and other glycoside hydrolases to facilitate the degradation of highly recalcitrant cellulose and other related plant cell wall polysaccharides. Clostridium thermocellum is a cellulosome producing bacterium that couples rapid reproduction rates to highly efficient degradation of crystalline cellulose. Herein, we have developed and applied a suite of difluoromethylphenyl aglycone, N-halogenated glycosylamine, and 2-deoxy-2-fluoroglycoside activity-based protein profiling (ABPP) probes to the direct labeling of the C. thermocellum cellulosomal secretome. These activity-based probes (ABPs) were synthesized with alkynes to harness the utility and multimodal possibilities of click chemistry, and to increase enzyme active site inclusion for LC-MS analysis. We directly analyzed ABP-labeled and unlabeled global MS data, revealing ABP selectivity for glycoside hydrolase (GH) enzymes, in addition to a large collection of integral cellulosome-containing proteins. By identifying reactivity and selectivity profiles for each ABP, we demonstrate our ability to widely profile the functional cellulose degrading machinery of the bacterium. Derivatization of the ABPs, including reactive groups, acetylation of the glycoside binding groups, and mono- and disaccharide binding groups, resulted in considerable variability in protein labeling. Our probe suite is applicable to aerobic and anaerobic microbial cellulose degrading systems, and facilitates a greater understanding of the organismal role associated with biofuel development. PMID:23176123

  12. Suite of Activity-Based Probes for Cellulose-Degrading Enzymes

    SciTech Connect

    Chauvigne-Hines, Lacie M.; Anderson, Lindsey N.; Weaver, Holly M.; Brown, Joseph N.; Koech, Phillip K.; Nicora, Carrie D.; Hofstad, Beth A.; Smith, Richard D.; Wilkins, Michael J.; Callister, Stephen J.; Wright, Aaron T.

    2012-12-19

    Microbial glycoside hydrolases play a dominant role in the biochemical conversion of cellulosic biomass to high-value biofuels. Anaerobic cellulolytic bacteria are capable of producing multicomplex catalytic subunits containing cell-adherent cellulases, hemicellulases, xylanases, and other glycoside hydrolases to facilitate the degradation of highly recalcitrant cellulose and other related plant cell wall polysaccharides. Clostridium thermocellum is a cellulosome producing bacterium that couples rapid reproduction rates to highly efficient degradation of crystalline cellulose. Herein, we have developed and applied a suite of difluoromethylphenyl aglycone, N-halogenated glycosylamine, and 2-deoxy-2-fluoroglycoside activity-based protein profiling (ABPP) probes to the direct labeling of the C. thermocellum cellulosomal secretome. These activity-based probes (ABPs) were synthesized with alkynes to harness the utility and multimodal possibilities of click chemistry, and to increase enzyme active site inclusion for LC-MS analysis. We directly analyzed ABP-labeled and unlabeled global MS data, revealing ABP selectivity for glycoside hydrolase (GH) enzymes in addition to a large collection of integral cellulosome-containing proteins. By identifying reactivity and selectivity profiles for each ABP, we demonstrate our ability to widely profile the functional cellulose degrading machinery of the bacterium. Derivatization of the ABPs, including reactive groups, acetylation of the glycoside binding groups, and mono- and disaccharide binding groups, resulted in considerable variability in protein labeling. Our probe suite is applicable to aerobic and anaerobic cellulose degrading systems, and facilitates a greater understanding of the organismal role associated within biofuel development.

  13. Development of Bioorthogonally Degradable Linkers and Polymers Using alpha-Azidoethers

    NASA Astrophysics Data System (ADS)

    Rajagopalan, Chandrasekhar Ramasubramanian

    Degradable polymers have gained a lot of attention in recent years for applications in biotechnology and medicine. External control over polymer degradation can be obtained by incorporating functional groups that cleave in the presence of triggers that would normally be absent in biological environments, i.e. are bioorthogonal. This thesis explores the use of chemically cleavable alpha-azidoethers as a new method to obtain external control over the degradation behavior of polymers. My first goal is to illustrate the potential of alpha-azidoethers toward developing cleavable linkers. We have studied the relationship between alpha-azidoether structure and hydrolytic stability, to prepare linkers that withstand background hydrolytic cleavage until they are exposed to the cleaving trigger. The cleavage kinetics of the alpha-azidoether functional group was quantified. In addition to the conventionally used tris(2-carboxyethyl)phosphine (TCEP), dihydrolipoic acid (DHLA), a previously unexplored, biocompatible reducing agent, was also evaluated as a cleaving trigger. Based on these results, we have proposed design rules for utilizing alpha-azidoethers as cleavable linkers in applications that require bioorthogonal control over linker cleavage. Secondly, the alpha-azidoether cleavable linker chemistry was implemented into the development of polymeric materials. Two different types of polymers were developed. Polyamides incorporating alpha-azidoethers along the backbone were synthesized, and their physical properties and chemically triggered degradation behavior were characterized. The degradation timescale of these polymers can be tuned simply by manipulating the concentration of the externally applied chemical trigger. The alpha-azidoether functional group was then utilized to develop a unique triggered-release polymeric adhesive for potential applications in dental adhesive formulations. A methacrylamide-phosphonate adhesive monomer incorporating an alpha

  14. DNase-activatable fluorescence probes visualizing the degradation of exogenous DNA in living cells

    NASA Astrophysics Data System (ADS)

    Gong, Ping; Shi, Bihua; Zhang, Pengfei; Hu, Dehong; Zheng, Mingbin; Zheng, Cuifang; Gao, Duyang; Cai, Lintao

    2012-03-01

    This work presents a method to visualize the degradation of exogenous DNA in living cells using a novel type of activatable fluorescence imaging probe. Deoxyribonuclease (DNase)-activatable fluorescence probes (DFProbes) are composed of double strands deoxyribonucleic acid (dsDNA) which is labeled with fluorophore (ROX or Cy3) and quencher on the end of one of its strands, and stained with SYBR Green I. In the absence of DNase, DFProbes produce the green fluorescence signal of SYBR Green I. In the presence of DNase, SYBR Green I is removed from the DFProbes and the labeled fluorophore is separated from the quencher owing to the degradation of DFProbes by DNase, resulting in the decrease of the green fluorescence signal and the occurrence of a red fluorescence signal due to fluorescence resonance energy transfer (FRET). DNase in biological samples was detected using DFProbes and the fluorescence imaging in living cells was performed using DFprobe-modified Au nanoparticles. The results show that DFProbes have good responses to DNase, and can clearly visualize the degradation of exogenous DNA in cells in real time. The well-designed probes might be useful in tracing the dynamic changes of exogenous DNA and nanocarriers in vitro and in vivo.This work presents a method to visualize the degradation of exogenous DNA in living cells using a novel type of activatable fluorescence imaging probe. Deoxyribonuclease (DNase)-activatable fluorescence probes (DFProbes) are composed of double strands deoxyribonucleic acid (dsDNA) which is labeled with fluorophore (ROX or Cy3) and quencher on the end of one of its strands, and stained with SYBR Green I. In the absence of DNase, DFProbes produce the green fluorescence signal of SYBR Green I. In the presence of DNase, SYBR Green I is removed from the DFProbes and the labeled fluorophore is separated from the quencher owing to the degradation of DFProbes by DNase, resulting in the decrease of the green fluorescence signal and the

  15. Modeling of drug release from bulk-degrading polymers.

    PubMed

    Lao, Luciana Lisa; Peppas, Nicholas A; Boey, Freddy Yin Chiang; Venkatraman, Subbu S

    2011-10-10

    This paper aims to provide a comprehensive review of the various models or simulations for predicting drug release from bulk-degrading systems. A brief description of bulk degradation processes and factors affecting the degradation rate, and consequently the release kinetics, is presented first. Next, several important classical models, often used as the basis for subsequent model development, are discussed. Both mathematical models and Monte-Carlo based simulations have been developed for controlled release from bulk-degrading systems. The mathematical models can be further subdivided into two categories. First, the diffusion-based models whose transport mechanism is mainly governed by diffusion, but with degradation-dependent diffusion coefficients. These are generally simpler and easier to use and are sufficient to illustrate mono-phasic release. Second, comprehensive models that combine diffusion with other theories such as erosion, drug dissolution and/or pore percolations. These models usually involve more complex equations but provide good matches for multi-phasic release profiles.

  16. A Review of Molecular-Level Mechanism of Membrane Degradation in the Polymer Electrolyte Fuel Cell

    PubMed Central

    Ishimoto, Takayoshi; Koyama, Michihisa

    2012-01-01

    Chemical degradation of perfluorosulfonic acid (PFSA) membrane is one of the most serious problems for stable and long-term operations of the polymer electrolyte fuel cell (PEFC). The chemical degradation is caused by the chemical reaction between the PFSA membrane and chemical species such as free radicals. Although chemical degradation of the PFSA membrane has been studied by various experimental techniques, the mechanism of chemical degradation relies much on speculations from ex-situ observations. Recent activities applying theoretical methods such as density functional theory, in situ experimental observation, and mechanistic study by using simplified model compound systems have led to gradual clarification of the atomistic details of the chemical degradation mechanism. In this review paper, we summarize recent reports on the chemical degradation mechanism of the PFSA membrane from an atomistic point of view. PMID:24958288

  17. Development of Degradable Polymer Composites from Starch and Poly(alkyl cyanoacrylate)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This report describes the development of degradable polymer composites that can be made at room temperature without special equipment. The developed composites are made from poly(alkyl cyanoacrylate) and starch. Alkyl cyanoacrylate monomers are mixed with starch and the polymerization reaction of ...

  18. Development of degradable polymer composites from starch and poly(alkyl cyanoacrylate)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This report describes the development of degradable polymer composites that can be made at room temperature without special equipments. The developed composites were made from poly(alkyl cyanoacrylate) and starch. Alkyl cyanoacrylate monomers were mixed with starch and the polymerization reaction ...

  19. Modelling drug degradation in a spray dried polymer dispersion using a modified Arrhenius equation.

    PubMed

    Patterson, Adele; Ferreira, Ana P; Banks, Elizabeth; Skeene, Kirsty; Clarke, Graham; Nicholson, Sarah; Rawlinson-Malone, Clare

    2015-01-15

    The Pharmaceutical industry is increasingly utilizing amorphous technologies to overcome solubility challenges. A common approach is the use of drug in polymer dispersions to prevent recrystallization of the amorphous drug. Understanding the factors affecting chemical and physical degradation of the drug within these complex systems, e.g., temperature and relative humidity, is an important step in the selection of a lead formulation, and development of appropriate packaging/storage control strategies. The Arrhenius equation has been used as the basis of a number of models to predict the chemical stability of formulated product. In this work, we investigate the increase in chemical degradation seen for one particular spray dried dispersion formulation using hydroxypropyl methylcellulose acetate succinate (HPMC-AS). Samples, prepared using polymers with different substitution levels, were placed on storage for 6 months under a range of different temperature and relative humidity conditions and the degradant level monitored using high-performance liquid chromatography (HPLC). While the data clearly illustrates the impact of temperature and relative humidity on the degradant levels detected, it also highlighted that these terms do not account for all the variability in the data. An extension of the Arrhenius equation to include a term for the polymer chemistry, specifically the degree of succinoyl substitution on the polymer backbone, was shown to improve the fit of the model to the data.

  20. Review of oxidative degradations of certain heterocyclic polymers

    NASA Technical Reports Server (NTRS)

    Mayo, F. R.

    1971-01-01

    The curing and decompositions of polyphenylenes and several nitrogen-containing condensation polymers, particularly polybenzimidazoles and pyrones, are reviewed critically. It is concluded that the condensations are usually imperfect and incomplete and that in most of the published work the late stages of the condensation are complicated by the beginnings of the charring and carbonization processes. Most discussions of mechanisms in this range are highly speculative and of little value. The most promising fields for further research are at lower temperatures, where slow oxidation processes deserve study, and at higher temperatures, where it may be possible to influence carbonization processes to obtain better products.

  1. Driving degradation within biodegradable polymers with embedded nanoparticles

    NASA Astrophysics Data System (ADS)

    Gorga, Russell; Firestone, Gabriel; Fontecha, Daniela; Bochinski, Jason; Clarke, Laura

    The ability to controllably trigger breaking of chemical bonds enables a substance that has robust material properties during use but can be re-worked or deteriorated upon command. Photothermal heating creates intense local heat at isolated nanoparticle locations within a sample and can result in very different material responses than those achievable with conventional (uniform) heating. In this process, irradiation with visible light resonant with the nanoparticle's surface plasmon resonance results in dramatic local heating of the particles and the surrounding material. This work studies intentional thermal degradation of poly ethyl cyanoacrylate-starch composites doped with metal nanoparticles, and explores differences in degradation speed, efficiency, and resultant mechanical properties when heated via the photothermal effect. This work was supported by the National Science Foundation, Grant #: CMMI-1462966.

  2. Mechanochromic Fluorescent Probe Molecules for Damage Detection in Aerospace Polymers and Composites

    NASA Astrophysics Data System (ADS)

    Toivola, Ryan E.

    The detection of damage in aerospace composites can be improved by incorporation of mechanochromic fluorescent probe molecules into the polymers used in composite parts. This study focuses on a novel series of mechanochromic probes, AJNDE15 and AJNDE17, which are incorporated in structural epoxy resin DGEBA-DETA. Chapter 1 details the characterization of the DGEBA-DETA epoxy system used in this study. The important characteristics of DGEBA-DETA's response to mechanical loading will be discussed within the larger field of glassy amorphous polymer deformation. The mechanical, thermal, and chemical properties of DGEBA-DETA relevant to this work will be measured using standardized techniques and instrumentation. Chapters 2 and 3 focus on the mechanochromic probes AJNDE15 and AJNDE17 in the DGEBA-DETA system. Chapter 2 presents research designed to identify the mechanism through which the probes display mechanochromism. The possible mechanochromic mechanisms are introduced in a literature review. Research on these probes in DGEBA-DETA will be presented and discussed with respect to the possible mechanisms, and the mechanism that best fits the results will be identified as a mechanochemical reaction. Chapter 3 continues the analysis of the mechanochromism of the probes in DGEBA-DETA. The kinetics of the mechanochromic reaction will be studied and compared with the current understanding of glassy polymer deformation. Possible models for the molecular interactions responsible for mechanochromism in this system will be put forward. Research will be presented to evaluate the mechanochromism kinetics and for comparison with the behavior predicted by the models.

  3. Identification of triclosan-degrading bacteria in a triclosan enrichment culture using stable isotope probing.

    PubMed

    Lee, Do Gyun; Cho, Kun-Ching; Chu, Kung-Hui

    2014-02-01

    Triclosan, a widely used antimicrobial agent, is an emerging contaminant in the environment. Despite its antimicrobial character, biodegradation of triclosan has been observed in pure cultures, soils and activated sludge. However, little is known about the microorganisms responsible for the degradation in mixed cultures. In this study, active triclosan degraders in a triclosan-degrading enrichment culture were identified using stable isotope probing (SIP) with universally (13)C-labeled triclosan. Eleven clones contributed from active microorganisms capable of uptake the (13)C in triclosan were identified. None of these clones were similar to known triclosan-degraders/utilizers. These clones distributed among α-, β-, or γ-Proteobacteria: one belonging to Defluvibacter (α-Proteobacteria), seven belonging to Alicycliphilus (β-Proteobacteria), and three belonging to Stenotrophomonas (γ-Proteobacteria). Successive additions of triclosan caused a significant shift in the microbial community structure of the enrichment culture, with dominant ribotypes belonging to the genera Alicycliphilus and Defluvibacter. Application of SIP has successfully identified diverse uncultivable triclosan-degrading microorganisms in an activated sludge enrichment culture. The results of this study not only contributed to our understanding of the microbial ecology of triclosan biodegradation in wastewater, but also suggested that triclosan degraders are more phylogenetically diverse than previously reported.

  4. Probing of cosolvents in polymer latex materials by using solvatochromic fluorescence.

    PubMed

    Brouwer, Albert M; Raja, Tanzeela N; Biemans, Koen; Nabuurs, Tijs; Tennebroek, Ronald

    2008-01-01

    The process of film formation is of great importance for the application of organic coatings. In waterborne coatings, organic cosolvents are still indispensable, but regulations force the industry to reduce their amounts. Here we describe a method that uses the solvatochromic fluorescence of a probe molecule copolymerized in an emulsion polymerization process with different monomers to shed light on the partitioning of cosolvents in polymer latex materials. The formulation of the latex with organic cosolvents that are not very water soluble leads to a quantifiable redshift of the emission of the probe. The transfer of the cosolvent upon mixing of cosolvent-containing and cosolvent-free compartments can also be monitored.

  5. Positronium as a probe in natural polymers: decomposition in starch.

    PubMed

    Roudaut, G; Duplâtre, G

    2009-11-07

    Ortho-positronium (o-Ps) is used as a probe in positron annihilation lifetime spectroscopy (PALS) experiments, to characterise the behaviour of free volumes in natural starch samples, as a function of temperature (T). Up to about 540 K, the o-Ps intensity, I(3), remains constant at 26.2% while its lifetime, tau(3), is found to increase linearly. Both parameters undergo a decrease above this T, due to the onset of decomposition, which results in a shrinking of the sample pellets. The results indicate that the glass transition temperature should be above 501 K. Data from thermal gravimetry analysis (TGA) measurements are well described by supposing a first order process for the survival probability (p) of the starch lattice, with an activation energy, E(act) = (1.52 +/- 0.05) eV, and a frequency factor, ln(k(0), s(-1)) = 25.3 +/- 0.4. In the decomposition region, the PALS data show the unexpected correlation (tau(3n))(3) = I(3n), linking the normalised values of tau(3), tau(3n), and of I(3), I(3n). This is explained by considering that the changes in I(3) with T arise from those in the surviving volume fraction of the lattice, p, whereas the changes in tau(3) reflect the shrinking of the radius of the free volumes, the latter decreasing in proportion to p(1/3). Quantitative approaches on these bases lead to satisfactory fitting of all PALS data, yielding an activation energy, E(act) = (1.53 +/- 0.03) eV, and frequency factor, ln(k(0), s(-1)) = 25.4 +/- 0.2, in excellent agreement with the values derived from TGA.

  6. Probing the surface profile and friction behavior of heterogeneous polymers: a molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Dai, L.; Sorkin, V.; Zhang, Y. W.

    2017-04-01

    We perform molecular dynamics simulations to investigate molecular structure alternation and friction behavior of heterogeneous polymer (perfluoropolyether) surfaces using a nanoscale probing tip (tetrahedral amorphous carbon). It is found that depending on the magnitude of the applied normal force, three regimes exist: the shallow depth-sensing (SDS), deep depth-sensing (DDS), and transitional depth-sensing (TDS) regimes; TDS is between SDS and DDS. In SDS, the tip is floating on the polymer surface and there is insignificant permanent alternation in the polymer structure due to largely recoverable atomic deformations, and the surface roughness profile can be accurately measured. In DDS, the tip is plowing through the polymer surface and there is significant permanent alternation in the molecular structure. In this regime, the lateral friction force rises sharply and fluctuates violently when overcoming surface pile-ups. In SDS, the friction can be described by a modified Amonton’s law including the adhesion effect; meanwhile, in DDS, the adhesion effect is negligible but the friction coefficient is significantly higher. The underlying reason for the difference in these regimes rests upon different contributions by the repulsion and attraction forces between the tip and polymer surfaces to the friction force. Our findings here reveal important insights into lateral depth-sensing on heterogeneous polymer surfaces and may help improve the precision of depth-sensing devices.

  7. Semiconducting polymer nanoparticles as photoacoustic molecular imaging probes in living mice.

    PubMed

    Pu, Kanyi; Shuhendler, Adam J; Jokerst, Jesse V; Mei, Jianguo; Gambhir, Sanjiv S; Bao, Zhenan; Rao, Jianghong

    2014-03-01

    Photoacoustic imaging holds great promise for the visualization of physiology and pathology at the molecular level with deep tissue penetration and fine spatial resolution. To fully utilize this potential, photoacoustic molecular imaging probes have to be developed. Here, we introduce near-infrared light absorbing semiconducting polymer nanoparticles as a new class of contrast agents for photoacoustic molecular imaging. These nanoparticles can produce a stronger signal than the commonly used single-walled carbon nanotubes and gold nanorods on a per mass basis, permitting whole-body lymph-node photoacoustic mapping in living mice at a low systemic injection mass. Furthermore, the semiconducting polymer nanoparticles possess high structural flexibility, narrow photoacoustic spectral profiles and strong resistance to photodegradation and oxidation, enabling the development of the first near-infrared ratiometric photoacoustic probe for in vivo real-time imaging of reactive oxygen species--vital chemical mediators of many diseases. These results demonstrate semiconducting polymer nanoparticles to be an ideal nanoplatform for developing photoacoustic molecular probes.

  8. Semiconducting polymer nanoparticles as photoacoustic molecular imaging probes in living mice

    NASA Astrophysics Data System (ADS)

    Pu, Kanyi; Shuhendler, Adam J.; Jokerst, Jesse V.; Mei, Jianguo; Gambhir, Sanjiv S.; Bao, Zhenan; Rao, Jianghong

    2014-03-01

    Photoacoustic imaging holds great promise for the visualization of physiology and pathology at the molecular level with deep tissue penetration and fine spatial resolution. To fully utilize this potential, photoacoustic molecular imaging probes have to be developed. Here, we introduce near-infrared light absorbing semiconducting polymer nanoparticles as a new class of contrast agents for photoacoustic molecular imaging. These nanoparticles can produce a stronger signal than the commonly used single-walled carbon nanotubes and gold nanorods on a per mass basis, permitting whole-body lymph-node photoacoustic mapping in living mice at a low systemic injection mass. Furthermore, the semiconducting polymer nanoparticles possess high structural flexibility, narrow photoacoustic spectral profiles and strong resistance to photodegradation and oxidation, enabling the development of the first near-infrared ratiometric photoacoustic probe for in vivo real-time imaging of reactive oxygen species--vital chemical mediators of many diseases. These results demonstrate semiconducting polymer nanoparticles to be an ideal nanoplatform for developing photoacoustic molecular probes.

  9. Orthogonal Supramolecular Polymer Formation on Highly Oriented Pyrolytic Graphite (HOPG) Surfaces Characterized by Scanning Probe Microscopy.

    PubMed

    Gong, Yongxiang; Zhang, Siqi; Geng, Yanfang; Niu, Chunmei; Yin, Shouchun; Zeng, Qingdao; Li, Min

    2015-10-27

    Formation of an orthogonal supramolecular polymer on a highly oriented pyrolytic graphite (HOPG) surface was demonstrated for the first time by means of scanning probe microscopy (SPM). Atomic force microscopy (AFM) was employed to characterize the variation of both the thickness and the topography of the film formed from (1) monomer 1, (2) monomer 1/Zn(2+), and (3) monomer 1/Zn(2+)/cross-linker 2, respectively. Scanning tunneling microscopy (STM) was used to monitor the self-assembly behavior of monomer 1 itself, as well as 1/Zn(2+) ions binary system on graphite surface, further testifying for the formation of linear polymer via coordination interaction at the single molecule level. These results, given by the strong surface characterization tool of SPM, confirm the formation of the orthogonal polymer on the surface of graphite, which has great significance in regard to fabricating a complex superstructure on surfaces.

  10. Dual-Color Fluorescence Imaging of Magnetic Nanoparticles in Live Cancer Cells Using Conjugated Polymer Probes

    PubMed Central

    Sun, Minjie; Sun, Bin; Liu, Yun; Shen, Qun-Dong; Jiang, Shaojun

    2016-01-01

    Rapid growth in biological applications of nanomaterials brings about pressing needs for exploring nanomaterial-cell interactions. Cationic blue-emissive and anionic green-emissive conjugated polymers are applied as dual-color fluorescence probes to the surface of negatively charged magnetic nanoparticles through sequentially electrostatic adsorption. These conjugated polymers have large extinction coefficients and high fluorescence quantum yield (82% for PFN and 62% for ThPFS). Thereby, one can visualize trace amount (2.7 μg/mL) of fluorescence-labeled nanoparticles within cancer cells by confocal laser scanning microscopy. Fluorescence labeling by the conjugated polymers is also validated for quantitative determination of the internalized nanoparticles in each individual cell by flow cytometry analysis. Extensive overlap of blue and green fluorescence signals in the cytoplasm indicates that both conjugated polymer probes tightly bind to the surface of the nanoparticles during cellular internalization. The highly charged and fluorescence-labeled nanoparticles non-specifically bind to the cell membranes, followed by cellular uptake through endocytosis. The nanoparticles form aggregates inside endosomes, which yields a punctuated staining pattern. Cellular internalization of the nanoparticles is dependent on the dosage and time. Uptake efficiency can be enhanced three-fold by application of an external magnetic field. The nanoparticles are low cytotoxicity and suitable for simultaneously noninvasive fluorescence and magnetic resonance imaging application. PMID:26931282

  11. Dual-Color Fluorescence Imaging of Magnetic Nanoparticles in Live Cancer Cells Using Conjugated Polymer Probes.

    PubMed

    Sun, Minjie; Sun, Bin; Liu, Yun; Shen, Qun-Dong; Jiang, Shaojun

    2016-03-02

    Rapid growth in biological applications of nanomaterials brings about pressing needs for exploring nanomaterial-cell interactions. Cationic blue-emissive and anionic green-emissive conjugated polymers are applied as dual-color fluorescence probes to the surface of negatively charged magnetic nanoparticles through sequentially electrostatic adsorption. These conjugated polymers have large extinction coefficients and high fluorescence quantum yield (82% for PFN and 62% for ThPFS). Thereby, one can visualize trace amount (2.7 μg/mL) of fluorescence-labeled nanoparticles within cancer cells by confocal laser scanning microscopy. Fluorescence labeling by the conjugated polymers is also validated for quantitative determination of the internalized nanoparticles in each individual cell by flow cytometry analysis. Extensive overlap of blue and green fluorescence signals in the cytoplasm indicates that both conjugated polymer probes tightly bind to the surface of the nanoparticles during cellular internalization. The highly charged and fluorescence-labeled nanoparticles non-specifically bind to the cell membranes, followed by cellular uptake through endocytosis. The nanoparticles form aggregates inside endosomes, which yields a punctuated staining pattern. Cellular internalization of the nanoparticles is dependent on the dosage and time. Uptake efficiency can be enhanced three-fold by application of an external magnetic field. The nanoparticles are low cytotoxicity and suitable for simultaneously noninvasive fluorescence and magnetic resonance imaging application.

  12. Probe-Level Analysis of Expression Microarrays Characterizes Isoform-Specific Degradation during Mouse Oocyte Maturation

    PubMed Central

    Salisbury, Jesse; Hutchison, Keith W.; Wigglesworth, Karen; Eppig, John J.; Graber, Joel H.

    2009-01-01

    Background Gene expression microarrays have provided many insights into changes in gene expression patterns between different tissue types, developmental stages, and disease states. Analyses of these data focused primarily measuring the relative abundance of transcripts of a gene, while treating most or all transcript isoforms as equivalent. Differences in the selection between transcript isoforms can, however, represent critical changes to either the protein product or the posttranscriptional regulation of the transcript. Novel analyses on existing microarray data provide fresh insights and new interpretations into transcriptome-wide changes in expression. Methodology A probe-level analysis of existing gene expression arrays revealed differences in mRNA processing, primarily affecting the 3′-untranslated region. Working with the example of microarrays drawn from a transcriptionally silent period of mouse oocyte development, probe-level analysis (implemented here as rmodel) identified genes whose transcript isoforms have differing stabilities. Comparison of micorarrays measuring cDNA generated from oligo-dT and random primers revealed further differences in the polyadenylation status of some transcripts. Additional analysis provided evidence for sequence-targeted cleavage, including putative targeting sequences, as one mechanism of degradation for several hundred transcripts in the maturing oocyte. Conclusions The capability of probe-level analysis to elicit novel findings from existing expression microarray data was demonstrated. The characterization of differences in stability between transcript isoforms in maturing mouse oocytes provided some mechanistic details of degradation. Similar analysis of existing archives of expression microarray data will likely provide similar discoveries. PMID:19834616

  13. Degradation of different elastomeric polymers in simulated geothermal environments at 300°C

    SciTech Connect

    Sugama, Toshifumi; Pyatina, Tatiana; Redline, Erica Marie; McElhanon, James R.; Blankenship, Douglas A.

    2015-07-17

    This study evaluates the degradation of six different elastomeric polymers used for O-rings: EPDM, FEPM, type I- and II-FKM, FFKM, and FSR, in five different simulated geothermal environments at 300 °C: 1) non-aerated steam/cooling cycles, 2) aerated steam/cooling cycles, 3) water-based drilling fluid, 4) CO2-rich geo-brine fluid, and, 5) heat–cool water quenching cycles. The factors assessed included the extent of oxidation, changes in thermal behavior, micro-defects, permeation of ionic species from the test environments into the O-rings, silicate-related scale-deposition, and changes in the O-rings' elastic modulus. The reliability of the O-rings to maintain their integrity depended on the elastomeric polymer composition and the exposure environment. FSR disintegrated while EPDM was oxidized only to some degree in all the environments, FKM withstood heat-water quenching but underwent chemical degradation, FEPM survived in all the environments with the exception of heat-water quenching where it underwent severe oxidation-induced degradation, and FFKM displayed outstanding compatibility with all the tested environments. This study discusses the degradation mechanisms of the polymers under the aforementioned conditions.

  14. Polymer electrolyte membrane water electrolysis: Restraining degradation in the presence of fluctuating power

    NASA Astrophysics Data System (ADS)

    Rakousky, Christoph; Reimer, Uwe; Wippermann, Klaus; Kuhri, Susanne; Carmo, Marcelo; Lueke, Wiebke; Stolten, Detlef

    2017-02-01

    Polymer electrolyte membrane (PEM) water electrolysis generates 'green' hydrogen when conducted with electricity from renewable - but fluctuating - sources like wind or solar photovoltaic. Unfortunately, the long-term stability of the electrolyzer performance is still not fully understood under these input power profiles. In this study, we contrast the degradation behavior of our PEM water electrolysis single cells that occurs under operation with constant and intermittent power and derive preferable operating states. For this purpose, five different current density profiles are used, of which two were constant and three dynamic. Cells operated at 1 A cm-2 show no degradation. However, degradation was observed for the remaining four profiles, all of which underwent periods of high current density (2 A cm-2). Hereby, constant operation at 2 A cm-2 led to the highest degradation rate (194 μV h-1). Degradation can be greatly reduced when the cells are operated with an intermittent profile. Current density switching has a positive effect on durability, as it causes reversible parts of degradation to recover and results in a substantially reduced degradation per mole of hydrogen produced. Two general degradation phenomena were identified, a decreased anode exchange current density and an increased contact resistance at the titanium porous transport layer (Ti-PTL).

  15. Degradable Polymers and Block Copolymers from Electron-deficient Carbonyl Compounds (STIR) (7.3 Polymer Chemistry - Synthesis: Architecture and Composition)

    DTIC Science & Technology

    2015-04-23

    Park, NC 27709-2211 Polymerization ; degradable polymers ; renewable resources; organocatalysis REPORT DOCUMENTATION PAGE 11. SPONSOR/MONITOR’S REPORT... polymerization of ethyl glyoxylate with DBU Statement of the problem studied Polyacetals are a readily degradable class of polymers with potential uses... polymerization of the ethyl glyoxylate, which is soluble in organic solvents and can be more easily dehydrated. Purification of ethyl glyoxylate, which

  16. Polymer electrolyte fuel cell performance degradation at different synchrotron beam intensities.

    PubMed

    Eller, Jens; Büchi, Felix N

    2014-01-01

    The degradation of cell performance of polymer electrolyte fuel cells under monochromatic X-ray irradiation at 13.5 keV was studied in galvanostatic and potentiostatic operation modes in a through-plane imaging direction over a range of two orders of magnitude beam intensity at the TOMCAT beamline of the Swiss Light Source. The performance degradation was found to be a function of X-ray dose and independent of beam intensity, whereas the degradation rate correlates with beam intensity. The cell performance was more sensitive to X-ray irradiation at higher temperature and gas feed humidity. High-frequency resistance measurements and the analysis of product water allow conclusions to be drawn on the dominating degradation processes, namely change of hydrophobicity of the electrode and sulfate contamination of the electrocatalyst.

  17. Natural polymers supported copper nanoparticles for pollutants degradation

    NASA Astrophysics Data System (ADS)

    Haider, Sajjad; Kamal, Tahseen; Khan, Sher Bahadar; Omer, Muhammad; Haider, Adnan; Khan, Farman Ullah; Asiri, Abdullah M.

    2016-11-01

    In this report, chitosan (CS) was adhered on cellulose microfiber mat (CMM) to prepare CS-CMM. This was used as host for copper (Cu) nanoparticles preparation. After adsorption of Cu2+ ions from an aqueous solution of CuSO4, the metal ions entrapped in CS coating layer was treated with sodium borohydride (NaBH4) to prepare Cu nanoparticles loaded CS-CMM (Cu/CS-CMM). Fourier transform infrared spectroscopy, and X-ray diffraction confirmed the formation of Cu/CS-CMM hybrid. Scanning electron microscopy analysis was performed to reveal the morphology of the prepared catalyst. The prepared Cu/CS-CMM was employed as a catalyst for the degradation of nitro-aromatic compounds of 2-nitrophenol (2NP) and 4-nitrophenol (4NP) as well as an organic cresyl blue (CB) dye. Remarkably, the turnover frequency in the case of 2NP and 4NP using Cu/CS-CMM reaches 103.3 and 88.6 h-1, outperforming previously reported Cu nanoparticles immobilized in hydrogel-based catalytic systems. The rate constants for 2NP, 4NP and CB were 1.2 × 10-3 s-1, 2.1 × 10-3 s-1 and, 1.3 × 10-3 s-1, respectively. Besides, we discussed the separation of the catalyst from the reaction mixture and its re-usability.

  18. Probing polymer crystallization at processing-relevant cooling rates with synchrotron radiation

    SciTech Connect

    Cavallo, Dario; Portale, Giuseppe; Androsch, René

    2015-12-17

    Processing of polymeric materials to produce any kind of goods, from films to complex objects, involves application of flow fields on the polymer melt, accompanied or followed by its rapid cooling. Typically, polymers solidify at cooling rates which span over a wide range, from a few to hundreds of °C/s. A novel method to probe polymer crystallization at processing-relevant cooling rates is proposed. Using a custom-built quenching device, thin polymer films are ballistically cooled from the melt at rates between approximately 10 and 200 °C/s. Thanks to highly brilliant synchrotron radiation and to state-of-the-art X-ray detectors, the crystallization process is followed in real-time, recording about 20 wide angle X-ray diffraction patterns per second while monitoring the instantaneous sample temperature. The method is applied to a series of industrially relevant polymers, such as isotactic polypropylene, its copolymers and virgin and nucleated polyamide-6. Their crystallization behaviour during rapid cooling is discussed, with particular attention to the occurrence of polymorphism, which deeply impact material’s properties.

  19. Cathepsin B-sensitive polymers for compartment-specific degradation and nucleic acid release

    PubMed Central

    Chu, David S.H.; Johnson, Russell N.; Pun, Suzie H.

    2011-01-01

    Degradable cationic polymers are desirable for in vivo nucleic acid delivery because they offer significantly decreased toxicity over non-degradable counterparts. Peptide linkers provide chemical stability and high specificity for particular endopeptidases but have not been extensively studied for nucleic acid delivery applications. In this work, enzymatically degradable peptide-HPMA copolymers were synthesized by RAFT polymerization of HPMA with methacrylated peptide macromonomers, resulting in polymers with low polydispersity and near quantitative incorporation of peptides. Three peptide-HPMA copolymers were evaluated: (i) pHCathK10, containing peptides composed of the linker phe-lys-phe-leu (FKFL), a substrate of the endosomal/lysosomal endopeptidase cathepsin B, connected to oligo-(l)-lysine for nucleic acid binding, (ii) pHCath(d)K10, containing the FKFL linker with oligo-(d)-lysine, and (iii) pH(d)Cath(d)K10, containing all (d) amino acids. Cathepsin B degraded copolymers pHCathK10 and pHCath(d)K10 within one hour while no degradation of pH(d)Cath(d)K10 was observed. Polyplexes formed with pHCathK10 copolymers show DNA release by 4 hrs of treatment with cathepsin B; comparatively, polyplexes formed with pHCath(d)K10 and pH(d)Cath(d)K10 show no DNA release within 8 hrs. Transfection efficiency in HeLa and NIH/3T3 cells were comparable between the copolymers but pHCathK10 was less toxic. This work demonstrates the successful application of peptide linkers for degradable cationic polymers and DNA release. PMID:22036879

  20. Effect of dynamic operation on chemical degradation of a polymer electrolyte membrane fuel cell

    NASA Astrophysics Data System (ADS)

    Jung, Minjae; Williams, Keith A.

    2011-03-01

    Dynamic operation is known as one of the factors for accelerating chemical degradation of the polymer electrolyte membrane in a polymer electrolyte membrane fuel cell (PEMFC). However, little effort has been made dealing with the quantification of the degradation process. In this investigation, cyclic current operation is carried out on a fuel cell system, and the frequency effect of cyclic operation on chemical degradation is investigated. The dynamic behavior of a fuel cell system is analyzed first with the modified Randles model, where the charge double layer is modeled by three components; a charge transfer resistance (Rct), and two RC cells for the Warburg impedance. After calculating each parameter value through exponential curve fitting, the dynamic behaviors of the three components are simulated using MATLAB Simulink®. Fluoride release as a function of the frequency of cyclic operation is evaluated by measuring the concentration of fluoride ion in effluent from a fuel cell exhaust. The frequency effect on chemical degradation is explained by comparing the simulated results and the fluoride release results. Two possible reasons for the accelerated degradation at cyclic operation are also suggested.

  1. Resistance of radiation-induced tropical wood-polymer composites to fungal degradation

    NASA Astrophysics Data System (ADS)

    Chia, L. H. L.; Lim, V. S. L.; Yap, M. G. S.

    The resistance of six tropical hardwoods to fungal degradation by two wild-type strains of Phanerochaete chrysosporium Burdsall was investigated using vermiculite burial and wood-block weight loss techniques. Radiation-induced wood-polymer composites (WPC), based on two hardwoods Ramin and Rubber-wood with methyl methacrylate, were prepared, and samples were also exposed to the wood-rotting fungus. A significant improvement in resistance to fungal decay was observed in the WPC. Scanning-electron micrographs of the two woods and their composites after fungal degradation are presented and discussed.

  2. Thermal Degradation studies of nitroplasticized estane 5703 utilizing [sup 13] C enriched model polymers.

    SciTech Connect

    Wrobleski, Debra A.; Langlois, D. A.; Orler, E. B.; Schoonover, J. R.; Osborn, J. C.; Small, J. H.

    2002-01-01

    Predicting the lifetime of PBX 9501 is critical to assurance of the reliability of the nuclear weapons stockpile. Ln support of the Lifetime Prediction Model, we have been investigating the physical and chemical aging processes that can potentially affect the lifetime of PBX 9501. Surveillance data of stockpile PBX 9501 binder have shown a decrease in Estane molecular weight as a fiinction of age. Estane is a poly(ester urethane) consisting of poly(buly1ene adipate) as the flexible soft segment and 4,4{prime}-methylenediphenyl-1,1{prime}-diisocyanate (MDI) chain extended with 1,4-butanediol (BDO) as the rigid hard segment efforts have focused on chemical reactions that may cause chain scission of Estane through hydrolytic degradation of the polyester soft segments. Thermal aging of Estane in the absence of water shows no signs of hydrolytic degradation, whereas, appearance of high molecular weight species has been observed for Estane aged at elevated temperatures in the presence of nitroplasticizer. These high molecular weight species are most likely due to branching reactions that eventually leads to formation of an insoluble, cross-linked gel. While the mechanisms of hydrolytic degradation of polyesters has been addressed, the degradations reactions of poly(ester urethane) (PESU) in the presence of NP are not well understood. We have prepared a series of isotopically enriched PESU model compounds chemically similar to Estane for aging experiments in order to understand possible cross-linking mechanisms. Changes in physical properties are observed with less than 1% chemical cross-linking. Isotopic enrichment of 13C from 1.1 % natural abundance to 100% improves the sensitivity of spectroscopic techniques so that small quantities of degradation products can be observed. Because degradation reaction mechanisms of importance may occur at the hard segment portion of the polymer, we have prepared 13C PESU with 13C labeled at the methylene carbon. These model polymers

  3. Local Imaging of Optoelectronic Properties and Film Degradation in Polymer/Fullerene Solar Cells with Electrostatic Force Microscopy

    NASA Astrophysics Data System (ADS)

    Cox, Phillip Alexander

    With power conversion efficiencies on the rise, organic photovoltaics (OPVs) hold promise as a next-generation thin-film solar technology. However, both device performance and stability are inextricably linked to local film structure. Methods capable of probing nanoscale electronic properties as a function of film structure are thus a crucial component of the rational design of efficient and robust devices. This dissertation describes the use of three scanning probe methods for studying local charge generation and photodegradation in polymer/fullerene solar cells. First, we show that time-resolved electrostatic force microscopy (trEFM) is capable of resolving local photocurrent from sub-bandgap excitation down to attoampere level currents, a result unattainable by traditional contact-mode methods. We find that the local charging rates measured with trEFM are proportional to external quantum efficiency (EQE) measurements made on completed devices, making trEFM images equivalent to local EQE maps across the entire solar spectrum. For both phase-segregated and well-mixed MDMO-PPV:PCBM film morphologies, we show that the local distribution of photocurrent is invariant to excitation wavelength, providing local evidence for the controversial result that the probability of generating separated charge carriers does not depend on whether excitons are formed at the singlet state or charge transfer state. Next, we describe how local dissipation imaging can be performed with commercially-available frequency-modulated electrostatic force microscopy (FM-EFM) and show that dissipation maps are highly sensitive to photo-oxidative effects in organic semiconductors. We show that photo-oxidation induced changes in cantilever energy dissipation are proportional to device performance losses. We further develop dissipation imaging by implementing ringdown imaging, which directly measures the quality factor of the cantilever, enabling quantitative dissipation mapping. Using organic

  4. Novel Phenanthrene-Degrading Bacteria Identified by DNA-Stable Isotope Probing.

    PubMed

    Jiang, Longfei; Song, Mengke; Luo, Chunling; Zhang, Dayi; Zhang, Gan

    2015-01-01

    Microorganisms responsible for the degradation of phenanthrene in a clean forest soil sample were identified by DNA-based stable isotope probing (SIP). The soil was artificially amended with either 12C- or 13C-labeled phenanthrene, and soil DNA was extracted on days 3, 6 and 9. Terminal restriction fragment length polymorphism (TRFLP) results revealed that the fragments of 219- and 241-bp in HaeIII digests were distributed throughout the gradient profile at three different sampling time points, and both fragments were more dominant in the heavy fractions of the samples exposed to the 13C-labeled contaminant. 16S rRNA sequencing of the 13C-enriched fraction suggested that Acidobacterium spp. within the class Acidobacteria, and Collimonas spp. within the class Betaproteobacteria, were directly involved in the uptake and degradation of phenanthrene at different times. To our knowledge, this is the first report that the genus Collimonas has the ability to degrade PAHs. Two PAH-RHDα genes were identified in 13C-labeled DNA. However, isolation of pure cultures indicated that strains of Staphylococcus sp. PHE-3, Pseudomonas sp. PHE-1, and Pseudomonas sp. PHE-2 in the soil had high phenanthrene-degrading ability. This emphasizes the role of a culture-independent method in the functional understanding of microbial communities in situ.

  5. Novel Phenanthrene-Degrading Bacteria Identified by DNA-Stable Isotope Probing

    PubMed Central

    Luo, Chunling; Zhang, Dayi; Zhang, Gan

    2015-01-01

    Microorganisms responsible for the degradation of phenanthrene in a clean forest soil sample were identified by DNA-based stable isotope probing (SIP). The soil was artificially amended with either 12C- or 13C-labeled phenanthrene, and soil DNA was extracted on days 3, 6 and 9. Terminal restriction fragment length polymorphism (TRFLP) results revealed that the fragments of 219- and 241-bp in HaeIII digests were distributed throughout the gradient profile at three different sampling time points, and both fragments were more dominant in the heavy fractions of the samples exposed to the 13C-labeled contaminant. 16S rRNA sequencing of the 13C-enriched fraction suggested that Acidobacterium spp. within the class Acidobacteria, and Collimonas spp. within the class Betaproteobacteria, were directly involved in the uptake and degradation of phenanthrene at different times. To our knowledge, this is the first report that the genus Collimonas has the ability to degrade PAHs. Two PAH-RHDα genes were identified in 13C-labeled DNA. However, isolation of pure cultures indicated that strains of Staphylococcus sp. PHE-3, Pseudomonas sp. PHE-1, and Pseudomonas sp. PHE-2 in the soil had high phenanthrene-degrading ability. This emphasizes the role of a culture-independent method in the functional understanding of microbial communities in situ. PMID:26098417

  6. Sensitivity enhancement of electro-optic polymer probing system using photo-isomerization and Fabry-Pérot effects

    NASA Astrophysics Data System (ADS)

    Kuo, Wen-Kai; Su, Tzu-Mao; Ke, Zong-You; Lin, Hui-Chi; Wu, Chien-Jang

    2013-07-01

    A sensitivity enhancement method for an external electro-optic (EO) probing system using a poled polymer as an EO sensor is proposed. A pumping laser, which induces the photo-isomerization effect in a prepoled EO polymer, and a tunable probing laser, which induces Fabry-Pérot effect, are combined to enhance the polymer EO sensor sensitivity. Results of an experiment with an EO sensor made of Disperse Red 1 poly(methy1 methacrylate) that demonstrates this combined effect are reported.

  7. Sixteenth Quarterly Report Regulation of Coal Polymer Degradation by Fungi

    SciTech Connect

    John A. Bumpus

    1998-07-31

    Three phenomena which concern coal solubilization and depolymerization were studied during this reporting period. Previous investigations have shown that lignin peroxidases mediate the oxidation of soluble coal macromolecule. Because it appears to be a substrate, soluble coal macromolecule is also an inhibitor of veratryl alcohol oxidation, a reaction that is mediated by these enzymes. The mechanism of inhibition is complex in that oxidation (as assayed by decolorization) of soluble coal macromolecule requires the presence of veratryl alcohol and veratryl alcohol oxidation occurs only after a substantial lag period during which the soluble coal macromolecule is oxidized. In a previous quarterly report we proposed a reaction mechanism by which this may occur. During the present reporting period we showed that our proposed reaction mechanism is consistent with classical enzyme kinetic theory describing enzyme activity in the presence of a potent inhibitor (i.e., an inhibitor with a very low KI ). The oxidative decolorization and depolymerization of soluble coal macromolecule was also studied. Because wood rotting fungi produce hydrogen peroxide via a variety of reactions, we studied the effect of hydrogen peroxide on soluble coal macromolecule decolorization and depolymerization. Results showed that substantial decolorization occurred only at hydrogen peroxide concentrations that are clearly non-physiological (i.e., 50 mM or greater). It was noted, however, that when grown on solid lignocellulosic substrates, wood rotting fungi, overtime, cumulatively could produce amounts of hydrogen peroxide that might cause significant oxidative degradation of soluble coal macromolecule. Thirdly, we have shown that during oxalate mediated solubilization of low rank coal, a pH increase is observed. During this reporting period we have shown that the pH of solutions containing only sodium oxalate also undergo an increase in pH, but to a lesser extent than that observed in mixtures

  8. Synthesis and Testing of Polymers Susceptible to Degradation by Proteolytic Enzymes

    DTIC Science & Technology

    1975-05-01

    problem of disposal of plastics and synthetic fleers after use 1s well known. Some plastics evolve poisonous or corrosive gases during combustion...200°C, but a melting peak near 60°C Indicated that crystalline polycaprolactone sequences were still present. The polymer was soluble 1n m- cresol ...new material, a degradation study 1s 1r4"-ted as follows: Into 24 ml corrosion resistant borosilicats glass vials is added 50-200 mg of powdered

  9. α-Amino acid containing degradable polymers as functional biomaterials: rational design, synthetic pathway, and biomedical applications.

    PubMed

    Sun, Huanli; Meng, Fenghua; Dias, Aylvin A; Hendriks, Marc; Feijen, Jan; Zhong, Zhiyuan

    2011-06-13

    Currently, biomedical engineering is rapidly expanding, especially in the areas of drug delivery, gene transfer, tissue engineering, and regenerative medicine. A prerequisite for further development is the design and synthesis of novel multifunctional biomaterials that are biocompatible and biologically active, are biodegradable with a controlled degradation rate, and have tunable mechanical properties. In the past decades, different types of α-amino acid-containing degradable polymers have been actively developed with the aim to obtain biomimicking functional biomaterials. The use of α-amino acids as building units for degradable polymers may offer several advantages: (i) imparting chemical functionality, such as hydroxyl, amine, carboxyl, and thiol groups, which not only results in improved hydrophilicity and possible interactions with proteins and genes, but also facilitates further modification with bioactive molecules (e.g., drugs or biological cues); (ii) possibly improving materials biological properties, including cell-materials interactions (e.g., cell adhesion, migration) and degradability; (iii) enhancing thermal and mechanical properties; and (iv) providing metabolizable building units/blocks. In this paper, recent developments in the field of α-amino acid-containing degradable polymers are reviewed. First, synthetic approaches to prepare α-amino acid-containing degradable polymers will be discussed. Subsequently, the biomedical applications of these polymers in areas such as drug delivery, gene delivery and tissue engineering will be reviewed. Finally, the future perspectives of α-amino acid-containing degradable polymers will be evaluated.

  10. Effect of Boric Acid on Volatile Products of Thermooxidative Degradation of Epoxy Polymers

    NASA Astrophysics Data System (ADS)

    Nazarenko, O. B.; Bukhareva, P. B.; Melnikova, T. V.; Visakh, P. M.

    2016-01-01

    The polymeric materials are characterized by high flammability. The use of flame retardants in order to reduce the flammability of polymers can lead to the formation of toxic gaseous products under fire conditions. In this work we studied the effect of boric acid on the volatile products of thermooxidative degradation of epoxy polymers. The comparative investigations were carried out on the samples of the unfilled epoxy resin and epoxy resin filled with a boric acid at percentage 10 wt. %. The analysis of the volatile decomposition products and thermal stability of the samples under heating in an oxidizing medium was performed using a thermal mass-spectrometric analysis. It is found that the incorporation of boric acid into the polymer matrix increases the thermal stability of epoxy composites and leads to a reduction in the 2-2.7 times of toxic gaseous products

  11. Degradable Polymer-Coated Gold Nanoparticles for Co-Delivery of DNA and siRNA

    PubMed Central

    Bishop, Corey J.; Tzeng, Stephany Y.; Green, Jordan J.

    2014-01-01

    Gold nanoparticles have utility for in vitro, ex vivo, and in vivo imaging applications as well as for serving as a scaffold for therapeutic delivery and theranostic applications. Starting with gold nanoparticles as a core, layer-by-layer degradable polymer coatings enable co-delivery of both DNA and short interfering RNA simultaneously. To engineer release kinetics, polymers which degrade through two different mechanisms can be utilized to construct hybrid inorganic/polymeric particles. During fabrication of the nanoparticles, the zeta potential reverses upon the addition of each oppositely charged polyelectrolyte layer and the final nanoparticle size reaches approximately 200 nm in diameter. When the hybrid gold/polymer/nucleic acid nanoparticles are added to human primary brain cancer cells in vitro, they are internalizable by cells and reach the cytoplasm and nucleus as visualized by transmission electron microscopy and observed through exogenous gene expression. This nanoparticle delivery leads to both exogenous DNA expression and siRNA-mediated knockdown, with the knockdown efficacy superior to that of Lipofectamine® 2000, a commercially available transfection reagent. These gold/polymer/nucleic acid hybrid nanoparticles are an enabling theranostic platform technology capable of delivering combinations of genetic therapies to human cells. PMID:25246314

  12. Degradable polymer-coated gold nanoparticles for co-delivery of DNA and siRNA.

    PubMed

    Bishop, Corey J; Tzeng, Stephany Y; Green, Jordan J

    2015-01-01

    Gold nanoparticles have utility for in vitro, ex vivo and in vivo imaging applications as well as for serving as a scaffold for therapeutic delivery and theranostic applications. Starting with gold nanoparticles as a core, layer-by-layer degradable polymer coatings enable the simultaneous co-delivery of DNA and short interfering RNA (siRNA). To engineer release kinetics, polymers which degrade through two different mechanisms can be utilized to construct hybrid inorganic/polymeric particles. During fabrication of the nanoparticles, the zeta potential reverses upon the addition of each oppositely charged polyelectrolyte layer and the final nanoparticle size reaches approximately 200nm in diameter. When the hybrid gold/polymer/nucleic acid nanoparticles are added to human primary brain cancer cells in vitro, they are internalizable by cells and reach the cytoplasm and nucleus as visualized by transmission electron microscopy and observed through exogenous gene expression. This nanoparticle delivery leads to both exogenous DNA expression and siRNA-mediated knockdown, with the knockdown efficacy superior to that of Lipofectamine® 2000, a commercially available transfection reagent. These gold/polymer/nucleic acid hybrid nanoparticles are an enabling theranostic platform technology capable of delivering combinations of genetic therapies to human cells.

  13. Mesoporous Nano-Silica Serves as the Degradation Inhibitor in Polymer Dielectrics

    PubMed Central

    Yang, Yang; Hu, Jun; He, Jinliang

    2016-01-01

    A new generation of nano-additives for robust high performance nanodielectrics is proposed. It is demonstrated for the first time that mesoporous material could act as “degradation inhibitor” for polymer dielectrics to sequestrate the electrical degradation products then restrain the electrical aging process especially under high temperature conditions, which is superior to the existing additives of nanodielectrics except further increasing the dielectric strength. Polyethylenimine (PEI) loaded nano-scaled mesoporous silica MCM-41 (nano-MS) is doped into the dielectric matrix to prepare the PP/MCM-41-PEI nanocomposites. PEI provides the amines to capture the electrical degradation products while the MCM-41 brackets afford large adsorption surface, bring down the activating temperature of the absorbent then enhance the absorptive capacity. The electrical aging tests confirm the contribution of the mesoporous structure to electrical aging resistance and FT-IR analysis of the electrical degraded regions demonstrates the chemical absorption especially under high temperature conditions. Take the experimental data as examples, extending the aging durability and dielectric strength of polymer dielectrics by 5 times and 16%, respectively, can have substantial commercial significance in energy storage, power electronics and power transmission areas. PMID:27338622

  14. Polymer Film-Based Screening and Isolation of Polylactic Acid (PLA)-Degrading Microorganisms.

    PubMed

    Kim, Mi Yeon; Kim, Changman; Moon, Jungheun; Heo, Jinhee; Jung, Sokhee P; Kim, Jung Rae

    2017-02-28

    Polylactic acid (PLA) has been highlighted as an alternative renewable polymer for the replacement of petroleum-based plastic materials, and is considered to be biodegradable. On the other hand, the biodegradation of PLA by terminal degraders, such as microorganisms, requires a lengthy period in the natural environment, and its mechanism is not completely understood. PLA biodegradation studies have been conducted using mainly undefined mixed cultures, but only a few bacterial strains have been isolated and examined. For further characterization of PLA biodegradation, in this study, the PLA-degrading bacteria from digester sludge were isolated and identified using a polymer film-based screening method. The enrichment of sludge on PLA granules was conducted with the serial transference of a subculture into fresh media for 40 days, and the attached biofilm was inoculated on a PLA film on an agar plate. 3D optical microscopy showed that the isolates physically degraded the PLA film due to bacterial degradation. 16S rRNA gene sequencing identified the microbial colonies to be Pseudomonas sp. MYK1 and Bacillus sp. MYK2. The two isolates exhibited significantly higher specific gas production rates from PLA biodegradation compared with that of the initial sludge inoculum.

  15. Mesoporous Nano-Silica Serves as the Degradation Inhibitor in Polymer Dielectrics.

    PubMed

    Yang, Yang; Hu, Jun; He, Jinliang

    2016-06-24

    A new generation of nano-additives for robust high performance nanodielectrics is proposed. It is demonstrated for the first time that mesoporous material could act as "degradation inhibitor" for polymer dielectrics to sequestrate the electrical degradation products then restrain the electrical aging process especially under high temperature conditions, which is superior to the existing additives of nanodielectrics except further increasing the dielectric strength. Polyethylenimine (PEI) loaded nano-scaled mesoporous silica MCM-41 (nano-MS) is doped into the dielectric matrix to prepare the PP/MCM-41-PEI nanocomposites. PEI provides the amines to capture the electrical degradation products while the MCM-41 brackets afford large adsorption surface, bring down the activating temperature of the absorbent then enhance the absorptive capacity. The electrical aging tests confirm the contribution of the mesoporous structure to electrical aging resistance and FT-IR analysis of the electrical degraded regions demonstrates the chemical absorption especially under high temperature conditions. Take the experimental data as examples, extending the aging durability and dielectric strength of polymer dielectrics by 5 times and 16%, respectively, can have substantial commercial significance in energy storage, power electronics and power transmission areas.

  16. Mesoporous Nano-Silica Serves as the Degradation Inhibitor in Polymer Dielectrics

    NASA Astrophysics Data System (ADS)

    Yang, Yang; Hu, Jun; He, Jinliang

    2016-06-01

    A new generation of nano-additives for robust high performance nanodielectrics is proposed. It is demonstrated for the first time that mesoporous material could act as “degradation inhibitor” for polymer dielectrics to sequestrate the electrical degradation products then restrain the electrical aging process especially under high temperature conditions, which is superior to the existing additives of nanodielectrics except further increasing the dielectric strength. Polyethylenimine (PEI) loaded nano-scaled mesoporous silica MCM-41 (nano-MS) is doped into the dielectric matrix to prepare the PP/MCM-41-PEI nanocomposites. PEI provides the amines to capture the electrical degradation products while the MCM-41 brackets afford large adsorption surface, bring down the activating temperature of the absorbent then enhance the absorptive capacity. The electrical aging tests confirm the contribution of the mesoporous structure to electrical aging resistance and FT-IR analysis of the electrical degraded regions demonstrates the chemical absorption especially under high temperature conditions. Take the experimental data as examples, extending the aging durability and dielectric strength of polymer dielectrics by 5 times and 16%, respectively, can have substantial commercial significance in energy storage, power electronics and power transmission areas.

  17. Degradation of different elastomeric polymers in simulated geothermal environments at 300°C

    DOE PAGES

    Sugama, Toshifumi; Pyatina, Tatiana; Redline, Erica Marie; ...

    2015-07-17

    This study evaluates the degradation of six different elastomeric polymers used for O-rings: EPDM, FEPM, type I- and II-FKM, FFKM, and FSR, in five different simulated geothermal environments at 300 °C: 1) non-aerated steam/cooling cycles, 2) aerated steam/cooling cycles, 3) water-based drilling fluid, 4) CO2-rich geo-brine fluid, and, 5) heat–cool water quenching cycles. The factors assessed included the extent of oxidation, changes in thermal behavior, micro-defects, permeation of ionic species from the test environments into the O-rings, silicate-related scale-deposition, and changes in the O-rings' elastic modulus. The reliability of the O-rings to maintain their integrity depended on the elastomeric polymermore » composition and the exposure environment. FSR disintegrated while EPDM was oxidized only to some degree in all the environments, FKM withstood heat-water quenching but underwent chemical degradation, FEPM survived in all the environments with the exception of heat-water quenching where it underwent severe oxidation-induced degradation, and FFKM displayed outstanding compatibility with all the tested environments. This study discusses the degradation mechanisms of the polymers under the aforementioned conditions.« less

  18. Probing the dynamics of high-viscosity entangled polymers under shear using Neutron Spin Echo spectroscopy

    NASA Astrophysics Data System (ADS)

    Kawecki, M.; Gutfreund, P.; Adlmann, F. A.; Lindholm, E.; Longeville, S.; Lapp, A.; Wolff, M.

    2016-09-01

    Neutron Spin Echo spectroscopy provides unique insight into molecular and submolecular dynamics as well as intra- and inter-molecular interactions in soft matter. These dynamics may change drastically under shear flow. In particular in polymer physics a stress plateau is observed, which might be explained by an entanglement-disentanglement transition. However, such a transition is difficult to identify directly by experiments. Neutron Spin Echo has been proven to provide information about entanglement length and degree by probing the local dynamics of the polymer chains. Combining shear experiments and neutron spin echo is challenging since, first the beam polarisation has to be preserved during scattering and second, Doppler scattered neutrons may cause inelastic scattering. In this paper we present a new shear device adapted for these needs. We demonstrate that a high beam polarisation can be preserved and present first data on an entangled polymer solution under shear. To complement the experiments on the dynamics we present novel SANS data revealing shear- induced conformational changes in highly entangled polymers.

  19. Occurrence, degradation, and effect of polymer-based materials in the environment.

    PubMed

    Lambert, Scott; Sinclair, Chris; Boxall, Alistair

    2014-01-01

    There is now a plethora of polymer-based materials (PBMs) on the market, because of the increasing demand for cheaper consumable goods, and light-weight industrial materials. Each PBM constitutes a mixture of their representative polymer/sand their various chemical additives. The major polymer types are polyethylene, polypropylene,and polyvinyl chloride, with natural rubber and biodegradable polymers becoming increasingly more important. The most important additives are those that are biologically active, because to be effective such chemicals often have properties that make them resistant to photo-degradation and biodegradation. During their lifecycle,PBMs can be released into the environment form a variety of sources. The principal introduction routes being general littering, dumping of unwanted waste materials,migration from landfills and emission during refuse collection. Once in the environment,PBMs are primarily broken down by photo-degradation processes, but due to the complex chemical makeup of PBMs, receiving environments are potentially exposed to a mixture of macro-, meso-, and micro-size polymer fragments, leached additives, and subsequent degradation products. In environments where sunlight is absent (i.e., soils and the deep sea) degradation for most PBMs is minimal .The majority of literature to date that has addressed the environmental contamination or disposition of PBMs has focused on the marine environment. This is because the oceans are identified as the major sink for macro PBMs, where they are known to present a hazard to wildlife via entanglement and ingestion. The published literature has established the occurrence of microplastics in marine environment and beach sediments, but is inadequate as regards contamination of soils and freshwater sediments. The uptake of microplastics for a limited range of aquatic organisms has also been established, but there is a lack of information regarding soil organisms, and the long-term effects of

  20. Stress and Damage in Polymer Matrix Composite Materials Due to Material Degradation at High Temperatures

    NASA Technical Reports Server (NTRS)

    McManus, Hugh L.; Chamis, Christos C.

    1996-01-01

    This report describes analytical methods for calculating stresses and damage caused by degradation of the matrix constituent in polymer matrix composite materials. Laminate geometry, material properties, and matrix degradation states are specified as functions of position and time. Matrix shrinkage and property changes are modeled as functions of the degradation states. The model is incorporated into an existing composite mechanics computer code. Stresses, strains, and deformations at the laminate, ply, and micro levels are calculated, and from these calculations it is determined if there is failure of any kind. The rationale for the model (based on published experimental work) is presented, its integration into the laminate analysis code is outlined, and example results are given, with comparisons to existing material and structural data. The mechanisms behind the changes in properties and in surface cracking during long-term aging of polyimide matrix composites are clarified. High-temperature-material test methods are also evaluated.

  1. Degradation kinetics of polymers in solution: Time-dependence of molecular weight distributions. [Quarterly report, January--March 1996

    SciTech Connect

    McCoy, B.J.; Madras, G.

    1996-02-27

    Polymer degradation occurs when polymer chains are broken under the influence of thermal, mechanical, or chemical energy. Chain-end depolymerization and random- and midpoint-chain scission are mechanisms that have been observed in liquid-phase polymer degradation. Here we develop mathematical models, unified by continuous-mixture kinetics, to show how these different mechanisms affect polymer degradation in solution. Rate expressions for the fragmentation of molecular-weight distributions (MWDs) govern the evolution of the MWDs. The governing integro-differential equations can be solved analytically for realistic conditions. Moment analysis for first-order continuous kinetics shows the temporal behavior of MWDs. Chain-end depolymerization yields monomer product and polymer molecular-weight moments that vary linearly with time. In contrast, random- and midpoint-chain scission models display exponential time behavior. The mathematical results reasonably portray experimental observations for polymer degradation. This approach, based on the time evolution of continuous distributions of chain length or molecular weight, provides a framework for interpreting several types of polymer degradation processes.

  2. Spectroscopic and kinetic studies on the degradation of methylene blue using the supramolecular coordination polymer [(Ph3Sn)4FeCN(6)] as catalyst.

    PubMed

    Ibrahim, Amany M A; Al-Ashqar, Sawsan M A

    2012-06-15

    The structure of the supramolecular coordination polymer (SCP), [(Ph(3)Sn)(4)Fe(CN)(6)], 1, consists of octahedral [Fe(CN)(6)](4-) building blocks which are connected by the TBPY-5 configured Ph(3)Sn(CN…)(2) fragments creating 3D-network structure that contains terminal cyanide groups. The catalytic behavior of the SCP 1 was utilized for Fenton and photo-Fenton degradation of methylene blue dye (MB). The plot of kinetic degradation indicates pseudo first-order rate with respect to the MB dye concentration, K(obs.)=0.071 min(-1). On the other hand, the observed rate constant of the photo catalytic degradation of MB equals to 1.45 min(-1) indicating that irradiation enhances, significantly, the rate of degradation of MB dye. Discoloration of the dye was obtained in less than 3h. Meanwhile, the conjugated structure and the phenyl rings of the MB molecule were destroyed or even broken down into small organic acids and inorganic ions, as indicated by FT-IR spectra. Disodium salt of terephthalic acid photoluminescence probing technology and radical scavenging measurements were carried out to identify the reactive oxygen species. The different parameters that affect MB degradation rate were evaluated. Moreover, the efficiency of recycled the SCP 1 and the mechanism of degradation of MB dye was investigated.

  3. Construction and applications of DNA probes for detection of polychlorinated biphenyl-degrading genotypes in toxic organic-contaminated soil environments

    SciTech Connect

    Walia, S.; Khan, A.; Rosenthal, N. )

    1990-01-01

    Several DNA probes for polychlorinated biphenyl (PCB)-degrading genotypes were constructed from PCB-degrading bacteria. These laboratory-engineered DNA probes were used for the detection, enumeration, and isolation of specific bacteria degrading PCBs. Dot blot analysis of purified DNA from toxic organic chemical-contaminated soil bacterial communities showed positive DNA-DNA hybridization with a 32P-labeled DNA probe (pAW6194, cbpABCD). Less than 1% of bacterial colonies isolated from garden topsoil and greater than 80% of bacteria isolated from PCB-contaminated soils showed DNA homologies with 32P-labeled DNA probes. Some of the PCB-degrading bacterial isolates detected by the DNA probe method did not show biphenyl clearance. The DNA probe method was found to detect additional organisms with greater genetic potential to degrade PCBs than the biphenyl clearance method did. Results from this study demonstrate the usefulness of DNA probes in detecting specific PCB-degrading bacteria, abundance of PCB-degrading genotypes, and genotypic diversity among PCB-degrading bacteria in toxic chemical-polluted soil environments. We suggest that the DNA probe should be used with caution for accurate assessment of PCB-degradative capacity within soils and further recommend that a combination of DNA probe and biodegradation assay be used to determine the abundance of PCB-degrading bacteria in the soil bacterial community.

  4. Photocatalytic degradation of dimethoate using LbL fabricated TiO2/polymer hybrid films.

    PubMed

    Priya, D Neela; Modak, Jayant M; Trebše, Polonca; Zabar, Romina; Raichur, Ashok M

    2011-11-15

    Degradation of dimethoate under UV irradiation using TiO(2)/polymer films prepared by the layer-by-layer (LbL) method was investigated. The thin films were fabricated on glass slides and the surface morphology and roughness of the thin films were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The effect of lamp intensity, catalyst loading in the layers, number of bilayers, pH and initial dimethoate concentration on the degradation of dimethoate was systematically studied. The degradation was monitored using high performance liquid chromatography (HPLC) analysis and total organic carbon (TOC) measurements as a function of irradiation time, to see the change in concentration of dimethoate and mineralization, respectively. Complete degradation of dimethoate was achieved under TiO(2) optimum loading of 4 g/L at an UV irradiation time of 180 min. Increase in the lamp intensity, catalyst loading and number of bilayers increased the rate of degradation. At a pH of 4.62, complete degradation of dimethoate was observed. The degradation efficiency decreased with increase in initial dimethoate concentration. The degradation byproducts were analyzed and confirmed by gas chromatography-mass spectra (GC-MS). Toxicity of the irradiated samples was measured using the luminescence of bacteria Vibrio fischeri after 30 min of incubation and the results showed more toxicity than the parent compound. Catalyst reusability studies revealed that the fabricated thin films could be repeatedly used for up to ten times without affecting the photocatalytic activity of the films. The findings of the present study are very useful for the treatment of wastewaters contaminated with pesticides.

  5. Anaerobic Methyl tert-Butyl Ether-Degrading Microorganisms Identified in Wastewater Treatment Plant Samples by Stable Isotope Probing

    PubMed Central

    Sun, Weimin; Sun, Xiaoxu

    2012-01-01

    Anaerobic methyl tert-butyl ether (MTBE) degradation potential was investigated in samples from a range of sources. From these 22 experimental variations, only one source (from wastewater treatment plant samples) exhibited MTBE degradation. These microcosms were methanogenic and were subjected to DNA-based stable isotope probing (SIP) targeted to both bacteria and archaea to identify the putative MTBE degraders. For this purpose, DNA was extracted at two time points, subjected to ultracentrifugation, fractioning, and terminal restriction fragment length polymorphism (TRFLP). In addition, bacterial and archaeal 16S rRNA gene clone libraries were constructed. The SIP experiments indicated bacteria in the phyla Firmicutes (family Ruminococcaceae) and Alphaproteobacteria (genus Sphingopyxis) were the dominant MTBE degraders. Previous studies have suggested a role for Firmicutes in anaerobic MTBE degradation; however, the putative MTBE-degrading microorganism in the current study is a novel MTBE-degrading phylotype within this phylum. Two archaeal phylotypes (genera Methanosarcina and Methanocorpusculum) were also enriched in the heavy fractions, and these organisms may be responsible for minor amounts of MTBE degradation or for the uptake of metabolites released from the primary MTBE degraders. Currently, limited information exists on the microorganisms able to degrade MTBE under anaerobic conditions. This work represents the first application of DNA-based SIP to identify anaerobic MTBE-degrading microorganisms in laboratory microcosms and therefore provides a valuable set of data to definitively link identity with anaerobic MTBE degradation. PMID:22327600

  6. Tetracycline-HCl-loaded poly(DL-lactide-co-glycolide) microspheres prepared by a spray drying technique: influence of gamma-irradiation on radical formation and polymer degradation.

    PubMed

    Bittner, B; Mäder, K; Kroll, C; Borchert, H H; Kissel, T

    1999-05-01

    Tetracycline-HCl (TCH)-loaded microspheres were prepared from poly(lactide-co-glycolide) (PLGA) by spray drying. The drug was incorporated in the polymer matrix either in solid state or as w/o emulsion. The spin probe 4-hydroxy-2,2,6, 6-tetramethyl-piperidine-1-oxyl (TEMPOL) and the spin trap tert-butyl-phenyl-nitrone (PBN) were co-encapsulated into the TCH-loaded and placebo particles. We investigated the effects of gamma-irradiation on the formation of free radicals in polymer and drug and the mechanism of chain scission after sterilization. Gamma-Irradiation was performed at 26.9 and 54.9 kGy using a 60Co source. The microspheres were characterized especially with respect to the formation of radicals and in vitro polymer degradation. Electron paramagnetic resonance (EPR) spectroscopy, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), high-performance liquid chromatography (HPLC), gas chromatography-mass spectroscopy (GC-MS), and scanning electron microscopy (SEM) were used for characterization of the microspheres. Using EPR spectroscopy, we successfully detected gamma-irradiation induced free radicals within the TCH-loaded microspheres, while unloaded PLGA did not contain radicals under the same conditions. The relatively low glass transition temperature of the poly(dl-lactide-co-glycolide) (37-39 degrees C) seems to favor subsequent reactions of free radicals due to the high mobility of the polymeric chains. Because of the high melting point of TCH (214 degrees C), the radicals can only be stabilized in drug loaded microspheres. In order to determine the mechanism of polymer degradation after exposure to gamma-rays, the spin trap PBN and the spin probe TEMPOL were encapsulated in the microspheres. gamma-Irradiation of microspheres containing PBN resulted in the formation of a lipophilic spin adduct, indicating that a polymeric radical was generated by random chain scission. Polymer degradation by an unzipping mechanism would have

  7. Degradable/non-degradable polymer composites for in-situ tissue engineering small diameter vascular prosthesis application.

    PubMed

    Wang, Fujun; Mohammed, Abedalwafa; Li, Chaojing; Ge, Peng; Wang, Lu; King, Martin W

    2014-01-01

    Various tissue-engineered vascular grafts have been studied in order to overcome the clinical disadvantages associated with conventional prostheses. However, previous tissue-engineered vascular grafts have possessed insufficient mechanical properties and thus have generally required either preoperative cellular manipulation or the use of bioreactors to improve their performance. In this study, we focused on the concept of in situ cellularization and developed a tissue-engineered vascular graft with degradable/non-degradable polymer composites for arterial reconstruction that would facilitate the renewal of autologous tissue without any pretreatment. Additionally, these composites are designed to improve the mechanical performance of a small-diameter vascular prosthesis scaffold that is made from a flexible membrane of poly(e-caprolactone) (PCL). The PCL scaffold was reinforced by embedding a tubular fabric that was knitted from polyethylene terephthalate (PET) yarns within the freeze-dried composite structure. Adding this knitted fabric component significantly improved the mechanical properties of the composite scaffold, such as its tensile strength and initial modulus, radial compliance, compression recovery, and suture retention force. Finally, this reinforced composite structure is a promising candidate for use as a tissue-engineered scaffold for a future small diameter vascular prosthesis.

  8. Release of engineered nanomaterials from polymer nanocomposites: the effect of matrix degradation.

    PubMed

    Duncan, Timothy V

    2015-01-14

    Polymer nanocomposites-polymer-based materials that incorporate filler elements possessing at least one dimension in the nanometer range-are increasingly being developed for commercial applications ranging from building infrastructure to food packaging to biomedical devices and implants. Despite a wide range of intended applications, it is also important to understand the potential for exposure to these nanofillers, which could be released during routine use or abuse of these materials so that it can be determined whether they pose a risk to human health or the environment. This article is the second of a pair that review what is known about the release of engineered nanomaterials (ENMs) from polymer nanocomposites. Two roughly separate ENM release paradigms are considered in this series: the release of ENMs via passive diffusion, desorption, and dissolution into external liquid media and the release of ENMs assisted by matrix degradation. The present article is focused primarily on the second paradigm and includes a thorough, critical review of the associated body of peer-reviewed literature on ENM release by matrix degradation mechanisms, including photodegradation, thermal decomposition, mechanical wear, and hydrolysis. These release mechanisms may be especially relevant to nanocomposites that are likely to be subjected to weathering, including construction and infrastructural materials, sporting equipment, and materials that might potentially end up in landfills. This review pays particular attention to studies that shed light on specific release mechanisms and synergistic mechanistic relationships. The review concludes with a short section on knowledge gaps and future research needs.

  9. Effect of pinhole location on degradation in polymer electrolyte fuel cells

    NASA Astrophysics Data System (ADS)

    Bodner, Merit; Hochenauer, Christoph; Hacker, Viktor

    2015-11-01

    This work analyses the impact of the location of pinholes in polymer electrolyte fuel cells on the degradation of the electrodes. Defects with a diameter of 0.45 mm were created in a 25 cm2 membrane electrode assembly (MEA) of a fuel cell. The MEA was operated and characterised using a segmented single cell. The effects of the pinholes on degradation were measured and evaluated. Defects affected the fuel cell behaviour during periods of hydrogen starvation, thus accelerating the degradation process of the carbon support as well as the loss of active platinum catalyst surface area. Furthermore, the effects of the induced pinholes on membrane degradation and performance decay were determined. Pinholes close to the anode inlet in general have shown a more severe effect on the fuel cell operation parameters, such as open circuit voltage, performance, membrane resistance and hydrogen crossover, than pinholes at any other locations. Also, electrode degradation was accelerated. These effects were mainly due to locally increased temperatures.

  10. Effect of catalyst layer defects on local membrane degradation in polymer electrolyte fuel cells

    NASA Astrophysics Data System (ADS)

    Tavassoli, Arash; Lim, Chan; Kolodziej, Joanna; Lauritzen, Michael; Knights, Shanna; Wang, G. Gary; Kjeang, Erik

    2016-08-01

    Aiming at durability issues of fuel cells, this research is dedicated to a novel experimental approach in the analysis of local membrane degradation phenomena in polymer electrolyte fuel cells, shedding light on the potential effects of manufacturing imperfections on this process. With a comprehensive review on historical failure analysis data from field operated fuel cells, local sources of iron oxide contaminants, catalyst layer cracks, and catalyst layer delamination are considered as potential candidates for initiating or accelerating the local membrane degradation phenomena. Customized membrane electrode assemblies with artificial defects are designed, fabricated, and subjected to membrane accelerated stress tests followed by extensive post-mortem analysis. The results reveal a significant accelerating effect of iron oxide contamination on the global chemical degradation of the membrane, but dismiss local traces of iron oxide as a potential stressor for local membrane degradation. Anode and cathode catalyst layer cracks are observed to have negligible impact on the membrane degradation phenomena. Notably however, distinct evidence is found that anode catalyst layer delamination can accelerate local membrane thinning, while cathode delamination has no apparent effect. Moreover, a substantial mitigating effect for platinum residuals on the site of delamination is observed.

  11. Impacts of air bleeding on membrane degradation in polymer electrolyte fuel cells

    NASA Astrophysics Data System (ADS)

    Inaba, Minoru; Sugishita, Masashi; Wada, Junpei; Matsuzawa, Koichi; Yamada, Hirohisa; Tasaka, Akimasa

    A long-term accelerated test (4600 h) of a 25 cm 2 single cell with excess air bleeding (5%) was carried out to investigate the effects of air bleeding on membrane degradation in polymer electrolyte fuel cells. The rate of membrane degradation was negligibly low (fluoride-ion release rate = 1.3 × 10 -10 mol cm -2 h -1 in average) up to 2000 h. However, membrane degradation rate was gradually increased after 2000 h. The CO tolerance of the anode gradually dropped, which indicated that the anode catalyst was deteriorated during the test. The results of the rotating ring-disk electrode measurements revealed that deterioration of Pt-Ru/C catalyst by potential cycling greatly enhances H 2O 2 formation in oxygen reduction reaction in the anode potential range (∼0 V). Furthermore, membrane degradation rate of the MEA increased after the anode catalyst was forced to be deteriorated by potential cycling. It was concluded that excess air bleeding deteriorated the anode catalyst, which greatly enhanced H 2O 2 formation upon air bleeding and resulted in the increased membrane degradation rate after 2000 h.

  12. Graft copolymerization onto polybutadiene: Cross-linking and thermal degradation of vinyl polymers and copolymers

    NASA Astrophysics Data System (ADS)

    Jiang, Dayue (David)

    This work consists of three parts. In Part I, the graft copolymerization of methyl methacrylate, methyl acrylate, methacylic acid and acrylic acid onto polybutadiene and its copolymers by benzoyl peroxide, BPO, or 2, 2'azobis(2-methylpropionitrile), AIBN, initiation were explored. The results show that these monomers can be grafted onto butadiene region of butadiene-containing polymers. The extent of both graft copolymerization and homopolymerization are dependent on the time and temperature of the reaction and the concentration of all of the reactants. One must specify the monomer, initiator and solvent for the efficient graft copolymerization. The methyl methacrylate adds directly to the radical sites which are formed on the backbone by the interaction of the polymer and the primary radical form the initiator, while for the other three monomers, the graft copolymerization occurs by addition of macro-radical to the double bonds. In Part II, the cross-linking of polybutadiene, butadiene-styrene copolymers, and polystyrene by irradiation, thermal and chemical processes, and Friedel-Crafts chemistry and the effect of cross-linking on the thermal stability were investigated. The proof of cross-linking of the polymer comes from the insolubility of the product after the cross-linking reaction and is characterized by gel content and swelling ratio. The results show that the thermal stability of the polymer can be improved by cross-linking. In Part III, the thermal degradation of three vinyl polymers, poly(vinylsulfonic acid) and its sodium salt and poly(vinylphosphonic acid) were studied by combination technique: TGA/FTIR. The results show that TGA/FTIR combined with analysis of residues provides an excellent opportunity to understand the degradation pathway of the compounds. The observation of foaming indicates that the char which is formed contains carbon as well as the inorganic salts which have been observed. The carbon is in a partially graphitized form. The salts

  13. Particulate retrieval of hydrolytically degraded poly(lactide-co-glycolide) polymers.

    PubMed

    Cordewener, F W; Dijkgraaf, L C; Ong, J L; Agrawal, C M; Zardeneta, G; Milam, S B; Schmitz, J P

    2000-04-01

    This article describes a technique for the retrieval of polymeric particulate debris following advanced hydrolytic in vitro degradation of a biodegradable polymer and presents the results of the subsequent particle analysis. Granular 80/20 poly(L-lactide-co-glycolide) (PLG) was degraded in distilled, deionized water in Pyrextrade mark test tubes at 80 degrees C for 6 weeks. Subsequently, a density gradient was created by layering isopropanol over the water, followed by a 48-h incubation. Two opaque layers formed in the PLG tubes, which were removed and filtered through 0.2-micrometer polycarbonate membrane filters. In addition, Fourier transform IR spectroscopy (FTIR) was performed to confirm the presence of polymer in the removed layers. The filters were gold sputter coated, and scanning electron microscopy (SEM) images were made. FTIR analysis confirmed that the removed material was PLG. SEM images of the extracts from the upper (lowest density) opaque layer showed a fine, powderlike substance and globular structures of 500-750 nm. The SEM images of the lower (highest density) opaque layer showed particles with a crystalline-like morphology ranging in size from 4 to 30 micrometer. Particulate PLG debris generated with the described technique can be useful for further studies of its biological role in complications associated with poly(alpha-hydroxy)ester implants. This study shows the presence of very persistent nano- and microparticles in the degradation pathway of PLG.

  14. Dose rate effects in radiation degradation of polymer-based cable materials

    NASA Astrophysics Data System (ADS)

    Plaček, V.; Bartoníček, B.; Hnát, V.; Otáhal, B.

    2003-08-01

    Cable ageing under the nuclear power plant (NPP) conditions must be effectively managed to ensure that the required plant safety and reliability are maintained throughout the plant service life. Ionizing radiation is one of the main stressors causing age-related degradation of polymer-based cable materials in air. For a given absorbed dose, radiation-induced damage to a polymer in air environment usually depends on the dose rate of the exposure. In this work, the effect of dose rate on the degradation rate has been studied. Three types of NPP cables (with jacket/insulation combinations PVC/PVC, PVC/PE, XPE/XPE) were irradiated at room temperature using 60Co gamma ray source at average dose rates of 7, 30 and 100 Gy/h with the doses up to 590 kGy. The irradiated samples have been tested for their mechanical properties, thermo-oxidative stability (using differential scanning calorimetry, DSC), and density. In the case of PVC and PE samples, the tested properties have shown evident dose rate effects, while the XPE material has shown no noticeable ones. The values of elongation at break and the thermo-oxidative stability decrease with the advanced degradation, density tends to increase with the absorbed dose. For XPE samples this effect can be partially explained by the increase of crystallinity. It was tested by the DSC determination of the crystalline phase amount.

  15. Degradable phosphate glass fiber reinforced polymer matrices: mechanical properties and cell response.

    PubMed

    Brauer, Delia S; Rüssel, Christian; Vogt, Sebastian; Weisser, Jürgen; Schnabelrauch, Matthias

    2008-01-01

    The development of biodegradable materials for internal fracture fixation is of great interest, as they would both eliminate the problem of stress shielding and obviate the need for a second operation to remove fixation devices. Preliminary investigations for the production of degradable fiber reinforced polymer composite materials are detailed. Composites were produced of phosphate invert glass fibers of the glass system P(2)O(5)-CaO-MgO-Na(2)O-TiO(2), which showed a low solubility in previous work. The fibers were embedded into a matrix of a degradable organic polymer network based on methacrylate-modified oligolactide. Fracture behavior, bending strength and elastic modulus were evaluated during 3-point bending tests and the fracture surface of the composites was investigated using a scanning electron microscope. Short-term biocompatibility was tested in an FDA/EtBr viability assay using MC3T3-E1 murine pre-osteoblast cells and showed a good cell compatibility of the composite materials. Results suggested that these composite materials are biocompatible and show mechanical properties which are of interest for the production of degradable bone fixation devices.

  16. Photo-triggered molecular release based on auto-degradable polymer-containing organic-inorganic hybrids.

    PubMed

    Okada, Hiroshi; Tanaka, Kazuo; Ohashi, Wataru; Chujo, Yoshiki

    2014-07-01

    The photo-triggered molecular release from the organic-inorganic polymer hybrids is presented in this manuscript. Initially, the preparation of the auto-degradable polymer is explained with the photo-cleavable group at the end of the polymer main-chain. The silica-based dye-loaded hybrids containing these polymers were fabricated. It was found that by UV irradiation, the end capping was removed, and then the auto-degradation occurs through the polymer main-chain. Finally, the molecular release of the loaded dyes was accomplished in various media by the UV irradiation. In particular, it was shown that both of hydrophobic and hydrophilic dyes can be applied in this system.

  17. Mechanistical studies on the electron-induced degradation of polymers: polyethylene, polytetrafluoroethylene, and polystyrene.

    PubMed

    Ennis, Courtney P; Kaiser, Ralf I

    2010-12-07

    Mechanisms of the electron-induced degradation of three polymers utilized in aerospace applications (polyethylene (PE), polytetrafluoroethylene (PTFE), and polystyrene (PS)) were examined over a temperature range of 10 K to 300 K at ultra high vacuum conditions (∼10(-11) Torr). These processes simulate the interaction of secondary electrons generated in the track of galactic cosmic ray particles in the near-Earth space environment with polymer material. The chemical alterations at the macromolecular level were monitored on-line and in situ by Fourier-transform infrared spectroscopy and mass spectrometry. These data yielded important information on the temperature dependent kinetics on the formation of, for instance, trans-vinylene groups (-CH=CH-) in PE, benzene (C(6)H(6)) production in PS, fluorinated trans-vinylene (-CF=CF-) and terminal vinyl (-CF=CF(2)) groups in PTFE together with molecular hydrogen release in PE and PS. Additional data on the radiation-induced development of unsaturated, conjugated bonds were collected via UV-vis spectroscopy. Temperature dependent G-values for trans-vinylene formation (G(-CH=CH-) ≈ 25-2.5 × 10(-4) units (100 eV)(-1) from 10-300 K) and molecular hydrogen evolution (G(H(2)) ≈ 8-80 × 10(-5) molecules (100 eV)(-1) from 10-300 K) for irradiated PE were calculated to quantify the degree of polymer degradation following electron irradiation. These values are typically two to three orders of magnitude less than G-values previously published for the irradiation of polymers with energetic particles of higher mass.

  18. Smart lanthanide coordination polymer fluorescence probe for mercury(II) determination.

    PubMed

    Liu, Baoxia; Huang, Yankai; Zhu, Xu; Hao, Yuanqiang; Ding, Yujie; Wei, Wei; Wang, Qi; Qu, Peng; Xu, Maotian

    2016-03-17

    Lanthanide coordination polymers (LCPs) have recently emerged as attractive biosensor materials due to their flexible components, high tailorable properties and unique luminescence features. In this work, we designed a smart LCP probe of Tb-CIP/AMP {(CIP, ciprofloxacin) (AMP, adenosine monophosphate)} for Hg(2+) detection by using lanthanide ions as metal nodes, CIP as ligand molecule, and AMP as bridging linker and recognition unit. Tb-CIP/AMP emits strong green luminescence due to the inclusion of AMP, which withdraws the coordinated water molecules and shields Tb(3+) from the quenching effect of O-H vibration in water molecules. The subsequent addition of Hg(2+) into Tb-CIP/AMP can strongly quench the fluorescence because of the specific coordination interaction between AMP and Hg(2+). As a kind of Hg(2+) nanosensor, the probe exhibited excellent selectivity for Hg(2+) and high sensitivity with detection limit of 0.16 nM. In addition, the probe has long fluorescence lifetime up to millisecond and has been applied to detect Hg(2+) in drinking water and human urine samples with satisfactory results. We envision that our strategy, in the future, could be extended to the designation of other LCP-based hypersensitive time-gated luminescence assays in biological media and biomedical imaging.

  19. The Effect of Platinum Electrocatalyst on Membrane Degradation in Polymer Electrolyte Fuel Cells

    PubMed Central

    Bodner, Merit; Cermenek, Bernd; Rami, Mija; Hacker, Viktor

    2015-01-01

    Membrane degradation is a severe factor limiting the lifetime of polymer electrolyte fuel cells. Therefore, obtaining a deeper knowledge is fundamental in order to establish fuel cells as competitive product. A segmented single cell was operated under open circuit voltage with alternating relative humidity. The influence of the catalyst layer on membrane degradation was evaluated by measuring a membrane without electrodes and a membrane-electrode-assembly under identical conditions. After 100 h of accelerated stress testing the proton conductivity of membrane samples near the anode and cathode was investigated by means of ex situ electrochemical impedance spectroscopy. The membrane sample near the cathode inlet exhibited twofold lower membrane resistance and a resulting twofold higher proton conductivity than the membrane sample near the anode inlet. The results from the fluoride ion analysis have shown that the presence of platinum reduces the fluoride emission rate; which supports conclusions drawn from the literature. PMID:26670258

  20. The Effect of Platinum Electrocatalyst on Membrane Degradation in Polymer Electrolyte Fuel Cells.

    PubMed

    Bodner, Merit; Cermenek, Bernd; Rami, Mija; Hacker, Viktor

    2015-12-08

    Membrane degradation is a severe factor limiting the lifetime of polymer electrolyte fuel cells. Therefore, obtaining a deeper knowledge is fundamental in order to establish fuel cells as competitive product. A segmented single cell was operated under open circuit voltage with alternating relative humidity. The influence of the catalyst layer on membrane degradation was evaluated by measuring a membrane without electrodes and a membrane-electrode-assembly under identical conditions. After 100 h of accelerated stress testing the proton conductivity of membrane samples near the anode and cathode was investigated by means of ex situ electrochemical impedance spectroscopy. The membrane sample near the cathode inlet exhibited twofold lower membrane resistance and a resulting twofold higher proton conductivity than the membrane sample near the anode inlet. The results from the fluoride ion analysis have shown that the presence of platinum reduces the fluoride emission rate; which supports conclusions drawn from the literature.

  1. Degradable, pH-sensitive, membrane-destabilizing, comb-like polymers for intracellular delivery of nucleic acids.

    PubMed

    Lin, Yen-Ling; Jiang, Guohua; Birrell, Lisa K; El-Sayed, Mohamed E H

    2010-09-01

    This report describes the design and synthesis of a new series of degradable, pH-sensitive, membrane-destabilizing, comb-like polymers that can enhance the intracellular delivery of therapeutic nucleic acids. These comb-like polymers are based on a diblock polymer backbone where the first block is a copolymer of pH-sensitive ethyl acrylic acid (EAA) monomers and hydrophobic butyl methacrylate (BMA) or hexyl methacrylate monomers. The second block is a homopolymer of N-acryloxy succinimide (NASI) or ss-benzyl l-aspartate N-carboxy-anhydride (BLA-NCA) monomers, which are functionalized to allow controlled grafting of hydrophobic HMA and cationic trimethyl aminoethyl methacrylate (TMAEMA) copolymers via acid-labile hydrazone linkages. These comb-like polymers displayed high hemolytic activity in acidic solutions, which increased with the increase in polymer concentration. All comb-like polymers degraded into small fragments upon incubation in an acidic solution (pH 5.8) due to hydrolysis of the hydrazone linkages connecting the hydrophobic/cationic grafts to the polymer backbone. Comb-like polymers successfully complexed anti-GAPDH siRNA molecules into serum- and nuclease-stable particles, which successfully silenced GAPDH expression at both the mRNA and protein levels. These results collectively indicate the potential of these new comb-like polymers to serve as vehicles for effective intracellular delivery of therapeutic nucleic acids.

  2. Synthesis and radiation degradation of vinyl polymers with fluorine: search for improved lithographic resists. [Gamma rays

    SciTech Connect

    Pittman, C.U. Jr.; Chen, C.Y.; Ueda, M.; Helbert, J.N.; Kwiatkowski, J.H.

    1980-12-01

    Homopolymers of methyl ..cap alpha..-fluoroacrylate (MFA), trifluoroethyl methacrylate (TFEM), and hexafluoroisopropyl methacrylate (HFIM) were prepared, as were their methyl methacrylate (MMA) copolymers. Copolymers of vinylidene fluoride (VDF) and chlorotrifluoroethylene (CTFE) with MMA were also prepared. The radiation susceptibilities of these polymers were measured by the /sup 60/Co ..gamma..-irradiation method, in which molecular weights were measured by membrane osmometry and gel permeation chromatography (GPC). All the copolymers degraded by predominant chain scission except poly(methyl ..cap alpha..-fluoroacrylate), (PMFA), which crosslinks even at low doses (ca. 1 Mrad). The G/sub s/-G/sub x/ and G/sub s/ values of the chain scissioning polymers and copolymers are higher than those of poly(methyl methacrylate) PMMA reference. The high susceptibility of PMFA homopolymer to crosslinking is in contrast to that of poly(methyl ..cap alpha..-chloroacrylate), as we reported earlier. This effect is interpreted as resulting from extensive hydrogen fluoride and polyenyl radical formation, which leads to facile crosslinking. However, incorporation of the MFA monomer unit causes the (22/78) MFA/MMA copolymer to degrade with a larger value of G/sub s/ that PMMA. Apparently a second-order process leads to crosslinking in PMFA and this is retarded in the copolymer. In the homopolymers of HFIM and TFEM and in the HFIM-MMA and TFEM-MMA copolymers the HFIM and TFEM components facilitate degradation with negligible crosslinking. The increased degradation susceptibility of VDF and CTFE copolymers with MMA over that of PMMA is attributed to processes at the VDF or CTFE components (present in smaller concentrations (3 to 5 mole %) than the threshold levels (25 to 50% necessary for significant crosslinking).

  3. Modern mass spectrometry in the characterization and degradation of biodegradable polymers.

    PubMed

    Rizzarelli, Paola; Carroccio, Sabrina

    2014-01-15

    In the last decades, the solid-waste management related to the extensively growing production of plastic materials, in concert with their durability, have stimulated increasing interest in biodegradable polymers. At present, a variety of biodegradable polymers has already been introduced onto the market and can now be competitive with non biodegradable thermoplastics in different fields (packaging, biomedical, textile, etc.). However, a significant economical effort is still directed in tailoring structural properties in order to further broaden the range of applications without impairing biodegradation. Improving the performance of biodegradable materials requires a good characterization of both physico-chemical and mechanical parameters. Polymer analysis can involve many different features including detailed characterization of chemical structures and compositions as well as average molecular mass determination. It is of outstanding importance in troubleshooting of a polymer manufacturing process and for quality control, especially in biomedical applications. This review describes recent trends in the structural characterization of biodegradable materials by modern mass spectrometry (MS). It provides an overview of the analytical tools used to evaluate their degradation. Several successful applications of MALDI-TOF MS (matrix assisted laser desorption ionization time of flight) and ESI MS (electrospray mass spectrometry) for the determination of the structural architecture of biodegradable macromolecules, including their topology, composition, chemical structure of the end groups have been reported. However, MS methodologies have been recently applied to evaluate the biodegradation of polymeric materials. ESI MS represents the most useful technique for characterizing water-soluble polymers possessing different end group structures, with the advantage of being easily interfaced with solution-based separation techniques such as high-performance liquid

  4. Membrane degradation during combined chemical and mechanical accelerated stress testing of polymer electrolyte fuel cells

    NASA Astrophysics Data System (ADS)

    Lim, C.; Ghassemzadeh, L.; Van Hove, F.; Lauritzen, M.; Kolodziej, J.; Wang, G. G.; Holdcroft, S.; Kjeang, E.

    2014-07-01

    A cyclic open circuit voltage (COCV) accelerated stress test (AST) is designed to screen the simultaneous effect of chemical and mechanical membrane degradation in polymer electrolyte fuel cells. The AST consists of a steady state OCV phase to accelerate chemical degradation and periodic wet/dry cycles to provide mechanical degradation. The membrane degradation process induced by COCV AST operation is analyzed using a standard MEA with PFSA ionomer membrane. The OCV shows an initially mild decay rate followed by a higher decay rate in the later stages of the experiment. Membrane failure, defined by a threshold convective hydrogen leak rate, is obtained after 160 h of operation. Uniform membrane thinning is observed with pinhole formation being the primary cause of failure. Mechanical tensile tests reveal that the membrane becomes stiffer and more brittle during AST operation, which contributes to mechanical failure upon cyclic humidity induced stress. Solid state 19F NMR spectroscopy and fluoride emission measurements demonstrate fluorine loss from both side chain and main chain upon membrane exposure to high temperature and low humidity OCV condition.

  5. Degradation behavior of polymer blend of isotactic polypropylenes with and without unsaturated chain end group

    PubMed Central

    Nakatani, Hisayuki; Kurniawan, Dodik; Taniike, Toshiaki; Terano, Minoru

    2008-01-01

    In this work, the relationship between the unsaturated chain end group content and the thermal oxidative degradation rate was systematically studied with binary polymer blends of isotactic polypropylene (iPP) with and without the unsaturated chain end group. The iPPs with and without the unsaturated chain end group were synthesized by a metallocene catalyst in the absence of hydrogen and by a Ziegler catalyst in the presence of one, respectively. The thermal oxidative degradation rate of the binary iPP blends was estimated from the molecular weight and the apparent activation energy (ΔE), which were obtained through size exclusion chromatography (SEC) and thermogravimetric analysis (TGA) measurements, respectively. These values exhibited a negative correlation against the mole content of the unsaturated chain end group. The thermal oxidative degradation rate apparently depends on the content of the unsaturated chain end group. This tendency suggests that the unsaturated chain end acts as a radical initiator of the iPP degradation reaction. PMID:27877968

  6. Treatment of Osteomyelitis in Rats by Injection of Degradable Polymer Releasing Gentamicin

    PubMed Central

    Brin, Yaron S.; Golenser, Jacob; Mizrahi, Boaz; Maoz, Guy; Domb, Abraham J.; Peddada, Shyamal; Tuvia, Shmuel; Nyska, Abraham; Nyska, Meir

    2009-01-01

    We evaluated the potential of an injectable degradable polymer-Poly(sebacic-co-ricinoleic-ester-anhydride) containing gentamicin for the treatment of osteomyelitis. Osteomyelitis of both tibiae was induced in 13 female Fischer rats by injecting a suspension containing approximately 105 (CFU)/ml of S. Aureus into the tibial medullar canal. Three weeks later both tibiae were X rayed, drilled down the medullar canal, washed with 50µl gentamicin solution (80mg/2ml) and then injected with 50µl P(SARA) + gentamycin 20% w/v to the right tibia and 50µl P(SA-RA) without gentamicin to the left tibia. After an additional 3 weeks, the rats were sacrificed, and radiographs of the tibiae were taken. Histopathological evaluation of the tibiae was done in a blinded manner. X ray radiographs showed that all tibiae developed changes compatible with osteomyelitis in 3 weeks. Histological evaluation revealed significant differences between right and left tibiae in 10 rats. In the left tibia moderate intramedullary abscess formation occurred. In most treated tibiae typical changes included the absence (or minimal grade only) of abscesses. The treated group developed significantly less intramedullary abscesses; the p-value was 0.028. Locally injected degradable polymer releasing gentamicin proved to be efficient histologically in the treatment of osteomyelitis PMID:18692531

  7. Interferometric pump-probe characterization of the nonlocal response of optically transparent ion implanted polymers

    NASA Astrophysics Data System (ADS)

    Stefanov, Ivan L.; Hadjichristov, Georgi B.

    2012-03-01

    Optical interferometric technique is applied to characterize the nonlocal response of optically transparent ion implanted polymers. The thermal nonlinearity of the ion-modified material in the near-surface region is induced by continuous wave (cw) laser irradiation at a relatively low intensity. The interferometry approach is demonstrated for a subsurface layer of a thickness of about 100 nm formed in bulk polymethylmethacrylate (PMMA) by implantation with silicon ions at an energy of 50 keV and fluence in the range 1014-1017 cm-2. The laser-induced thermooptic effect in this layer is finely probed by interferometric imaging. The interference phase distribution in the plane of the ion implanted layer is indicative for the thermal nonlinearity of the near-surface region of ion implanted optically transparent polymeric materials.

  8. Resonance light scattering method for the determination of DNA with cationic methacrylate based polymer nanoparticle probes.

    PubMed

    Zou, Qi-Chao; Zhang, Jin-Zhi; Chai, Shi-Gan

    2011-11-01

    Narrowly distributed cationic poly (methyl methacrylate-co-diacetone acrylamide) (P(MMA-DAAM)) nanoparticles were successfully prepared by microemulsion polymerization. Photon correlation spectrometer (PCS) measurement and transmission electron microscope (TEM) observation revealed that z-average particle size of P(MMA-DAAM) is ∼27.5 nm. It was found that these cationic nanoparticles interact with DNA through electrostatic interaction to form P(MMA-DAAM)-DNA complex, which significantly enhances the resonance light scattering (RLS) signal. Therefore, a novel method using this polymer nanoparticle as a new probe for the detection of DNA by RLS technique is developed in this paper. The results showed this method is very convenient, sensitive, and reproducible.

  9. Degradation of polymer electrolyte membrane fuel cell by siloxane in biogas

    NASA Astrophysics Data System (ADS)

    Seo, Ji-Sung; Kim, Da-Yeong; Hwang, Sun-Mi; Seo, Min Ho; Seo, Dong-Jun; Yang, Seung Yong; Han, Chan Hui; Jung, Yong-Min; Guim, Hwanuk; Nahm, Kee Suk; Yoon, Young-Gi; Kim, Tae-Young

    2016-06-01

    We studied the degradation and durability of polymer electrolyte membrane fuel cell (PEMFC) at membrane-electrode-assembly (MEA) level by injection of octamethylcyclotetrasiloxane (D4) as a representative siloxane, which has been found in many industrial and personal products. Specifically, i) GC/MS analysis demonstrated that the ring-opening polymerization of D4 could result in the formation of various linear and cyclic siloxanes in both electrodes of MEA; ii) post-test analysis revealed that the transformed siloxanes were transported from the anode to the cathode via free-volumes in the polymer membrane; iii) RDE measurement and DFT calculation revealed that D4 was not directly responsible for the electrocatalytic activity of Pt; iv) electrochemical analysis demonstrated that the residual methyl groups of siloxane and various siloxanes did not hinder the proton transport in the polymer membrane; and v) siloxanes accumulated in the primary and secondary pores with the exception of an external surface of carbon, causing an increase in the oxygen reactant's resistance and resulting in a decrease of the cell performance. In addition, we confirmed that injection of D4 did not affect the carbon corrosion adversely because the siloxane had little influence on water sorption in the catalyst layer.

  10. Biodegradability of PP/HMSPP and natural and synthetic polymers blends in function of gamma irradiation degradation

    NASA Astrophysics Data System (ADS)

    Cardoso, Elisabeth C. L.; Scagliusi, Sandra R.; Lima, Luis F. C. P.; Bueno, Nelson R.; Brant, Antonio J. C.; Parra, Duclerc F.; Lugão, Ademar B.

    2014-01-01

    Polymers are used for numerous applications in different industrial segments, generating enormous quantities of discarding in the environment. Polymeric materials composites account for an estimated from 20 to 30% total volume of solid waste. Polypropylene (PP) undergoes crosslinking and extensive main chain scissions when submitted to ionizing irradiation; as one of the most widely used linear hydrocarbon polymers, PP, made from cheap petrochemical feed stocks, shows easy processing leading it to a comprehensive list of finished products. Consequently, there is accumulation in the environment, at 25 million tons per year rate, since polymeric products are not easily consumed by microorganisms. PP polymers are very bio-resistant due to involvement of only carbon atoms in main chain with no hydrolysable functional group. Several possibilities have been considered to minimize the environmental impact caused by non-degradable plastics, subjecting them to: physical, chemical and biological degradation or combination of all these due to the presence of moisture, air, temperature, light, high energy radiation or microorganisms. There are three main classes of biodegradable polymers: synthetic polymers, natural polymers and blends of polymers in which one or more components are readily consumed by microorganisms. This work aims to biodegradability investigation of a PP/HMSPP (high melt strength polypropylene) blended with sugarcane bagasse, PHB (poly-hydroxy-butyrate) and PLA (poly-lactic acid), both synthetic polymers, at a 10% level, subjected to gamma radiation at 50, 100, 150 and 200 kGy doses. Characterization will comprise IR, DSC, TGA, OIT and Laboratory Soil Burial Test (LSBT).

  11. Quantum dots coated with molecularly imprinted polymer as fluorescence probe for detection of cyphenothrin.

    PubMed

    Ren, Xiaohui; Chen, Ligang

    2015-02-15

    A newly designed molecularly imprinted polymer (MIP) material was fabricated and successfully utilized as recognition element to develop a quantum dots (QDs) based MIP-coated composite for selective recognition of the template cyphenothrin. The MIP-coated QDs were characterized by fluorescence spectrophotometer, Fourier transform infrared spectroscopy, transmission electron microscope, dynamic light scattering and X-ray powder diffraction. The fluorescence of the coated QDs is quenched on loading the MIP with cyphenothrin, and the effect is much stronger for the MIP than for the non-imprinted polymer, which indicates the MIP could as a recognition template composite. This method can detect down to 9.0 nmol L(-1) of cyphenothrin in water, and a linear relationship has been obtained covering the concentration range of 0.1-80.0 μmol L(-1). The method has been used in the determination of cyphenothrin in water samples and gave recoveries in the range from 88.5% to 97.1% with relative standard deviations in the range of 3.1-6.2%. The present study provides a new and general strategy to fabricate inorganic-organic MIP-coated QDs with highly selective recognition ability in aqueous media and is desirable for chemical probe application.

  12. Stable-Isotope Probing Identifies Uncultured Planctomycetes as Primary Degraders of a Complex Heteropolysaccharide in Soil

    PubMed Central

    Wang, Xiaoqing; Sharp, Christine E.; Jones, Gareth M.; Grasby, Stephen E.; Brady, Allyson L.

    2015-01-01

    The exopolysaccharides (EPSs) produced by some bacteria are potential growth substrates for other bacteria in soil. We used stable-isotope probing (SIP) to identify aerobic soil bacteria that assimilated the cellulose produced by Gluconacetobacter xylinus or the EPS produced by Beijerinckia indica. The latter is a heteropolysaccharide comprised primarily of l-guluronic acid, d-glucose, and d-glycero-d-mannoheptose. 13C-labeled EPS and 13C-labeled cellulose were purified from bacterial cultures grown on [13C]glucose. Two soils were incubated with these substrates, and bacteria actively assimilating them were identified via pyrosequencing of 16S rRNA genes recovered from 13C-labeled DNA. Cellulose C was assimilated primarily by soil bacteria closely related (93 to 100% 16S rRNA gene sequence identities) to known cellulose-degrading bacteria. However, B. indica EPS was assimilated primarily by bacteria with low identities (80 to 95%) to known species, particularly by different members of the phylum Planctomycetes. In one incubation, members of the Planctomycetes made up >60% of all reads in the labeled DNA and were only distantly related (<85% identity) to any described species. Although it is impossible with SIP to completely distinguish primary polysaccharide hydrolyzers from bacteria growing on produced oligo- or monosaccharides, the predominance of Planctomycetes suggested that they were primary degraders of EPS. Other bacteria assimilating B. indica EPS included members of the Verrucomicrobia, candidate division OD1, and the Armatimonadetes. The results indicate that some uncultured bacteria in soils may be adapted to using complex heteropolysaccharides for growth and suggest that the use of these substrates may provide a means for culturing new species. PMID:25934620

  13. Aspects of environmental degradation and fracture in polymer films and fibers

    NASA Astrophysics Data System (ADS)

    Walsh, Peter J.

    This thesis is focused in three areas: An investigation of a thermodynamic criterion for failure by environmental stress cracking using observations of the wetting behavior of stress-cracking liquids on glassy polymer substrates; Determination of the dominant chemical and physical degradation mechanisms associated with exposure of poly-p-phenylenebisbenzoxazole fiber to moisture moisture and UV-Vis spectrum light; And finally, the effect of constraint on fracture at a bi-material interface is investigated using a model epoxy-metallic adherend specimen. The wetting behavior of an ESC liquid on polycarbonate substrates has been evaluated as a function of substrate stress using a variation of Contact Adhesion Testing, a novel method of measuring small contact angles by refraction and conventional goniometry. The inelastic and elastic strain condition and time to the onset of crazing were also observed. A normalization of the time to onset of crazing using stress state, solubility difference and diffusion coefficients was shown to collapse the kinetic observations. A comprehensive study of the degradation mechanisms of PBO AS fiber exposed in a controlled manner to challenging chemical environments, moisture and UV-Visible spectrum light was undertaken. Fibers were characterized using a broad range of mechanical and physical tests including tensile testing, Elemental Analysis, scanning electron microscopy, small angle X-ray diffraction, wide angle X-ray diffraction and attenuated total reflectance infrared spectroscopy. Degradation by moisture is found to be primarily due to a loosening of the fiber's fibrillar structure. Degradation by UV-Visible spectrum light is found to be chemical in nature involving hydrolytic disruption of the oxazole ring and possible subsequent conversion to an amide bond. Approaches to alleviation of PBO AS fiber degradation were studied including super-critical carbon dioxide extraction of residual acid, the use of UV-Vis blocking coatings

  14. An analysis of degradation phenomena in polymer electrolyte membrane water electrolysis

    NASA Astrophysics Data System (ADS)

    Rakousky, Christoph; Reimer, Uwe; Wippermann, Klaus; Carmo, Marcelo; Lueke, Wiebke; Stolten, Detlef

    2016-09-01

    The durability of a polymer electrolyte membrane (PEM) water electrolysis single cell, assembled with regular porous transport layers (PTLs) is investigated for just over 1000 h. We observe a significant degradation rate of 194 μV h-1 and conclude that 78% of the detectable degradation can be explained by an increase in ohmic resistance, arising from the anodic Ti-PTL. Analysis of the polarization curves also indicates a decrease in the anodic exchange current density, j0, that results from the over-time contamination of the anode with Ti species. Furthermore, the average Pt-cathode particle size increases during the test, but we do not believe this phenomenon makes a significant contribution to increased cell voltages. To validate the anode Ti-PTL as a crucial source of increasing resistance, a second cell is assembled using Pt-coated Ti-PTLs. This yields a substantially reduced degradation rate of only 12 μV h-1, indicating that a non-corroding anode PTL is vital for PEM electrolyzers. It is our hope that forthcoming tailored PTLs will not only contribute to fast progress on cost-efficient stacks, but also to its long-term application of PEM electrolyzers involved in industrial processes.

  15. Novel degradable co-polymers of polypyrrole support cell proliferation and enhance neurite out-growth with electrical stimulation.

    PubMed

    Durgam, Hymavathi; Sapp, Shawn; Deister, Curt; Khaing, Zin; Chang, Emily; Luebben, Silvia; Schmidt, Christine E

    2010-01-01

    Synthetic polymers such as polypyrrole (PPy) are gaining significance in neural studies because of their conductive properties. We evaluated two novel biodegradable block co-polymers of PPy with poly(epsilon-caprolactone) (PCL) and poly(ethyl cyanoacrylate) (PECA) for nerve regeneration applications. PPy-PCL and PPy-PECA co-polymers can be processed from solvent-based colloidal dispersions and have essentially the same or greater conductivity (32 S/cm for PPy-PCL, 19 S/cm for PPy-PECA) compared to the PPy homo-polymer (22 S/cm). The PPy portions of the co-polymers permit electrical stimulation whereas the PCL or PECA blocks enable degradation by hydrolysis. For in vitro tests, films were prepared on polycarbonate sheets by air brushing layers of dispersions and pressing the films. We characterized the films for hydrolytic degradation, electrical conductivity, cell proliferation and neurite extension. The co-polymers were sufficient to carry out electrical stimulation of cells without the requirement of a metallic conductor underneath the co-polymer film. In vitro electrical stimulation of PPy-PCL significantly increased the number of PC12 cells bearing neurites compared to unstimulated PPy-PCL. For in vivo experiments, the PPy co-polymers were coated onto the inner walls of nerve guidance channels (NGCs) made of the commercially available non-conducting biodegradable polymer poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHB-HV). The NGCs were implanted in a 10 mm defect made in the sciatic nerve of rats, and harvested after 8 weeks. Histological staining showed axonal growth. The studies indicated that these new conducting degradable biomaterials have good biocompatibility and support proliferation and growth of PC12 cells in vitro (with and without electrical stimulation) and neurons in vivo (without electrical stimulation).

  16. Probing opto-mechanical stresses within azobenzene-containing photosensitive polymer films by a thin metal film placed above.

    PubMed

    Yadavalli, Nataraja Sekhar; Korolkov, Denis; Moulin, Jean-François; Krutyeva, Margarita; Santer, Svetlana

    2014-07-23

    Azo-modified photosensitive polymers offer the interesting possibility to reshape bulk polymers and thin films by UV-irradiation while being in the solid glassy state. The polymer undergoes considerable mass transport under irradiation with a light interference pattern resulting in the formation of surface relief grating (SRG). The forces inscribing this SRG pattern into a thin film are hard to assess experimentally directly. In the current study, we are proposing a method to probe opto-mechanical stresses within polymer films by characterizing the mechanical response of thin metal films (10 nm) deposited on the photosensitive polymer. During irradiation, the metal film not only deforms along with the SRG formation but ruptures in a regular and complex manner. The morphology of the cracks differs strongly depending on the electrical field distribution in the interference pattern, even when the magnitude and the kinetics of the strain are kept constant. This implies a complex local distribution of the opto-mechanical stress along the topography grating. In addition, the neutron reflectivity measurements of the metal/polymer interface indicate the penetration of a metal layer within the polymer, resulting in a formation of a bonding layer that confirms the transduction of light-induced stresses in the polymer layer to a metal film.

  17. Application of Universal Stress Proteins in Probing the Dynamics of Potent Degraders in Complex Terephthalate Metagenome

    PubMed Central

    Mbah, Andreas N.; Isokpehi, Raphael D.

    2013-01-01

    The culture-independent strategies to study microbial diversity and function have led to a revolution in environmental genomics, enabling fundamental questions about the distribution of microbes and their influence on bioremediation to be addressed. In this research we used the expression of universal stress proteins as a probe to determine the changes in degrading microbial population from a highly toxic terephthalate wastewater to a less toxic activated sludge bioreactor. The impact of relative toxicities was significantly elaborated at the levels of genus and species. The results indicated that 23 similar prokaryotic phyla were represented in both metagenomes irrespective of their relative abundance. Furthermore, the following bacteria taxa Micromonosporaceae, Streptomyces, Cyanothece sp. PCC 7822, Alicyclobacillus acidocaldarius, Bacillus halodurans, Leuconostoc mesenteroides, Lactococcus garvieae, Brucellaceae, Ralstonia solanacearum, Verminephrobacter eiseniae, Azoarcus, Acidithiobacillus ferrooxidans, Francisella tularensis, Methanothermus fervidus, and Methanocorpusculum labreanum were represented only in the activated sludge bioreactor. These highly dynamic microbes could serve as taxonomic biomarkers for toxic thresholds related to terephthalate and its derivatives. This paper, highlights the application of universal stress proteins in metagenomics analysis. Dynamics of microbial consortium of this nature can have future in biotechnological applications in bioremediation of toxic chemicals and radionuclides. PMID:24151583

  18. Degradable poly(apigenin) polymer inhibits tumor cell adhesion to vascular endothelial cells.

    PubMed

    Cochran, David B; Gray, Lindsay N; Anderson, Kimberly W; Dziubla, Thomas D

    2016-10-01

    Cancer and the inflammatory system share a complex intertwined relationship. For instance, in response to an injury or stress, vascular endothelial cells will express cell adhesion molecules as a means of recruiting leukocytes. However, circulating tumor cells (CTCs) have been shown to highjack this expression for the adhesion and invasion during the metastatic cascade. As such, the initiation of endothelial cell inflammation, either by surgical procedures (cancer resection) or chemotherapy can inadvertently increase the metastatic potential of CTCs. Yet, systemic delivery of anti-inflammatories, which weaken the entire immune system, may not be preferred in some treatment settings. In this work, we demonstrate that a long-term releasing flavone-based polymer and subsequent nanoparticle delivery system can inhibit tumor cell adhesion, through the suppression of endothelial cell adhesion molecule expression. The degradation of a this anti-inflammatory polymer provides longer term, localized release profile of active therapeutic drug in nanoparticle form as compared with that of the free drug, permitting more targeted anti-metastatic therapies. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 104B: 1438-1447, 2016.

  19. Decades-Scale Degradation of Commercial, Side-Chain, Fluorotelomer-Based Polymers in Soils and Water

    EPA Science Inventory

    Fluorotelomer-based polymers (FTPs) are a primary product of the jluorotelomer industry, yet the role of commercial FTPs in degrading to form perjluorocarboxylic acids (P FCAs), including perjluorooctanoic acid, and P FCA precursors, remains ill-defined. Here we report on a 376-d...

  20. Oxidation Responsive Polymers with a Triggered Degradation via Arylboronate Self-Immolative Motifs on a Polyphosphazene Backbone

    PubMed Central

    2017-01-01

    Oxidation responsive polymers with triggered degradation pathways have been prepared via attachment of self-immolative moieties onto a hydrolytically unstable polyphosphazene backbone. After controlled main-chain growth, postpolymerization functionalization allows the preparation of hydrolytically stable poly(organo)phosphazenes decorated with a phenylboronic ester caging group. In oxidative environments, triggered cleavage of the caging group is followed by self-immolation, exposing the unstable glycine-substituted polyphosphazene which subsequently undergoes to backbone degradation to low-molecular weight molecules. As well as giving mechanistic insights, detailed GPC and 1H and 31P NMR analysis reveal the polymers to be stable in aqueous solutions, but show a selective, fast degradation upon exposure to hydrogen peroxide containing solutions. Since the post-polymerization functionalization route allows simple access to polymer backbones with a broad range of molecular weights, the approach of using the inorganic backbone as a platform significantly expands the toolbox of polymers capable of stimuli-responsive degradation. PMID:28251035

  1. Effect of CO and oxygen on anode degradation in polymer electrolyte fuel cell

    NASA Astrophysics Data System (ADS)

    Nakamori, Yoji; Suzuki, Naotoshi; Tanaka, Kazuhisa; Aoki, Tsutomu; Nohira, Toshiyuki; Hagiwara, Rika

    2013-11-01

    CO tolerance of a polymer electrolyte fuel cell was measured before and after accelerated degradation cell operation in which hydrogen with 200, 500, 1000, and 1500 ppm of CO was supplied to the anode and air was supplied to the cathode in the open-circuit condition. The decrease in CO tolerance was more pronounced when the concentration of CO was increased. However, CO tolerance did not decrease when nitrogen, instead of air, was supplied to the cathode. The amount of fluoride ion in the drain water during the cell operation increased when hydrogen containing 500 ppm CO was supplied to the anode, which indicates the decomposition of perfluorocarbon ionomer. It was found that the combination of CO and oxygen deteriorated the ionomer because H2O2 that was produced as a by-product of the oxygen reduction reaction cannot be completely reduced to water. This is due to the decreased surface area of the Pt-Ru alloy catalyst because of CO adsorption, which results in the degradation of the CO tolerance.

  2. Impact of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Reaction Activity for Platinum Electrocatalysts

    SciTech Connect

    Christ, J. M.; Neyerlin, K. C.; Wang, H.; Richards, R.; Dinh, H. N.

    2014-10-30

    The impact of model membrane degradation compounds on the relevant electrochemical parameters for the oxygen reduction reaction (i.e. electrochemical surface area and catalytic activity), was studied for both polycrystalline Pt and carbon supported Pt electrocatalysts. Model compounds, representing previously published, experimentally determined polymer electrolyte membrane degradation products, were in the form of perfluorinated organic acids that contained combinations of carboxylic and/or sulfonic acid functionality. Perfluorinated carboxylic acids of carbon chain length C1 – C6 were found to have an impact on electrochemical surface area (ECA). The longest chain length acid also hindered the observed oxygen reduction reaction (ORR) performance, resulting in a 17% loss in kinetic current (determined at 0.9 V). Model compounds containing sulfonic acid functional groups alone did not show an effect on Pt ECA or ORR activity. Lastly, greater than a 44% loss in ORR activity at 0.9V was observed for diacid model compounds DA-Naf (perfluoro(2-methyl-3-oxa-5-sulfonic pentanoic) acid) and DA-3M (perfluoro(4-sulfonic butanoic) acid), which contained both sulfonic and carboxylic acid functionalities.

  3. Impact of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Reaction Activity for Platinum Electrocatalysts

    DOE PAGES

    Christ, J. M.; Neyerlin, K. C.; Wang, H.; ...

    2014-10-30

    The impact of model membrane degradation compounds on the relevant electrochemical parameters for the oxygen reduction reaction (i.e. electrochemical surface area and catalytic activity), was studied for both polycrystalline Pt and carbon supported Pt electrocatalysts. Model compounds, representing previously published, experimentally determined polymer electrolyte membrane degradation products, were in the form of perfluorinated organic acids that contained combinations of carboxylic and/or sulfonic acid functionality. Perfluorinated carboxylic acids of carbon chain length C1 – C6 were found to have an impact on electrochemical surface area (ECA). The longest chain length acid also hindered the observed oxygen reduction reaction (ORR) performance, resultingmore » in a 17% loss in kinetic current (determined at 0.9 V). Model compounds containing sulfonic acid functional groups alone did not show an effect on Pt ECA or ORR activity. Lastly, greater than a 44% loss in ORR activity at 0.9V was observed for diacid model compounds DA-Naf (perfluoro(2-methyl-3-oxa-5-sulfonic pentanoic) acid) and DA-3M (perfluoro(4-sulfonic butanoic) acid), which contained both sulfonic and carboxylic acid functionalities.« less

  4. Microscopic study of surface degradation of glass fiber-reinforced polymer rods embedded in concrete castings subjected to environmental conditioning

    SciTech Connect

    Bank, L.C.; Puterman, M.

    1997-12-31

    The surface degradation of glass fiber-reinforced polymer (GFRP) pultruded rods when embedded in concrete castings and subjected to environmental conditioning is discussed in this paper. Investigation of the degradation of the GFRP rods were performed using optical microscopy and scanning electron microscopy (SEM). Unidirectionally reinforced pultruded rods (6.3- and 12.7-mm diameters) containing E-glass fibers in polyester and vinylester matrices were conditioned at standard laboratory conditions (21 C, 65% relative humidity) or submerged in aqueous solutions (tap water) at 80 C for durations of 14 and 84 days. Observations of the surfaces and cross-sections of the rods by optical microscopy and SEM revealed a variety of degradation phenomena. Embedded hygrothermally conditioned rods were found to have developed surface blisters of different sizes and depths. SEM studies of the surface revealed degradation of the polymer matrix material and exposure and degradation of the fibers close to the surface of the rods. The rods with the vinylester resin matrix showed less extensive degradation than those with the polyester resin matrix; however, the degradation characteristics of the two types of rods appear to be similar.

  5. Remote Determination of Time-Dependent Stiffness of Surface-Degrading-Polymer Scaffolds Via Synchrotron-Based Imaging.

    PubMed

    Bawolin, N K; Chen, X B

    2017-04-01

    Surface-degrading polymers have been widely used to fabricate scaffolds with the mechanical properties appropriate for tissue regeneration/repair. During their surface degradation, the material properties of polymers remain approximately unchanged, but the scaffold geometry and thus mechanical properties vary with time. This paper presents a novel method to determine the time-dependent mechanical properties, particularly stiffness, of scaffolds from the geometric changes captured by synchrotron-based imaging, with the help of finite element analysis (FEA). Three-dimensional (3D) tissue scaffolds were fabricated from surface-degrading polymers, and during their degradation, the tissue scaffolds were imaged via the synchrotron-based imaging to characterize their changing geometry. On this basis, the stiffness behavior of scaffolds was estimated from the FEA, and the results obtained were compared to the direct measurements of scaffold stiffness from the load-displacement material testing. The comparison illustrates that the Young's moduli estimated from the FEA and characterized geometry are in agreement with the ones of direct measurements. The developed method of estimating the mechanical behavior was also demonstrated effective with a nondegrading scaffold that displays the nonlinear stress-strain behavior. The in vivo monitoring of Young's modulus by morphology characterization also suggests the feasibility of characterizing experimentally the difference between in vivo and in vitro surface degradation of tissue engineering constructs.

  6. Dilation and degradation of the brain extracellular matrix enhances penetration of infused polymer nanoparticles

    PubMed Central

    Neeves, Keith B.; Sawyer, Andrew J.; Foley, Conor P.; Saltzman, W. Mark; Olbricht, William L.

    2007-01-01

    This study investigates methods of manipulating the brain extracellular matrix (ECM) to enhance the penetration of nanoparticle drug carriers in convection-enhanced delivery (CED). A probe was fabricated with two independent microfluidic channels to infuse, either simultaneously or sequentially, nanoparticles and ECM-modifying agents. Infusions were performed in the striatum of the normal rat brain. Monodisperse polystyrene particles with a diameter of 54 nm were used as a model nanoparticle system. Because the size of these particles is comparable to the effective pore size of the ECM, their transport may be significantly hindered compared with the transport of low molecular weight molecules. To enhance the transport of the infused nanoparticles, we attempted to increase the effective pore size of the ECM by two methods: dilating the extracellular space and degrading selected constituents of the ECM. Two methods of dilating the extracellular space were investigated: co-infusion of nanoparticles and a hyperosmolar solution of mannitol, and pre-infusion of an isotonic buffer solution followed by infusion of nanoparticles. These treatments resulted in an increase in the nanoparticle distribution volume of 50% and 123%, respectively. To degrade hyaluronan, a primary structural component of the brain ECM, a pre-infusion of hyaluronidase (20,000 U/mL) was followed after 30 min by infusion of nanoparticles. This treatment resulted in an increase in the nanoparticle distribution of 64%. Our results suggest that both dilation and enzymatic digestion can be incorporated into CED protocols to enhance nanoparticle penetration. PMID:17920047

  7. Rigid spine reinforced polymer microelectrode array probe and method of fabrication

    DOEpatents

    Tabada, Phillipe; Pannu, Satinderpall S

    2014-05-27

    A rigid spine-reinforced microelectrode array probe and fabrication method. The probe includes a flexible elongated probe body with conductive lines enclosed within a polymeric material. The conductive lines connect microelectrodes found near an insertion end of the probe to respective leads at a connector end of the probe. The probe also includes a rigid spine, such as made from titanium, fixedly attached to the probe body to structurally reinforce the probe body and enable the typically flexible probe body to penetrate and be inserted into tissue, such as neural tissue. By attaching or otherwise fabricating the rigid spine to connect to only an insertion section of the probe body, an integrally connected cable section of the probe body may remain flexible.

  8. Polymer damage mitigation---predictive lifetime models of polymer insulation degradation and biorenewable thermosets through cationic polymerization for self-healing applications

    NASA Astrophysics Data System (ADS)

    Hondred, Peter Raymond

    Over the past 50 years, the industrial development and applications for polymers and polymer composites has become expansive. However, as with any young technology, the techniques for predicting material damage and resolving material failure are in need of continued development and refinement. This thesis work takes two approaches to polymer damage mitigation---material lifetime prediction and spontaneous damage repair through self-healing while incorporating bio-renewable feedstock. First, material lifetime prediction offers the benefit of identifying and isolating material failures before the effects of damage results in catastrophic failure. Second, self-healing provides a systematic approach to repairing damaged polymer composites, specifically in applications where a hands-on approach or removing the part from service are not feasible. With regard to lifetime prediction, we investigated three specific polymeric materials---polytetrafluoroethylene (PTFE), poly(ethylene-alt-tetrafluoroethylene) (ETFE), and Kapton. All three have been utilized extensively in the aerospace field as a wire insulation coating. Because of the vast amount of electrical wiring used in aerospace constructions and the potential for electrical and thermal failure, this work develops mathematical models for both the thermal degradation kinetics as well as a lifetime prediction model for electrothermal breakdown. Isoconversional kinetic methods, which plot activation energy as a function of the extent of degradation, present insight into the development each kinetic model. The models for PTFE, ETFE, and Kapton are one step, consecutive three-step, and competitive and consecutive five-step respectively. Statistical analysis shows that an nth order autocatalytic reaction best defined the reaction kinetics for each polymer's degradation. Self-healing polymers arrest crack propagation through the use of an imbedded adhesive that reacts when cracks form. This form of damage mitigation focuses on

  9. Mathematical modeling of degradation for bulk-erosive polymers: applications in tissue engineering scaffolds and drug delivery systems.

    PubMed

    Chen, Yuhang; Zhou, Shiwei; Li, Qing

    2011-03-01

    The degradation of polymeric biomaterials, which are widely exploited in tissue engineering and drug delivery systems, has drawn significant attention in recent years. This paper aims to develop a mathematical model that combines stochastic hydrolysis and mass transport to simulate the polymeric degradation and erosion process. The hydrolysis reaction is modeled in a discrete fashion by a fundamental stochastic process and an additional autocatalytic effect induced by the local carboxylic acid concentration in terms of the continuous diffusion equation. Illustrative examples of microparticles and tissue scaffolds demonstrate the applicability of the model. It is found that diffusive transport plays a critical role in determining the degradation pathway, whilst autocatalysis makes the degradation size dependent. The modeling results show good agreement with experimental data in the literature, in which the hydrolysis rate, polymer architecture and matrix size actually work together to determine the characteristics of the degradation and erosion processes of bulk-erosive polymer devices. The proposed degradation model exhibits great potential for the design optimization of drug carriers and tissue scaffolds.

  10. Mass spectrometry for the elucidation of the subtle molecular structure of biodegradable polymers and their degradation products.

    PubMed

    Kowalczuk, Marek; Adamus, Grażyna

    2016-01-01

    Contemporary reports by Polish authors on the application of mass spectrometric methods for the elucidation of the subtle molecular structure of biodegradable polymers and their degradation products will be presented. Special emphasis will be given to natural aliphatic (co)polyesters (PHA) and their synthetic analogues, formed through anionic ring-opening polymerization (ROP) of β-substituted β-lactones. Moreover, the application of MS techniques for the evaluation of the structure of biodegradable polymers obtained in ionic and coordination polymerization of cyclic ethers and esters as well as products of step-growth polymerization, in which bifunctional or multifunctional monomers react to form oligomers and eventually long chain polymers, will be discussed. Furthermore, the application of modern MS techniques for the assessment of polymer degradation products, frequently bearing characteristic end groups that can be revealed and differentiated by MS, will be discussed within the context of specific degradation pathways. Finally, recent Polish accomplishments in the area of mass spectrometry will be outlined.

  11. Design and synthesis of self-degradable antibacterial polymers by simultaneous chain- and step-growth radical copolymerization.

    PubMed

    Mizutani, Masato; Palermo, Edmund F; Thoma, Laura M; Satoh, Kotaro; Kamigaito, Masami; Kuroda, Kenichi

    2012-05-14

    Self-degradable antimicrobial copolymers bearing cationic side chains and main-chain ester linkages were synthesized using the simultaneous chain- and step-growth radical polymerization of t-butyl acrylate and 3-butenyl 2-chloropropionate, followed by the transformation of t-butyl groups into primary ammonium salts. We prepared a series of copolymers with different structural features in terms of molecular weight, monomer composition, amine functionality, and side chain structures to examine the effect of polymer properties on their antimicrobial and hemolytic activities. The acrylate copolymers containing primary amine side chains displayed moderate antimicrobial activity against E. coli but were relatively hemolytic. The acrylate copolymer with quaternary ammonium groups and the acrylamide copolymers showed low or no antimicrobial and hemolytic activities. An acrylate copolymer with primary amine side chains degraded to lower molecular weight oligomers with lower antimicrobial activity in aqueous solution. This degradation was due to amidation of the ester groups of the polymer chains by the nucleophilic addition of primary amine groups in the side chains resulting in cleavage of the polymer main chain. The degradation mechanism was studied in detail by model reactions between amine compounds and precursor copolymers.

  12. Probing interactions and phase separations of proteins, colloids, and polymers with light scattering

    NASA Astrophysics Data System (ADS)

    Parmar, Avanish Singh

    solutions at high salt concentration, over a wide range of pH values and temperatures for the common tracer particle polystyrene flocculates. We applied dynamic light scattering to measure the viscoelastic responses of polystyrene probe particles embedded in solutions and gels of two different polymers: polyacrylamide (PAAm) and poly-N-isopropylacrylamide (poly-NiPAAm).

  13. Controlled delivery of aspirin: effect of aspirin on polymer degradation and in vitro release from PLGA based phase sensitive systems.

    PubMed

    Tang, Yu; Singh, Jagdish

    2008-06-05

    The objective of this study was to develop poly (d,l-lactide-co-glycolide) (PLGA) based injectable phase sensitive in situ gel forming delivery system for controlled delivery of aspirin, and to characterize the effect of drug/polymer interaction on the in vitro release of aspirin and polymer degradation. Aspirin was dissolved into PLGA solution in 1-methyl-2-pyrrolidone. Poly(ethylene glycol)400 was used as plasticizer to reduce initial burst release. The solution formulation was injected into aqueous release medium to form a gel depot. Released samples were withdrawn periodically and assayed for aspirin content by high performance liquid chromatography. The effect of aspirin on the degradation of PLGA matrix was evaluated using Proton Nuclear Magnetic Resonance and Gel Permeation Chromatography. PLGA based in situ gel forming formulations controlled the in vitro release of aspirin for 7 days only. Analysis of PLGA matrix residuals revealed that PLGA in aspirin loaded formulations exhibited a significantly (p<0.05) faster degradation compared to blank formulations. These findings suggest that aspirin causes an unusually faster degradation of PLGA. Such faster degradation of PLGA has not been noticed for any other drugs reported in the literature.

  14. Functional Degradable Polymers by Radical Ring-Opening Copolymerization of MDO and Vinyl Bromobutanoate: Synthesis, Degradability and Post-Polymerization Modification.

    PubMed

    Hedir, Guillaume G; Bell, Craig A; O'Reilly, Rachel K; Dove, Andrew P

    2015-07-13

    The synthesis of vinyl bromobutanoate (VBr), a new vinyl acetate monomer derivative obtained by the palladium-catalyzed vinyl exchange reaction between vinyl acetate (VAc) and 4-bromobutyric acid is reported. The homopolymerization of this new monomer using the RAFT/MADIX polymerization technique leads to the formation of novel well-defined and controlled polymers containing pendent bromine functional groups able to be modified via postpolymerization modification. Furthermore, the copolymerization of vinyl bromobutanoate with 2-methylene-1,3-dioxepane (MDO) was also performed to deliver a range of novel functional degradable copolymers, poly(MDO-co-VBr). The copolymer composition was shown to be able to be tuned to vary the amount of ester repeat units in the polymer backbone, and hence determine the degradability, while maintaining a control of the final copolymers' molar masses. The addition of functionalities via simple postpolymerization modifications such as azidation and the 1,3-dipolar cycloaddition of a PEG alkyne to an azide is also reported and proven by (1)H NMR spectroscopy, FTIR spectroscopy, and SEC analyses. These studies enable the formation of a novel class of hydrophilic functional degradable copolymers using versatile radical polymerization methods.

  15. Acid-degradable hyperbranched polymer and its application in bottom anti-reflective coatings

    NASA Astrophysics Data System (ADS)

    Mercado, Ramil-Marcelo L.; Xu, Hao; Lowes, Joyce A.; Meador, Jim D.; Guerrero, Douglas J.

    2008-11-01

    A photosensitive developer-soluble bottom anti-reflective coating (DBARC) system is described for KrF and ArF lithographic applications. The system contains an acid-degradable branched polymer that is self-crosslinked into a polymeric film after spin coating and baking at high temperature, rendering a solvent-insoluble coating. The DBARC coating is tunable in terms having the appropriate light absorption (k value) and thickness for desirable reflection control. After the exposure of the resist, the DBARC layer decrosslinks into developer-soluble small molecules in the presence of photoacid generator (PAG). Thus the DBARC layer is removed simultaneously with the photoresist in the development process, instead of being etched away in a plasma-etching chamber in the case of traditional BARC layers. The etch budget is significantly improved so that a thin resist can be used for better resolution. Alternatively, the etch step can be omitted in the case of the formation of layers that may be damaged by exposure to plasma.

  16. Introduction of Environmentally Degradable Parameters to Evaluate the Biodegradability of Biodegradable Polymers

    PubMed Central

    Yang, Chao; Song, Cunjiang; Geng, Weitao; Li, Qiang; Wang, Yuanyuan; Kong, Meimei; Wang, Shufang

    2012-01-01

    Environmentally Degradable Parameter (EdK) is of importance in the describing of biodegradability of environmentally biodegradable polymers (BDPs). In this study, a concept EdK was introduced. A test procedure of using the ISO 14852 method and detecting the evolved carbon dioxide as an analytical parameter was developed, and the calculated EdK was used as an indicator for the ultimate biodegradability of materials. Starch and polyethylene used as reference materials were defined as the EdK values of 100 and 0, respectively. Natural soil samples were inoculated into bioreactors, followed by determining the rates of biodegradation of the reference materials and 15 commercial BDPs over a 2-week test period. Finally, a formula was deduced to calculate the value of EdK for each material. The EdK values of the tested materials have a positive correlation to their biodegradation rates in the simulated soil environment, and they indicated the relative biodegradation rate of each material among all the tested materials. Therefore, the EdK was shown to be a reliable indicator for quantitatively evaluating the potential biodegradability of BDPs in the natural environment. PMID:22675455

  17. Probing the diversity of chloromethane-degrading bacteria by comparative genomics and isotopic fractionation.

    PubMed

    Nadalig, Thierry; Greule, Markus; Bringel, Françoise; Keppler, Frank; Vuilleumier, Stéphane

    2014-01-01

    Chloromethane (CH3Cl) is produced on earth by a variety of abiotic and biological processes. It is the most important halogenated trace gas in the atmosphere, where it contributes to ozone destruction. Current estimates of the global CH3Cl budget are uncertain and suggest that microorganisms might play a more important role in degrading atmospheric CH3Cl than previously thought. Its degradation by bacteria has been demonstrated in marine, terrestrial, and phyllospheric environments. Improving our knowledge of these degradation processes and their magnitude is thus highly relevant for a better understanding of the global budget of CH3Cl. The cmu pathway, for chloromethane utilisation, is the only microbial pathway for CH3Cl degradation elucidated so far, and was characterized in detail in aerobic methylotrophic Alphaproteobacteria. Here, we reveal the potential of using a two-pronged approach involving a combination of comparative genomics and isotopic fractionation during CH3Cl degradation to newly address the question of the diversity of chloromethane-degrading bacteria in the environment. Analysis of available bacterial genome sequences reveals that several bacteria not yet known to degrade CH3Cl contain part or all of the complement of cmu genes required for CH3Cl degradation. These organisms, unlike bacteria shown to grow with CH3Cl using the cmu pathway, are obligate anaerobes. On the other hand, analysis of the complete genome of the chloromethane-degrading bacterium Leisingera methylohalidivorans MB2 showed that this bacterium does not contain cmu genes. Isotope fractionation experiments with L. methylohalidivorans MB2 suggest that the unknown pathway used by this bacterium for growth with CH3Cl can be differentiated from the cmu pathway. This result opens the prospect that contributions from bacteria with the cmu and Leisingera-type pathways to the atmospheric CH3Cl budget may be teased apart in the future.

  18. Control of enzymatic degradation of biodegradable polymers by treatment with biosurfactants, mannosylerythritol lipids, derived from Pseudozyma spp. yeast strains.

    PubMed

    Fukuoka, Tokuma; Shinozaki, Yukiko; Tsuchiya, Wataru; Suzuki, Ken; Watanabe, Takashi; Yamazaki, Toshimasa; Kitamoto, Dai; Kitamoto, Hiroko

    2016-02-01

    Cutinase-like esterase from the yeasts Pseudozyma antarctica (PaE) shows strong degradation activity in an agricultural biodegradable plastic (BP) model of mulch films composed of poly(butylene succinate-co-adipate) (PBSA). P. antarctica is known to abundantly produce a glycolipid biosurfactant, mannosylerythritol lipid (MEL). Here, the effects of MEL on PaE-catalyzed degradation of BPs were investigated. Based on PBSA dispersion solution, the degradation of PBSA particles by PaE was inhibited in the presence of MEL. MEL behavior on BP substrates was monitored by surface plasmon resonance (SPR) using a sensor chip coated with polymer films. The positive SPR signal shift indicated that MEL readily adsorbed and spread onto the surface of a BP film. The amount of BP degradation by PaE was monitored based on the negative SPR signal shift and was decreased 1.7-fold by MEL pretreatment. Furthermore, the shape of PBSA mulch films in PaE-containing solution was maintained with MEL pretreatment, whereas untreated films were almost completely degraded and dissolved. These results suggest that MEL covering the surface of BP film inhibits adsorption of PaE and PaE-catalyzed degradation of BPs. We applied the above results to control the microbial degradation of BP mulch films. MEL pretreatment significantly inhibited BP mulch film degradation by both PaE solution and BP-degradable microorganism. Moreover, the degradation of these films was recovered after removal of the coated MEL by ethanol treatment. These results demonstrate that the biodegradation of BP films can be readily and reversibly controlled by a physical approach using MEL.

  19. The organotin coordination polymer [(n-Bu3Sn)4Fe(CN)6H2O] as effective catalyst towards the oxidative degradation of methylene blue

    NASA Astrophysics Data System (ADS)

    Etaiw, S. E. H.; Saleh, Dalia I.

    2014-01-01

    The structure of the supramolecular coordination polymer SCP 1; [(n-Bu3Sn)4Fe(CN)6H2O] consists of octahedral [Fe(CN)6]4- building blocks which are connected by the TBPY-5 configured n-Bu3Sn(CN..)2 fragments creating 3D-network structure. Fenton and photo-Fenton oxidative discoloration of Methylene Blue (MB) has been investigated by hydrogen peroxide catalyzed with the SCP 1. The reaction exhibited pseudo first-order kinetics with respect to each of MB and H2O2. The irradiation of the reaction with UV-light enhanced the rate of MB mineralization, Kobs = 0.76 h-1. Mineralization of MB was investigated by FT-IR spectra. Disodium salt of terephthalic acid photoluminescence probing technology was carried out to identify the reactive oxygen species. The different parameters that affect MB degradation rate were evaluated. Moreover, the efficiency of recycled the SCP 1 and the mechanism of degradation of MB dye were investigated.

  20. The organotin coordination polymer [(n-Bu3Sn)4Fe(CN)6H2O] as effective catalyst towards the oxidative degradation of methylene blue.

    PubMed

    Etaiw, S E H; Saleh, Dalia I

    2014-01-03

    The structure of the supramolecular coordination polymer SCP 1; [(n-Bu3Sn)4Fe(CN)6H2O] consists of octahedral [Fe(CN)6](4-) building blocks which are connected by the TBPY-5 configured n-Bu3Sn(CN..)2 fragments creating 3D-network structure. Fenton and photo-Fenton oxidative discoloration of Methylene Blue (MB) has been investigated by hydrogen peroxide catalyzed with the SCP 1. The reaction exhibited pseudo first-order kinetics with respect to each of MB and H2O2. The irradiation of the reaction with UV-light enhanced the rate of MB mineralization, Kobs=0.76 h(-1). Mineralization of MB was investigated by FT-IR spectra. Disodium salt of terephthalic acid photoluminescence probing technology was carried out to identify the reactive oxygen species. The different parameters that affect MB degradation rate were evaluated. Moreover, the efficiency of recycled the SCP 1 and the mechanism of degradation of MB dye were investigated.

  1. An amphiphilic degradable polymer/hydroxyapatite composite with enhanced handling characteristics promotes osteogenic gene expression in bone marrow stromal cells.

    PubMed

    Kutikov, Artem B; Song, Jie

    2013-09-01

    Electrospun polymer/hydroxyapatite (HA) composites combining biodegradability with osteoconductivity are attractive for skeletal tissue engineering applications. However, most biodegradable polymers such as poly(lactic acid) (PLA) are hydrophobic and do not blend with adequate interfacial adhesion with HA, compromising the structural homogeneity, mechanical integrity and biological performance of the composite. To overcome this challenge, we combined a hydrophilic polyethylene glycol (PEG) block with poly(d,l-lactic acid) to improve the adhesion of the degradable polymer with HA. The amphiphilic triblock copolymer PLA-PEG-PLA (PELA) improved the stability of HA-PELA suspension at 25wt.% HA content, which was readily electrospun into HA-PELA composite scaffolds with uniform fiber dimensions. HA-PELA was highly extensible (failure strain>200% vs. <40% for HA-PLA), superhydrophilic (∼0° water contact angle vs. >100° for HA-PLA), and exhibited an 8-fold storage modulus increase (unlike deterioration for HA-PLA) upon hydration, owing to the favorable interaction between HA and PEG. HA-PELA also better promoted osteochondral lineage commitment of bone marrow stromal cells in unstimulated culture and supported far more potent osteogenic gene expression upon induction than HA-PLA. We demonstrate that the chemical incorporation of PEG is an effective strategy to improve the performance of degradable polymer/HA composites for bone tissue engineering applications.

  2. Direct imaging and probing of the p-n junction in a planar polymer light-emitting electrochemical cell.

    PubMed

    Hu, Yufeng; Gao, Jun

    2011-02-23

    A vast array of semiconductor applications relies on the ability to dope the materials by the controlled introduction of impurities in order to achieve desired charge carrier concentration and conduction type. In this way, various functional metal/semiconductor or semiconductor/semiconductor junctions can be constructed for device applications. Conjugated polymers are organic semiconductors that can be electrochemically doped to form a dynamic p-n junction. The electronic structure and even the existence of such a polymer p-n junction had been the subject of intense scrutiny and debate. In this work, the formation of the world's largest frozen polymer p-n junction and its light-emission are visualized. With a pair of micromanipulated probes, we mapped the potential distribution of the p-n junction under bias across the entire interelectrode gap of over 10 mm. Site-selective current-voltage measurements reveal that the polymer junction is a graded p-n junction, with a much more conductive p region than n region.

  3. Leucoagaricus gongylophorus Produces Diverse Enzymes for the Degradation of Recalcitrant Plant Polymers in Leaf-Cutter Ant Fungus Gardens

    SciTech Connect

    Aylward, Frank O.; Burnum-Johnson, Kristin E.; Tringe, Susannah G.; Teiling, Clotilde; Tremmel, Daniel; Moeller, Joseph; Scott, Jarrod J.; Barry, Kerrie W.; Piehowski, Paul D.; Nicora, Carrie D.; Malfatti, Stephanie; Monroe, Matthew E.; Purvine, Samuel O.; Goodwin, Lynne A.; Smith, Richard D.; Weinstock, George; Gerardo, Nicole; Suen, Garret; Lipton, Mary S.; Currie, Cameron R.

    2013-06-12

    Plants represent a large reservoir of organic carbon comprised largely of recalcitrant polymers that most metazoans are unable to deconstruct. Many herbivores gain access to nutrients in this material indirectly by associating with microbial symbionts, and leaf-cutter ants are a paradigmatic example. These ants use fresh foliar biomass as manure to cultivate fungus gardens composed primarily of Leucoagaricus gongylophorus, a basidiomycetous symbiont that produces specialized hyphal swellings that serve as a food source for the host ant colony. Although leaf-cutter ants are conspicuous herbivores that contribute substantially to carbon turnover in Neotropical ecosystems, the process through which plant biomass is degraded in their fungus gardens is not well understood. Here we present the first draft genome of L. gongylophorus, and using genomic, metaproteomic, and phylogenetic tools we investigate its role in lignocellulose degradation in the fungus gardens of both Atta cephalotes and Acromyrmex echinatior leaf-cutter ants. We show that L. gongylophorus produces a diversity of lignocellulases in fungus gardens, and is likely the primary driver of plant biomass degradation in these ecosystems. We also show that this fungus produces distinct sets of lignocellulases throughout the different stages of biomass degradation, including numerous cellulases and laccases that may be playing an important but previously uncharacterized role in lignocellulose degradation. Our study provides a comprehensive analysis of plant biomass degradation in leaf-cutter ant fungus gardens and provides insight into the molecular dynamics underlying the symbiosis between these dominant herbivores and their obligate fungal cultivar.

  4. Leucoagaricus gongylophorus produces diverse enzymes for the degradation of recalcitrant plant polymers in leaf-cutter ant fungus gardens.

    PubMed

    Aylward, Frank O; Burnum-Johnson, Kristin E; Tringe, Susannah G; Teiling, Clotilde; Tremmel, Daniel M; Moeller, Joseph A; Scott, Jarrod J; Barry, Kerrie W; Piehowski, Paul D; Nicora, Carrie D; Malfatti, Stephanie A; Monroe, Matthew E; Purvine, Samuel O; Goodwin, Lynne A; Smith, Richard D; Weinstock, George M; Gerardo, Nicole M; Suen, Garret; Lipton, Mary S; Currie, Cameron R

    2013-06-01

    Plants represent a large reservoir of organic carbon comprised primarily of recalcitrant polymers that most metazoans are unable to deconstruct. Many herbivores gain access to nutrients in this material indirectly by associating with microbial symbionts, and leaf-cutter ants are a paradigmatic example. These ants use fresh foliar biomass as manure to cultivate gardens composed primarily of Leucoagaricus gongylophorus, a basidiomycetous fungus that produces specialized hyphal swellings that serve as a food source for the host ant colony. Although leaf-cutter ants are conspicuous herbivores that contribute substantially to carbon turnover in Neotropical ecosystems, the process through which plant biomass is degraded in their fungus gardens is not well understood. Here we present the first draft genome of L. gongylophorus, and, using genomic and metaproteomic tools, we investigate its role in lignocellulose degradation in the gardens of both Atta cephalotes and Acromyrmex echinatior leaf-cutter ants. We show that L. gongylophorus produces a diversity of lignocellulases in ant gardens and is likely the primary driver of plant biomass degradation in these ecosystems. We also show that this fungus produces distinct sets of lignocellulases throughout the different stages of biomass degradation, including numerous cellulases and laccases that likely play an important role in lignocellulose degradation. Our study provides a detailed analysis of plant biomass degradation in leaf-cutter ant fungus gardens and insight into the enzymes underlying the symbiosis between these dominant herbivores and their obligate fungal cultivar.

  5. Using DNA-Stable Isotope Probing to Identify MTBE- and TBA-Degrading Microorganisms in Contaminated Groundwater

    PubMed Central

    Key, Katherine C.; Sublette, Kerry L.; Duncan, Kathleen; Mackay, Douglas M.; Scow, Kate M.; Ogles, Dora

    2014-01-01

    Although the anaerobic biodegradation of methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA) has been documented in the laboratory and the field, knowledge of the microorganisms and mechanisms involved is still lacking. In this study, DNA-stable isotope probing (SIP) was used to identify microorganisms involved in anaerobic fuel oxygenate biodegradation in a sulfate-reducing MTBE and TBA plume. Microorganisms were collected in the field using Bio-Sep® beads amended with 13C5-MTBE, 13C1-MTBE (only methoxy carbon labeled), or13C4-TBA. 13C-DNA and 12C-DNA extracted from the Bio-Sep beads were cloned and 16S rRNA gene sequences were used to identify the indigenous microorganisms involved in degrading the methoxy group of MTBE and the tert-butyl group of MTBE and TBA. Results indicated that microorganisms were actively degrading 13C-labeled MTBE and TBA in situ and the 13C was incorporated into their DNA. Several sequences related to known MTBE- and TBA-degraders in the Burkholderiales and the Sphingomonadales orders were detected in all three13C clone libraries and were likely to be primary degraders at the site. Sequences related to sulfate-reducing bacteria and iron-reducers, such as Geobacter and Geothrix, were only detected in the clone libraries where MTBE and TBA were fully labeled with 13C, suggesting that they were involved in processing carbon from the tert-butyl group. Sequences similar to the Pseudomonas genus predominated in the clone library where only the methoxy carbon of MTBE was labeled with 13C. It is likely that members of this genus were secondary degraders cross-feeding on 13C-labeled metabolites such as acetate. PMID:25525320

  6. Simultaneous determination of drug surface concentration and polymer degradation kinetics in biodegradable polymer/drug membranes: a model drug delivery system

    NASA Astrophysics Data System (ADS)

    Lee, Joo-Woon; Gardella, Joseph A.

    2004-06-01

    This paper reports new simultaneous ToF-SIMS analysis to determine both the earliest stage of polymer degradation and the surface concentration of a drug additive. The static SIMS spectra of a model Ph 3N/poly( L-lactic acid) (PLLA) (20:80 wt.%) blend matrix ( t˜0.4 μm on 1.0 cm 2) hydrolyzed in buffered conditions are simultaneously and independently analyzed in the low mass range for the surface accumulation profile of Ph 3N and in the high mass for the hydrolytic degradation kinetics of PLLA, respectively. The rate of PLLA degradation at pH 10.0 is ˜2 times faster than that at pH 7.4, but the corresponding rate of Ph 3N accumulation at the surface is accelerated by a factor of ˜10.5 times faster. The results provide new insight in evaluating the surface concentration of Ph 3N (p Kb=0) from the blends, indicating that the initial rapid increase in surface concentration of Ph 3N is related to but not singularly dependent on the rate of PLLA degradation.

  7. Blister Test for Measurements of Adhesion and Adhesion Degradation of Organic Polymers on AA2024-T3

    NASA Astrophysics Data System (ADS)

    Rincon Troconis, Brendy Carolina

    A key parameter for the performance of corrosion protective coatings applied to metals is adhesion. Surface preparation prior to coating application is known to be critical, but there is a lack of understanding of what controls adhesion. Numerous techniques have been developed in the last decades to measure the adhesion strength of coatings to metals. Nonetheless, they are generally non-quantitative, non-reproducible, performed in dry conditions, or overestimate adhesion. In this study, a quantitative and reproducible technique, the Blister Test (BT), is used. The BT offers the ability to study the effects of a range of parameters, including the presence or absence of a wetting liquid, and simulates the stress situation in the coating/substrate interface. The effects of roughness and surface topography were studied by the BT and Optical Profilometry, using AA2024-T3 substrates coated with polyvinyl butyral (PVB). Random abrasion generated a surface with lower average roughness than aligned abrasion due to the continual cross abrasion of the grooves. The BT could discern the effects of different mechanical treatments. An adhesion strength indicator was defined and found to be a useful parameter. The effectiveness of standard adhesion techniques such as ASTM D4541 (Pull-off Test) and ASTM D3359 (Tape Test) was compared to the BT. Also, different attempts to measure adhesion and adhesion degradation of organic polymers to AA2024-T3 were tested. The pull-off test does not produce adhesive failure across the entire interface, while the tape test is a very qualitative technique and does not discern between the effects of different coating systems on the adhesion performance. The BT produces adhesive failure of the primer studied, is very reproducible, and is able to rank different coating systems. Therefore, it was found to be superior to the others. The approaches tested for adhesion degradation were not aggressive enough to have a measurable effect. The effects of

  8. Decades-scale degradation of commercial, side-chain, fluorotelomer-based polymers in soils and water.

    PubMed

    Washington, John W; Jenkins, Thomas M; Rankin, Keegan; Naile, Jonathan E

    2015-01-20

    Fluorotelomer-based polymers (FTPs) are the primary product of the fluorotelomer industry. Here we report on a 376-day study of the degradability of two commercial acrylate-linked FTPs in four saturated soils and in water. Using an exhaustive serial extraction, we report GC/MS and LC/MS/MS results for 50 species including fluorotelomer alcohols and acids, and perfluorocarboxylates. Modeling of seven sampling rounds, each consisting of ≥5 replicate microcosm treatments, for one commercial FTP in one soil yielded half-life estimates of 65–112 years and, when the other commercial FTP and soils were evaluated, the estimated half-lives ranged from 33 to 112 years. Experimental controls, consisting of commercial FTP in water, degraded roughly at the same rate as in soil. A follow-up experiment, with commercial FTP in pH 10 water, degraded roughly 10-fold faster than the circum-neutral control suggesting that commercial FTPs can undergo OH–-mediated hydrolysis. 8:2Fluorotelomer alcohol generated from FTP degradation in soil was more stable than without FTP present suggesting a clathrate guest–host association with the FTP. To our knowledge, these are the only degradability-test results for commercial FTPs that have been generated using exhaustive extraction procedures. They unambiguously show that commercial FTPs, the primary product of the fluorotelomer industry, are a source of fluorotelomer and perfluorinated compounds to the environment.

  9. Probing Rubber Cross-Linking Generation of Industrial Polymer Networks at Nanometer Scale.

    PubMed

    Gabrielle, Brice; Gomez, Emmanuel; Korb, Jean-Pierre

    2016-06-23

    We present improved analyses of rheometric torque measurements as well as (1)H double-quantum (DQ) nuclear magnetic resonance (NMR) buildup data on polymer networks of industrial compounds. This latter DQ NMR analysis allows finding the distribution of an orientation order parameter (Dres) resulting from the noncomplete averaging of proton dipole-dipole couplings within the cross-linked polymer chains. We investigate the influence of the formulation (filler and vulcanization systems) as well as the process (curing temperature) ending to the final polymer network. We show that DQ NMR follows the generation of the polymer network during the vulcanization process from a heterogeneous network to a very homogeneous one. The time variations of microscopic Dres and macroscopic rheometric torques present power-law behaviors above a threshold time scale with characteristic exponents of the percolation theory. We observe also a very good linear correlation between the kinetics of Dres and rheometric data routinely performed in industry. All these observations confirm the description of the polymer network generation as a critical phenomenon. On the basis of all these results, we believe that DQ NMR could become a valuable tool for investigating in situ the cross-linking of industrial polymer networks at the nanometer scale.

  10. Monodisperse raspberry-like multihollow polymer/Ag nanocomposite microspheres for rapid catalytic degradation of methylene blue.

    PubMed

    Tian, Qiong; Yu, Xiaojing; Zhang, Lifeng; Yu, Demei

    2017-04-01

    Raspberry-like multihollow polymer microspheres were prepared by seeded swelling polymerization and decorated with silver nanoparticles (AgNPs) in the presence of polyvinylpyrrolidone (PVP) which acted as both reducing and stabilizing agent. Formation mechanism of the raspberry-like multihollow microsphere was discussed on the basis of water absorption of sulfonated groups in the seeded swelling polymerization. Effects of weight ratio of sodium 4-vinylbenzenesulfonate to styrene (NaSS/St) of the seed particles, the concentration of PVP and [Ag(NH3)2](+) ions on the properties of polymer/Ag nanocomposite microspheres were investigated by microscopic observation, nitrogen adsorption/desorption isotherms, UV-vis absorption spectra, X-ray diffraction patterns and thermogravimetric analysis. The results demonstrated that the raspberry-like multihollow microspheres were successfully fabricated by controlling over the NaSS/St of the seed particles in the seeded swelling polymerization by which the fabrication of hollow structure became simple and convenient. The spherical AgNPs were loaded on the polymer microsphere by in-situ chemical reduction due to the stabilization and reduction of PVP and the attraction between sulfonated groups and [Ag(NH3)2](+) ions. The raspberry-like multihollow polymer/Ag microspheres showed good catalytic activity and reusability in the degradation of methylene blue in the presence of NaBH4.

  11. The Chemical Behavior and Degradation Mitigation Effect of Cerium Oxide Nanoparticles in Perfluorosulfonic Acid Polymer Electrolyte Membranes

    SciTech Connect

    Pearman, Benjamin P; Mohajeri, Nahid; Slattery, Darlene; Hampton, Michael; Seal, Sudipta; Cullen, David A

    2013-01-01

    Perfluorosulfonic acid membranes, the polymer of choice for polymer electrolyte hydrogen fuel cells, are susceptible to degradation due to attacks on polymer chains from radicals. Mitigation of this attack by cerium-based radical scavengers is an approach that has shown promise. In this work, two formulations of single-crystal cerium oxide nanoparticles, with an order of magnitude difference in particle size, are incorporated into said membranes and subjected to proton conductivity measurements and ex-situ durability tests. We found that ceria is reduced to Ce(III) ions in the acidic environment of a heated, humidified membrane which negatively impacts proton conductivity. In liquid and gas Fenton testing, fluoride emission is reduced by an order of magnitude, drastically increasing membrane longevity. Side-product analysis demonstrated that in the liquid Fenton test, the main point of attack are weak polymer end groups, while in the gas Fenton test, there is additional side-chain attack. Both mechanisms are mitigated by the addition of the ceria nanoparticles, whereby the extent of the durability improvement is found to be independent of particle size.

  12. A mechanistic model for drug release in PLGA biodegradable stent coatings coupled with polymer degradation and erosion.

    PubMed

    Zhu, Xiaoxiang; Braatz, Richard D

    2015-07-01

    Biodegradable poly(d,l-lactic-co-glycolic acid) (PLGA) coating for applications in drug-eluting stents has been receiving increasing interest as a result of its unique properties compared with biodurable polymers in delivering drug for reducing stents-related side effects. In this work, a mathematical model for describing the PLGA degradation and erosion and coupled drug release from PLGA stent coating is developed and validated. An analytical expression is derived for PLGA mass loss that predicts multiple experimental studies in the literature. An analytical model for the change of the number-average degree of polymerization [or molecular weight (MW)] is also derived. The drug transport model incorporates simultaneous drug diffusion through both the polymer solid and the liquid-filled pores in the coating, where an effective drug diffusivity model is derived taking into account factors including polymer MW change, stent coating porosity change, and drug partitioning between solid and aqueous phases. The model is used to describe in vitro sirolimus release from PLGA stent coating, and demonstrates the significance of simultaneous sirolimus release via diffusion through both polymer solid and pore space. The proposed model is compared to existing drug transport models, and the impact of model parameters, limitations and possible extensions of the model are also discussed.

  13. Probing effects of polymer adsorption in colloidal particle suspensions by light scattering as relevant for the aquatic environment: An overview.

    PubMed

    Tiraferri, Alberto; Borkovec, Michal

    2015-12-01

    Modification of particle surfaces by adsorption of polymers is a process that governs particle behavior in aqueous environmental systems. The present article briefly reviews the current understanding of the adsorption mechanisms and the properties of the resulting layers, and it discusses two environmentally relevant cases of particle modification by polymers. In particular, the discussion focuses on the usefulness of methods based on light scattering to probe such adsorbed layers together with the resulting properties of the particle suspensions, and it highlights advantages and disadvantages of these techniques. Measurement of the electrophoretic mobility allows to follow the development of the adsorption layer and to characterize the charge of the modified particles. At saturation, the surface charge is governed by the charge of the adsorbed film. Dynamic light scattering provides information on the film thickness and on the behavior of the modified suspensions. The charge and the structure of the adsorbed layer influence the stability of the particles, as well as the applicability of the classical theory of Derjaguin, Landau, Verwey, and Overbeek (DLVO). This fundamental knowledge is presented in the light of environmental systems and its significance for applied systems is underlined. In particular, the article discusses two examples of environmental processes involving adsorption of polymers, namely, the modification of particles by natural adsorption of humic substances and the tailoring of surface properties of iron-based particles used to remediate contaminated aquifers.

  14. Development of Quantum Dot Probes for Studies of Synergy Between Components of the Wood-Degrading Fungal Enzymes

    SciTech Connect

    Yang, Haw; Nixon, B. Tracy; Tien, Ming

    2011-09-01

    “Development of Quantum Dot Probes for Studies of Synergy Between Components of the Wood-Degrading Fungal Enzymes,” aims to develop quantum dot-based tagging and imaging technologies tailored for simultaneously monitoring, in real time and in the natural fungal / lignocellulose environment, the mode of action of several lignocellulosic enzymes at the single-molecule level. With a three-year research scope, it is designed to be the first project of a long-term research program for which the overarching goal is to bridge the aforementioned knowledge gap by a quantitative determination of the biochemical and biophysical properties of these fungal enzymes in realistic plant biomass-microbe milieus.

  15. Abnormal strong burn-in degradation of highly efficient polymer solar cells caused by spinodal donor-acceptor demixing

    NASA Astrophysics Data System (ADS)

    Li, Ning; Perea, José Darío; Kassar, Thaer; Richter, Moses; Heumueller, Thomas; Matt, Gebhard J.; Hou, Yi; Güldal, Nusret S.; Chen, Haiwei; Chen, Shi; Langner, Stefan; Berlinghof, Marvin; Unruh, Tobias; Brabec, Christoph J.

    2017-02-01

    The performance of organic solar cells is determined by the delicate, meticulously optimized bulk-heterojunction microstructure, which consists of finely mixed and relatively separated donor/acceptor regions. Here we demonstrate an abnormal strong burn-in degradation in highly efficient polymer solar cells caused by spinodal demixing of the donor and acceptor phases, which dramatically reduces charge generation and can be attributed to the inherently low miscibility of both materials. Even though the microstructure can be kinetically tuned for achieving high-performance, the inherently low miscibility of donor and acceptor leads to spontaneous phase separation in the solid state, even at room temperature and in the dark. A theoretical calculation of the molecular parameters and construction of the spinodal phase diagrams highlight molecular incompatibilities between the donor and acceptor as a dominant mechanism for burn-in degradation, which is to date the major short-time loss reducing the performance and stability of organic solar cells.

  16. Abnormal strong burn-in degradation of highly efficient polymer solar cells caused by spinodal donor-acceptor demixing

    PubMed Central

    Li, Ning; Perea, José Darío; Kassar, Thaer; Richter, Moses; Heumueller, Thomas; Matt, Gebhard J.; Hou, Yi; Güldal, Nusret S.; Chen, Haiwei; Chen, Shi; Langner, Stefan; Berlinghof, Marvin; Unruh, Tobias; Brabec, Christoph J.

    2017-01-01

    The performance of organic solar cells is determined by the delicate, meticulously optimized bulk-heterojunction microstructure, which consists of finely mixed and relatively separated donor/acceptor regions. Here we demonstrate an abnormal strong burn-in degradation in highly efficient polymer solar cells caused by spinodal demixing of the donor and acceptor phases, which dramatically reduces charge generation and can be attributed to the inherently low miscibility of both materials. Even though the microstructure can be kinetically tuned for achieving high-performance, the inherently low miscibility of donor and acceptor leads to spontaneous phase separation in the solid state, even at room temperature and in the dark. A theoretical calculation of the molecular parameters and construction of the spinodal phase diagrams highlight molecular incompatibilities between the donor and acceptor as a dominant mechanism for burn-in degradation, which is to date the major short-time loss reducing the performance and stability of organic solar cells. PMID:28224984

  17. Platinum oxidation responsible for degradation of platinum-cobalt alloy cathode catalysts for polymer electrolyte fuel cells

    NASA Astrophysics Data System (ADS)

    Hidai, Shoichi; Kobayashi, Masaki; Niwa, Hideharu; Harada, Yoshihisa; Oshima, Masaharu; Nakamori, Yoji; Aoki, Tsutomu

    2012-10-01

    Platinum oxidation of Pt-Co alloy catalysts for polymer electrolyte fuel cells was investigated for a series of Pt-Co alloy catalysts with different specification. The chemical state of platinum evaluated by soft X-ray photoemission spectroscopy was compared with the electrochemical properties to elucidate the origin of catalyst degradation. Increase in the particle size of Pt-Co alloy catalysts caused the decrease in the concentration of platinum hydroxide and improved the catalyst durability. Applying potential cycling below 1.0 V, only platinum hydroxide was observed, while platinum oxides, PtO and PtO2, appeared after potential cycling up to 1.2 V. The peak shift of Pt 4f spectra after the potential cycling implies that these platinum hydroxide and oxide are dissolved and deposited on another platinum catalyst in a reduced metallic state, which causes the catalyst degradation.

  18. Surface modification of neural probes with conducting polymer poly(hydroxymethylated-3,4- ethylenedioxythiophene) and its biocompatibility.

    PubMed

    Xiao, Yinghong; Martin, David C; Cui, Xinyan; Shenai, Mahesh

    2006-02-01

    A novel conducting polymer, poly(hydroxymethylated-3,4-ethylenedioxythiophene) (PEDOT-MeOH), was electrochemically deposited onto the electrodes of micromachined neural probes. Uniformly distributed film was obtained from aqueous solution when doped with polystyrenesulfonate. The surface morphology was rough and had good cellular adhesion. Impedance spectroscopy showed that the magnitude of coated electrode was lower than that of the bare gold over a range of frequencies from 10(0)to 10(5) Hz. Since the biocompatibility of the interface between the neural probes and brain tissue plays an important role when the probes are implanted in the central nervous system for long-term application, biomolecules were incorporated into the coating. Nonapeptide CDPGYIGSR was codeposited as the counterion in the conducting films. The surface morphology of the coating was fuzzy, providing many bioactive sites for interaction with neural cells. The magnitude of impedance was as low as 53 kOmega at the biologically relevant frequency of 1 kHz. An in vitro experiment demonstrated that the neuroblastoma cells grew preferentially on the PEDOT-MeOH/CDPGYIGSR-coated electrode sites and spread beyond the electrode area.

  19. Enhancement of Interface Characteristics of Neural Probe Based on Graphene, ZnO Nanowires, and Conducting Polymer PEDOT.

    PubMed

    Ryu, Mingyu; Yang, Jae Hoon; Ahn, Yumi; Sim, Minkyung; Lee, Kyung Hwa; Kim, Kyungsoo; Lee, Taeju; Yoo, Seung-Jun; Kim, So Yeun; Moon, Cheil; Je, Minkyu; Choi, Ji-Woong; Lee, Youngu; Jang, Jae Eun

    2017-03-29

    In the growing field of brain-machine interface (BMI), the interface between electrodes and neural tissues plays an important role in the recording and stimulation of neural signals. To minimize tissue damage while retaining high sensitivity, a flexible and a smaller electrode with low impedance is required. However, it is a major challenge to reduce electrode size while retaining the conductive characteristics of the electrode. In addition, the mechanical mismatch between stiff electrodes and soft tissues creates damaging reactive tissue responses. Here, we demonstrate a neural probe structure based on graphene, ZnO nanowires, and conducting polymer that provides flexibility and low impedance performance. A hybrid Au and graphene structure was utilized to achieve both flexibility and good conductivity. Using ZnO nanowires to increase the effective surface area drastically decreased the impedance value and enhanced the signal-to-noise ratio (SNR). A poly[3,4-ethylenedioxythiophene] (PEDOT) coating on the neural probe improved the electrical characteristics of the electrode while providing better biocompatibility. In vivo neural signal recordings showed that our neural probe can detect clearer signals.

  20. Photocurrent Spectroscopy of Perovskite Layers and Solar Cells: A Sensitive Probe of Material Degradation.

    PubMed

    Holovský, Jakub; De Wolf, Stefaan; Werner, Jérémie; Remeš, Zdeněk; Müller, Martin; Neykova, Neda; Ledinský, Martin; Černá, Ladislava; Hrzina, Pavel; Löper, Philipp; Niesen, Bjoern; Ballif, Christophe

    2017-02-16

    Optical absorptance spectroscopy of polycrystalline CH3NH3PbI3 films usually indicates the presence of a PbI2 phase, either as a preparation residue or due to film degradation, but gives no insight on how this may affect electrical properties. Here, we apply photocurrent spectroscopy to both perovskite solar cells and coplanar-contacted layers at various stages of degradation. In both cases, we find that the presence of a PbI2 phase restricts charge-carrier transport, suggesting that PbI2 encapsulates CH3NH3PbI3 grains. We also find that PbI2 injects holes into the CH3NH3PbI3 grains, increasing the apparent photosensitivity of PbI2. This phenomenon, known as modulation doping, is absent in the photocurrent spectra of solar cells, where holes and electrons have to be collected in pairs. This interpretation provides insights into the photogeneration and carrier transport in dual-phase perovskites.

  1. Multiple DNA extractions coupled with stable-isotope probing of anthracene-degrading bacteria in contaminated soil.

    PubMed

    Jones, Maiysha D; Singleton, David R; Sun, Wei; Aitken, Michael D

    2011-05-01

    In many of the DNA-based stable-isotope probing (SIP) studies published to date in which soil communities were investigated, a single DNA extraction was performed on the soil sample, usually using a commercial DNA extraction kit, prior to recovering the (13)C-labeled (heavy) DNA by density-gradient ultracentrifugation. Recent evidence suggests, however, that a single extraction of a soil sample may not lead to representative recovery of DNA from all of the organisms in the sample. To determine whether multiple DNA extractions would affect the DNA yield, the eubacterial 16S rRNA gene copy number, or the identification of anthracene-degrading bacteria, we performed seven successive DNA extractions on the same aliquot of contaminated soil either untreated or enriched with [U-(13)C]anthracene. Multiple extractions were necessary to maximize the DNA yield and 16S rRNA gene copy number from both untreated and anthracene-enriched soil samples. Sequences within the order Sphingomonadales, but unrelated to any previously described genus, dominated the 16S rRNA gene clone libraries derived from (13)C-enriched DNA and were designated "anthracene group 1." Sequences clustering with Variovorax spp., which were also highly represented, and sequences related to the genus Pigmentiphaga were newly associated with anthracene degradation. The bacterial groups collectively identified across all seven extracts were all recovered in the first extract, although quantitative PCR analysis of SIP-identified groups revealed quantitative differences in extraction patterns. These results suggest that performing multiple DNA extractions on soil samples improves the extractable DNA yield and the number of quantifiable eubacterial 16S rRNA gene copies but have little qualitative effect on the identification of the bacterial groups associated with the degradation of a given carbon source by SIP.

  2. Multiple DNA Extractions Coupled with Stable-Isotope Probing of Anthracene-Degrading Bacteria in Contaminated Soil▿†

    PubMed Central

    Jones, Maiysha D.; Singleton, David R.; Sun, Wei; Aitken, Michael D.

    2011-01-01

    In many of the DNA-based stable-isotope probing (SIP) studies published to date in which soil communities were investigated, a single DNA extraction was performed on the soil sample, usually using a commercial DNA extraction kit, prior to recovering the 13C-labeled (heavy) DNA by density-gradient ultracentrifugation. Recent evidence suggests, however, that a single extraction of a soil sample may not lead to representative recovery of DNA from all of the organisms in the sample. To determine whether multiple DNA extractions would affect the DNA yield, the eubacterial 16S rRNA gene copy number, or the identification of anthracene-degrading bacteria, we performed seven successive DNA extractions on the same aliquot of contaminated soil either untreated or enriched with [U-13C]anthracene. Multiple extractions were necessary to maximize the DNA yield and 16S rRNA gene copy number from both untreated and anthracene-enriched soil samples. Sequences within the order Sphingomonadales, but unrelated to any previously described genus, dominated the 16S rRNA gene clone libraries derived from 13C-enriched DNA and were designated “anthracene group 1.” Sequences clustering with Variovorax spp., which were also highly represented, and sequences related to the genus Pigmentiphaga were newly associated with anthracene degradation. The bacterial groups collectively identified across all seven extracts were all recovered in the first extract, although quantitative PCR analysis of SIP-identified groups revealed quantitative differences in extraction patterns. These results suggest that performing multiple DNA extractions on soil samples improves the extractable DNA yield and the number of quantifiable eubacterial 16S rRNA gene copies but have little qualitative effect on the identification of the bacterial groups associated with the degradation of a given carbon source by SIP. PMID:21398486

  3. Nanoscale probing of a polymer-blend thin film with tip-enhanced Raman spectroscopy.

    PubMed

    Yeo, Boon-Siang; Amstad, Esther; Schmid, Thomas; Stadler, Johannes; Zenobi, Renato

    2009-04-01

    Fundamental advances have been made in the spatially resolved chemical analysis of polymer thin films. Tip-enhanced Raman spectroscopy (TERS) is used to investigate the surface composition of a mixed polyisoprene (PI) and polystyrene (PS) thin film. High-quality TER spectra are collected from these nonresonant Raman-active polymers. A wealth of structural information is obtained, some of which cannot be acquired with conventional analytical techniques. PI and PS are identified at the surface and subsurface, respectively. Differences in the band intensities suggest strongly that the polymer layers are not uniformly thick, and that nanopores are present under the film surface. The continuous PS subsurface layer and subsurface nanopores have hitherto not been identified. These data are obtained with nanometer spatial resolution. Confocal far-field Raman spectroscopy and X-ray photoelectron spectroscopy are employed to corroborate some of the results. With routine production of highly enhancing TERS tips expected in the near future, it is predicted that TERS will be of great use for the rigorous chemical analysis of polymer and other composite systems with nanometer spatial resolution.

  4. Probing the association behavior of poly(ethylene glycol)-based amphiphilic comb-like polymer in NaCl solution.

    PubMed

    Basak, P; Nisha, C K; Manorama, S V; Maiti, Souvik; Jayachandran, K N

    2003-06-15

    The effect of salt on the associative behavior of intramolecular aggregates obtained from poly(ethylene glycol)-based amphiphilic comb-like polymers in aqueous medium at pH 6.2 has been investigated by surface tension, fluorescence probe, dynamic light-scattering, and viscometry techniques. Results reveal that the addition of salt screens the electrostatic repulsion between the charges along the polymer backbone in the aggregates and consequently (1) reduces the surface activity at the air/water interface, (2) leads to the contraction of the polymer backbone, and (3) reduces the hydrodynamic sizes of the aggregates. In contrast, the hydrophobicity of the aggregates remains unperturbed.

  5. H-bonding vs non-H-bonding in 100% pyrene methacrylate comb polymers: self-assembly probed by time-resolved emission spectra and temperature dependent fluorescence.

    PubMed

    Kaushlendra, K; Asha, S K

    2014-05-08

    The differences in self-organization behavior in novel 100% pyrene labeled comb methacrylate polymers probed as a function of their varied origins of excimer formation are presented. The different structural variations in the polymers included the presence or absence of hydrogen bonding interactions in the form of urethane linkages, short or long alkyl spacer segments separating the pyrene units from the polymer backbone and linear versus kinked urethane linkage. The effect of variable concentration and temperature on the chemical shift of the NH proton of the urethane linkage was probed using (1)H NMR experiments conducted at temperatures varying from 25 to 70 °C at two different concentrations (2.5 and 25 mmol) in DMSO-d6 as solvent. The photophysical properties of the polymers in dilute DMF solutions were investigated by steady state emission, fluorescence decay studies, time-resolved emission spectra (TRES), and variable temperature emission studies. It was observed that the polymer poly(PBH) having a non-hydrogen-bondable ester linkage in the pendant chains formed an excimer completely via a static mechanism and the ground state aggregate species were not broken even at higher temperatures. The polymer poly(PIC) having a short hydrogen-bondable urethane linkage formed an excimer via a static as well as dynamic mechanism. The other hydrogen-bondable urethane methacrylate polymers having a linear linker poly(PHH) and kinked linker (PIHP) formed excimer mostly via a dynamic mechanism with a very small contribution from the static route. The TRES studies carried out for the polymers provided significant insight into the excimer formation mechanism in these polymers. The variable temperature fluorescence studies highlighted the differences in the H-bonded vs non-H-bonded polymer as a function of their excimer recovery upon cooling.

  6. Aging Degradation of Austenitic Stainless Steel Weld Probed by Electrochemical Method and Impact Toughness Evaluation

    NASA Astrophysics Data System (ADS)

    Singh, Raghuvir; Das, Goutam; Mahato, B.; Singh, P. K.

    2017-01-01

    The present study discriminates the spinodal decomposition and G-phase precipitation in stainless steel welds by double loop electrochemical potentio-kinetic reactivation method and correlates it with the degradation in toughness property. The welds produced with different heat inputs were aged up to 10,000 hours at 673 K to 723 K (400 to 450 °C) and evaluated subsequently for the degree of sensitization (DOS) and impact toughness. The DOS values obtained were attributed to the spinodal decomposition and precipitation of G-phase. Study shows that the DOS correlates well with the impact toughness of the 304LN weld. Prolonged aging at 673 K and 723 K (400 °C and 450 °C) increased the DOS values while the impact toughness was decreased. The weld fabricated at 1 kJ/mm of heat input, produced higher DOS, compared to that at 3 kJ/mm. The geometrical location along the weld is shown to influence the DOS; higher values were obtained at the root than at the topside of the weld. Vermicular and columnar microstructure, in addition to the spinodal decomposition and G-phase precipitation, observed in the root side of the weld appear risky for the impact toughness.

  7. Aging Degradation of Austenitic Stainless Steel Weld Probed by Electrochemical Method and Impact Toughness Evaluation

    NASA Astrophysics Data System (ADS)

    Singh, Raghuvir; Das, Goutam; Mahato, B.; Singh, P. K.

    2017-03-01

    The present study discriminates the spinodal decomposition and G-phase precipitation in stainless steel welds by double loop electrochemical potentio-kinetic reactivation method and correlates it with the degradation in toughness property. The welds produced with different heat inputs were aged up to 10,000 hours at 673 K to 723 K (400 to 450 °C) and evaluated subsequently for the degree of sensitization (DOS) and impact toughness. The DOS values obtained were attributed to the spinodal decomposition and precipitation of G-phase. Study shows that the DOS correlates well with the impact toughness of the 304LN weld. Prolonged aging at 673 K and 723 K (400 °C and 450 °C) increased the DOS values while the impact toughness was decreased. The weld fabricated at 1 kJ/mm of heat input, produced higher DOS, compared to that at 3 kJ/mm. The geometrical location along the weld is shown to influence the DOS; higher values were obtained at the root than at the topside of the weld. Vermicular and columnar microstructure, in addition to the spinodal decomposition and G-phase precipitation, observed in the root side of the weld appear risky for the impact toughness.

  8. Heterogeneity in polymer solar cells: local morphology and performance in organic photovoltaics studied with scanning probe microscopy.

    PubMed

    Groves, Chris; Reid, Obadiah G; Ginger, David S

    2010-05-18

    The use of organic photovoltaics (OPVs) could reduce production costs for solar cells because these materials are solution processable and can be manufactured by roll-to-roll printing. The nanoscale texture, or film morphology, of the donor/acceptor blends used in most OPVs is a critical variable that can dominate both the performance of new materials being optimized in the lab and efforts to move from laboratory-scale to factory-scale production. Although efficiencies of organic solar cells have improved significantly in recent years, progress in morphology optimization still occurs largely by trial and error, in part because much of our basic understanding of how nanoscale morphology affects the optoelectronic properties of these heterogeneous organic semiconductor films has to be inferred indirectly from macroscopic measurements. In this Account, we review the importance of nanoscale morphology in organic semiconductors and the use of electrical scanning probe microscopy techniques to directly probe the local optoelectronic properties of OPV devices. We have observed local heterogeneity of electronic properties and performance in a wide range of systems, including model polymer-fullerene blends such as poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM), newer polyfluorene copolymer-PCBM blends, and even all polymer donor-acceptor blends. The observed heterogeneity in local photocurrent poses important questions, chiefly what information is contained and what is lost when using average values obtained from conventional measurements on macroscopic devices and bulk samples? We show that in many cases OPVs are best thought of as a collection of nanoscopic photodiodes connected in parallel, each with their own morphological and therefore electronic and optical properties. This local heterogeneity forces us to carefully consider the adequacy of describing OPVs solely by "average" properties such as the bulk carrier mobility

  9. Evaluating Atmospheric pressure Solids Analysis Probe (ASAP) mass spectrometry for the analysis of low molecular weight synthetic polymers.

    PubMed

    Smith, Michael J P; Cameron, Neil R; Mosely, Jackie A

    2012-10-07

    Atmospheric pressure Solids Analysis Probe (ASAP) mass spectrometry has facilitated the ionisation of oligomers from low molecular weight synthetic polymers, poly(ethylene glycol) (PEG: M(n) = 1430) and poly(styrene) (PS: M(n) = 1770), directly from solids, providing a fast and efficient method of identification. Ion source conditions were evaluated and it was found that the key instrument parameter was the ion source desolvation temperature which, when set to 600 °C was sufficient to vapourise the heavier oligomers for ionisation. PS, a non-polar polymer that is very challenging to analyse by MALDI or ESI without the aid of metal salts to promote cationisation, was ionised promptly by ASAP resulting in the production of radical cations. A small degree of in-source dissociation could be eliminated by control of the instrument ion source voltages. The fragmentation observed through in-source dissociation could be duplicated in a controlled manner through Collision-Induced Dissociation (CID) of the radical cations. PEG, which preferentially ionises through adduction with alkali metal cations in MALDI and ESI, was observed as a protonated molecular ion by ASAP. In-source dissociation could not be eliminated entirely and the fragmentation observed resulted from cleavage of the C-C and C-O backbone bonds, as opposed to only C-O bond cleavage observed from tandem mass spectrometry.

  10. Modeling of degradation effects considering side reactions for a pouch type Li-ion polymer battery with carbon anode

    NASA Astrophysics Data System (ADS)

    Fu, Rujian; Choe, Song-Yul; Agubra, Victor; Fergus, Jeffrey

    2014-09-01

    When a lithium ion polymer battery (LiPB) is being cycled, one major cause for degradations is the irreversible side reactions between ions and solvent of electrolyte taking place at the surface of anode particles. SEM analysis of cycled battery cells has revealed that the deposits from the side reactions are dispersed not only on particles, but also between the composite anode and the separator. Thus, the solid electrolyte interface (SEI) becomes thicker and extra deposit layers are formed between composite anode and separator. Also, XPS analysis showed that the deposits are composed of Li2CO3, which is ionic conductive and electronic nonconductive. Based on the mechanisms and findings, we identified four degradation parameters, including volume fraction of accessible active anode, SEI resistance, resistance of deposit layer and diffusion coefficient of electrolyte, to describe capacity and power fade caused by the side reactions. These degradation parameters have been incorporated into an electrochemical thermal model that has been previously developed. The terminal voltage and capacity of the integrated model are compared with experimental data obtained for up to 300 cycles. Finally, the resistance of the deposit layer calculated by the model is validated against the thickness of the deposit layer measured by SEM.

  11. Impact of biofibers and coupling agents on the weathering characteristics of composites polymer degradation and stability

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This paper explores the ultraviolet (UV) weathering performance of high density polyethylene (HDPE) composites with different biofiber fillers and coupling agent. Biofiber polymer composite (BFPC) material samples were prepared using oak, cotton burr and stem (CBS) or guayule bagasse as fiber source...

  12. Rapid, Efficient and Versatile Strategies for Functionally Sophisticated Polymers and Nanoparticles: Degradable Polyphosphoesters and Anisotropic Distribution of Chemical Functionalities

    NASA Astrophysics Data System (ADS)

    Zhang, Shiyi

    The overall emphasis of this dissertation research included two kinds of asymmetrically-functionalized nanoparticles with anisotropic distributions of chemical functionalities, three degradable polymers synthesized by organocatalyzed ring-opening polymerizations, and two polyphosphoester-based nanoparticle systems for various biomedical applications. Inspired by the many hierarchical assembly processes that afford complex materials in Nature, the construction of asymmetrically-functionalized nanoparticles with efficient surface chemistries and the directional organization of those building blocks into complex structures have attracted much attention. The first method generated a Janus-faced polymer nanoparticle that presented two orthogonally click-reactive surface chemistries, thiol and azido. This robust method involved reactive functional group transfer by templating against gold nanoparticle substrates. The second method produced nanoparticles with sandwich-like distribution of crown ether functionalities through a stepwise self-assembly process that utilized crown ether-ammonium supramolecular interactions to mediate inter-particle association and the local intra-particle phase separation of unlike hydrophobic polymers. With the goal to improve the efficiency of the production of degradable polymers with tunable chemical and physical properties, a new type of reactive polyphosphoester was synthesized bearing alkynyl groups by an organocatalyzed ring-opening polymerization, the chemical availability of the alkyne groups was investigated by employing "click" type azide-alkyne Huisgen cycloaddition and thiol-yne radical-mediated reactions. Based on this alkyne-functionalized polyphosphoester polymer and its two available "click" type reactions, two degradable nanoparticle systems were developed. To develop the first system, the well defined poly(ethylene oxide)-block-polyphosphester diblock copolymer was transformed into a multifunctional Paclitaxel drug

  13. Biocompatible photoresistant far-red emitting, fluorescent polymer probes, with near-infrared two-photon absorption, for living cell and zebrafish embryo imaging.

    PubMed

    Adjili, Salim; Favier, Arnaud; Fargier, Guillaume; Thomas, Audrey; Massin, Julien; Monier, Karine; Favard, Cyril; Vanbelle, Christophe; Bruneau, Sylvia; Peyriéras, Nadine; Andraud, Chantal; Muriaux, Delphine; Charreyre, Marie-Thérèse

    2015-04-01

    Exogenous probes with far-red or near-infrared (NIR) two-photon absorption and fluorescence emission are highly desirable for deep tissue imaging while limiting autofluorescence. However, molecular probes exhibiting such properties are often hydrophobic. As an attractive alternative, we synthesized water-soluble polymer probes carrying multiple far-red fluorophores and demonstrated here their potential for live cell and zebrafish embryo imaging. First, at concentrations up to 10 μm, these polymer probes were not cytotoxic. They could efficiently label living HeLa cells, T lymphocytes and neurons at an optimal concentration of 0.5 μm. Moreover, they exhibited a high resistance to photobleaching in usual microscopy conditions. In addition, these polymer probes could be successfully used for in toto labeling and in vivo two-photon microscopy imaging of developing zebrafish embryos, with remarkable properties in terms of biocompatibility, internalization, diffusion, stability and wavelength emission range. The near-infrared two-photon absorption peak at 910 nm is particularly interesting since it does not excite the zebrafish endogenous fluorescence and is likely to enable long-term time-lapse imaging with limited photodamage.

  14. Enumeration of polysaccharide-degrading Bacteroides species in human feces by using species-specific DNA probes.

    PubMed Central

    Kuritza, A P; Shaughnessy, P; Salyers, A A

    1986-01-01

    DNA probes that are specific for each of five predominant species of human colonic Bacteroides (B. thetaiotaomicron, B. uniformis, B. distasonis, "Bacteroides group 3452-A", and B. ovatus) were used to detect and enumerate these species in fecal samples from two adult volunteers. These five species are capable of fermenting many of the complex polysaccharides that are thought to be sources of carbon and energy for bacteria in the colon. Estimates for the concentrations of some of these species in feces have not been previously available because of the difficulties in differentiating colonic Bacteroides spp. by conventional biochemical tests. Our results indicate that all the species except B. ovatus were present in high numbers (greater than 10(9)/g [dry weight]) in the feces of both volunteers. However, the concentrations of the more versatile polysaccharide-degrading species within this group of organisms (7.6 X 10(9) to 12.0 X 10(9)/g [dry weight] for B. thetaiotaomicron; 2.9 X 10(9) to 6.3 X 10(9)/g [dry weight] for "Bacteroides group 3452-A") did not differ significantly from the concentrations of less versatile polysaccharide-degrading species (1.2 X 10(10) to 2.0 X 10(10)/g [dry weight] for B. uniformis; 5.8 X 10(9) to 8.4 X 10(9)/g [dry weight] for B. distasonis). B. ovatus was not detectable by our method. Since our lower limit of detection is approximately 1 X 10(9) to 2 X 10(9)/g (dry weight) of feces, this is consistent with earlier estimates that indicated that the concentration of B. ovatus in feces is near or below this value.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:3954350

  15. Enumeration of polysaccharide-degrading Bacteroides species in human feces by using species-specific DNA probes.

    PubMed

    Kuritza, A P; Shaughnessy, P; Salyers, A A

    1986-02-01

    DNA probes that are specific for each of five predominant species of human colonic Bacteroides (B. thetaiotaomicron, B. uniformis, B. distasonis, "Bacteroides group 3452-A", and B. ovatus) were used to detect and enumerate these species in fecal samples from two adult volunteers. These five species are capable of fermenting many of the complex polysaccharides that are thought to be sources of carbon and energy for bacteria in the colon. Estimates for the concentrations of some of these species in feces have not been previously available because of the difficulties in differentiating colonic Bacteroides spp. by conventional biochemical tests. Our results indicate that all the species except B. ovatus were present in high numbers (greater than 10(9)/g [dry weight]) in the feces of both volunteers. However, the concentrations of the more versatile polysaccharide-degrading species within this group of organisms (7.6 X 10(9) to 12.0 X 10(9)/g [dry weight] for B. thetaiotaomicron; 2.9 X 10(9) to 6.3 X 10(9)/g [dry weight] for "Bacteroides group 3452-A") did not differ significantly from the concentrations of less versatile polysaccharide-degrading species (1.2 X 10(10) to 2.0 X 10(10)/g [dry weight] for B. uniformis; 5.8 X 10(9) to 8.4 X 10(9)/g [dry weight] for B. distasonis). B. ovatus was not detectable by our method. Since our lower limit of detection is approximately 1 X 10(9) to 2 X 10(9)/g (dry weight) of feces, this is consistent with earlier estimates that indicated that the concentration of B. ovatus in feces is near or below this value.(ABSTRACT TRUNCATED AT 250 WORDS)

  16. Polymers.

    ERIC Educational Resources Information Center

    Tucker, David C.

    1986-01-01

    Presents an open-ended experiment which has students exploring polymer chemistry and reverse osmosis. This activity involves construction of a polymer membrane, use of it in a simple osmosis experiment, and application of its principles in solving a science-technology-society problem. (ML)

  17. Experimental and modeling approaches for the formation of hydroperoxide during the auto-oxidation of polymers: Thermal-oxidative degradation of polyethylene oxide

    NASA Astrophysics Data System (ADS)

    Chen, Liang; Yamane, Shogo; Sago, Tomohiro; Hagihara, Hideaki; Kutsuna, Shuzo; Uchimaru, Tadafumi; Suda, Hiroyuki; Sato, Hiroaki; Mizukado, Junji

    2016-07-01

    ROOH was a key intermediate compound in oxidation of polymer because it was only source of radOH radicals. ROOH was believed to be produced by ROOrad abstraction H-atom from polymer, which is thermodynamically unfavorable, but it may be facilitated due to the high polymer concentration. However, ROOH also could be produced by ROOrad reaction with HO2rad. For examining the formation scheme of ROOH, kinetics and mechanism for the thermal-oxidative degradation of PEO at 473 K in air was investigated by using the experimental and modeling approaches. The contribution of HO2rad reaction with ROOrad to the formation of ROOH was estimated.

  18. Probing surface adhesion forces of Enterococcus faecalis to medical-grade polymers using atomic force microscopy.

    PubMed

    Sénéchal, Annie; Carrigan, Shawn D; Tabrizian, Maryam

    2004-05-11

    The aim of this study was to compare the initial adhesion forces of the uropathogen Enterococcus faecalis with the medical-grade polymers polyurethane (PU), polyamide (PA), and poly(tetrafluoroethylene) (PTFE). To quantify the cell-substrate adhesion forces, a method was developed using atomic force microscopy (AFM) in liquid that allows for the detachment of individual live cells from a polymeric surface through the application of increasing force using unmodified cantilever tips. Results show that the lateral force required to detach E. faecalis cells from a substrate differed depending on the nature of the polymeric surface: a force of 19 +/- 4 nN was required to detach cells from PU, 6 +/- 4 nN from PA, and 0.7 +/- 0.3 nN from PTFE. Among the unfluorinated polymers (PU and PA), surface wettability was inversely proportional to the strength of adhesion. AFM images also demonstrated qualitative differences in bacterial adhesion; PU was covered by clusters of cells with few cell singlets present, whereas PA was predominantly covered by individual cells. Moreover, extracellular material could be observed on some clusters of PU-adhered cells as well as in the adjacent region surrounding cells adhered on PA. E. faecalis adhesion to the fluorinated polymer (PTFE) showed different characteristics; only a few individual cells were found, and bacteria were easily damaged, and thus detached, by the tip. This work demonstrates the utility of AFM for measurement of cell-substrate lateral adhesion forces and the contribution these forces make toward understanding the initial stages of bacterial adhesion. Further, it suggests that initial adhesion can be controlled, through appropriate biomaterial design, to prevent subsequent formation of aggregates and biofilms.

  19. Exploiting fluorescent polymers to probe the self-assembly of virus-like particles.

    PubMed

    Cadena-Nava, Ruben D; Hu, Yufang; Garmann, Rees F; Ng, Benny; Zelikin, Alexander N; Knobler, Charles M; Gelbart, William M

    2011-03-17

    The inside surfaces of the protein shells of many viruses are positively charged, thereby enhancing the self-assembly of capsid proteins around their (oppositely charged) RNA genome. These proteins have been shown to organize similarly around a variety of nonbiological, negatively charged, polymers, for example, poly(styrene sulfonate) (PSS), forming virus-like particles (VLPs). We have demonstrated recently that the VLPs formed from cowpea chlorotic mottle virus (CCMV) capsid protein increase in size (from T=2 to T=3 structures) upon increase in PSS molecular weight (from 400 kDa to 3.4 MDa), and that the total charge on the PSS exceeds that of the capsid protein by as much as a factor of 9. Here, we extend studies of this kind to PSS molecules that are sufficiently small that two or more can be packaged into VLPs. The use of 38 kDa PSS polymers that have been fluorescently labeled with Rhodamine B allows us to determine the number of PSS molecules per capsid. Electron micrographs of the VLPs show a bimodal distribution of particle diameters, with one peak centered around 19 nm, typical of a T=1 triangulation number, and the other around 21 nm, consistent with a pseudo T=2 structure; increasing the molar ratio of protein to PSS in the reaction mix shifts the VLP distribution from T=1 to T=2 structures. By combining fluorescence and gel electrophoresis measurements, it is determined that, on average, there are two polymers in each T=1 capsid and three in each T=2, with the PSS charge less than that of the capsid protein by as much as a factor of 2. VLPs of this kind provide a versatile model system for determining the principles underlying self-assembly of controlled numbers of cargo molecules in nanocontainers of increasing size.

  20. Investigation of Oxidative Degradation in Polymers Using (17)O NMR Spectroscopy

    SciTech Connect

    Alam, Todd M.; Celina, Mathew; Assink, Roger A.; Clough, Roger L.; Gillen, Kenneth T.; Wheeler David R.

    1999-07-20

    The thermal oxidation of pentacontane (C{sub 50}H{sub 102}), and of the homopolymer polyisoprene, has been investigated using {sup 17}O NMR spectroscopy. By performing the oxidation using {sup 17}O labeled O{sub 2} gas, it is possible to easily identify degradation products, even at relatively low concentrations. It is demonstrated that details of the degradation mechanism can be obtained from analysis of the {sup 17}O NMR spectra as a function of total oxidation. Pentacontane reveals the widest variety of reaction products, and exhibits changes in the relative product distributions with increasing O{sub 2} consumption. At low levels of oxygen incorporation, peroxides are the major oxidation product, while at later stages of degradation these species are replaced by increasing concentrations of ketones, alcohols, carboxylic acids and esters. Analyzing the product distribution can help in identification of the different free-radical decomposition pathways of hydroperoxides, including recombination, proton abstraction and chain scission, as well as secondary reactions. The {sup 17}O NMR spectra of thermally oxidized polyisoprene reveal fewer degradation functionalities, but exhibit an increased complexity in the type of observed degradation species due to structural features such as unsaturation and methyl branching. Alcohols and ethers formed from hydrogen abstraction and free radical termination.

  1. Probing photocurrent generation mechanisms in hybrid IR-senstive quantum dot/conjugated polymer solar cells

    NASA Astrophysics Data System (ADS)

    Strein, Elisabeth

    The work in this dissertation aims to improve the ability of hybrid polymer/quantum dot solar cells to harvest and utilize sunlight by contributing mechanistic insights into photocurrent generation. The mechanisms of charge transfer and energy transfer are explored spectroscopically in chapter three and both are found to contribute to photocurrent. Chapter four looks at excitation energy in excess of the bandgap and finds a rise in polaron yield which correlates with excess photon energy. Chapter two discusses details of the experimental techniques used to access the data discussed in the chapters that follow.

  2. Positron Annihilation Spectroscopy as a Probe of Microscopic Structure and Physical Aging in Polymer.

    NASA Astrophysics Data System (ADS)

    Yu, Minzi

    Positron annihilation is studied as a characterization method for the properties of polymers. Previous studies indicate that the ortho-positronium lifetime tau _3 and intensity I_3 is correlated to the free volume "hole" size and number density of holes in a polymer. Positron annihilation lifetime (PAL) studies in polymers measure the change in free volume, and they are sensitive to different physical environments. PAL studies of the temperature dependence of a bisphenol-A polycarbonate shows that the free volume increases with increasing temperature, and it also obtains the transition temperatures T_{rm g} and T_beta^', from the tau_3 curve and the I_3 curve, respectively. The isothermal aging in polycarbonate shows that: I_3 decreases while tau_3 remains constant during a long-time annealing at a temperature far below T_{rm g}; and I_3 remains constant while tau_3 goes through a "over shooting" in the first few hours after quenching and annealing at a temperature just below T_{rm g}. The free volume in polycarbonate increases (as a result of an increase in tau_3 ) with applied tensile strain up to 4%, then levels off. Similarly, the free volume in polymethyl methacrylate (PMMA) decreases (as the result of tau_3 ) with applied compressional strain also up to -4% then levels off. A negative change in both tau_3 and I _3 has been observed when polycarbonate is under 3% tensile strain and after release of strain. A more advance technique of positron annihilation, PAL-momentum correlation which can give more detailed information about free volume structure in polymers, has also been studied and improved. Two 5-cm-diameter, 5-cm-long CsF scintillation detectors for lifetime measurement, and a 30-cm-diameter Anger camera whose y-analog pulse gives one-dimensional ACAR information, comprise a new experimental arrangement of PAL-momentum correlation system. Its triple -coincidence counting rate is about 2.5 per minute per microcurie of positron source and system time

  3. Fluorescence pH probe based on microstructured polymer optical fiber.

    PubMed

    Yang, X H; Wang, L L

    2007-12-10

    A kind of optical pH sensor was demonstrated that is based on a pH-sensitive fluorescence dye-doped (eosin) cellulose acetate (CA) thin-film modified microstructured polymer optical fiber (MPOF). It was obtained by directly inhaling an eosin-CA-acetic acid mixed solution into array holes in a MPOF and then removing the solvent (acetic acid). The sensing film showed different fluorescence intensities to different pH solutions in a pH range of 2.5-4.5. Furthermore, the pH response range could be tailored through doping a surfactant, hexadecyl trimethyl ammonium bromide (CTAB), in the sensing film.

  4. One-pot synthesis of ZnS/polymer composites in supercritical CO2-ethanol solution and their applications in degradation of dyes.

    PubMed

    Xie, Yun; Zhang, Chengliang; Miao, Shiding; Liu, Zhimin; Ding, Kunlun; Miao, Zhenjiang; An, Guimin; Yang, Zhenzhong

    2008-02-01

    A facile method to decorate the polymeric hollow spheres with ZnS nanoparticles has been presented. In this method, the precursors, Zn(Ac)(2)H(2)O and CH(3)CSNH(2), were first adsorbed by the polymer substrate in supercritical CO(2)-ethanol solution at 35 degrees C. Followed by heating the mixture at 100 degrees C for 2 h, ZnS/polymer composites were obtained. The as-produced ZnS/polymer composites were characterized by means of IR spectra, X-ray diffraction, transmission electron microscopy, high-resolution transmission electron microscopy. It was demonstrated that crystalline ZnS nanoparticles with size of 3-5 nm were uniformly decorated on the polymer spheres under suitable conditions. The resultant ZnS/polymer composites exhibited high efficiency for degrading eosin B, methyl orange and methylene blue under UV light irradiation.

  5. Investigation of the Thermal Degradation of Alkyl isocyanate Polymers by Direct Pyrolysis Mass Spectroscopy

    DTIC Science & Technology

    1988-09-20

    attributed to an EI fragment originating from the isocya- nurate. Both the TIC curve and TGA analysis show that complete decompo- 4’. 0’ sition of this...contrast, the TGA analysis shows that 0J. complete decomposition is delayed until -450 C. This difference is attributed to the high vacuum conditions...the polymer are removed at lower temperature than in the TGA analysis . The TIC curve clearly shows a peak with three sharp maxima appearing at

  6. 16S rDNA-based probes for two polycyclic aromatic hydrocarbon (PAH)-degrading soil Mycobacteria

    SciTech Connect

    Govindaswami, M.; Feldhake, D.J.; Loper, J.C.

    1994-12-31

    PAHs are a class of widespread pollutants, some of which have been shown to be genotoxic, hence the fate of these compounds in the environment is of considerable interest. Research on the biodegradation of 4 and 5 ring PAHs has been limited by the general lack of microbial isolates or consortia which can completely degrade these toxicants. Heitkamp and Cerniglia have described an oxidative soil Mycobacterium-strain PYR-1 that metabolizes pyrene and fluoranthene more rapidly than the 2 and 3 ring naphthalene and phenanthrene; although some metabolites of benzo-(a)-pyrene (BaP) were detected, no mineralization of BaP was observed. In 1991 Grosser et al. reported the isolation of a Mycobacterium sp. which mineralizes pyrene and also causing some mineralization of BaP. Their study describes a comparative analysis of these two strains, which show very similar colony morphology, growth rate and yellow-orange pigmentation. Genetic differences were shown by DNA amplification fingerprinting (DAF) using two arbitrary GC-rich octanucleotide primers, and by sequence comparison of PCR amplified 16S rDNA, although both strains show similarity closest to that of the genus Mycobacteria. These 16S rDNA sequences are in use for the construction of strain-specific DNA probes to monitor the presence, survival and growth of these isolates in PAH-contaminated soils in studies of biodegradation.

  7. The key microorganisms for anaerobic degradation of pentachlorophenol in paddy soil as revealed by stable isotope probing.

    PubMed

    Tong, Hui; Liu, Chengshuai; Li, Fangbai; Luo, Chunling; Chen, Manjia; Hu, Min

    2015-11-15

    Pentachlorophenol (PCP) is a common residual persistent pesticide in paddy soil and has resulted in harmful effect on soil ecosystem. The anaerobic microbial transformation of PCP, therefore, has been received much attentions, especially the functional microbial communities for the reductive transformation. However, the key functional microorganisms for PCP mineralization in the paddy soil still remain unknown. In this work, DNA-based stable isotope probing (SIP) was applied to explore the key microorganisms responsible for PCP mineralization in paddy soil. The SIP results indicated that the dominant bacteria responsible for PCP biodegradation belonged to the genus Dechloromonas of the class β-Proteobacteria. In addition, the increased production of (13)CH4 and (13)CO2 indicated that the addition of lactate enhanced the rate of biodegradation and mineralization of PCP. Two archaea classified as the genera of Methanosaeta and Methanocella of class Methanobacteria were enriched in the heavy fraction when with lactate, whereas no archaea was detected in the absence of lactate. These findings provide direct evidence for the species of bacteria and archaea responsible for anaerobic PCP or its breakdown products mineralization and reveal a new insight into the microorganisms linked with PCP degradation in paddy soil.

  8. Nanostructured fluids from degradable nonionic surfactants for the cleaning of works of art from polymer contaminants.

    PubMed

    Baglioni, M; Raudino, M; Berti, D; Keiderling, U; Bordes, R; Holmberg, K; Baglioni, P

    2014-09-21

    Nanostructured fluids containing anionic surfactants are among the best performing systems for the cleaning of works of art. Though efficient, their application may result in the formation of a precipitate, due to the combination with divalent cations that might leach out from the artifact. We propose here two new aqueous formulations based on nonionic surfactants, which are non-toxic, readily biodegradable and insensitive to the presence of divalent ions. The cleaning properties of water-nonionic surfactant-2-butanone (MEK) were assessed both on model surfaces and on a XIII century fresco that could not be cleaned using conventional methods. Structural information on nanofluids has been gathered by means of small-angle neutron scattering, dynamic light scattering and nuclear magnetic resonance with diffusion monitoring. Beside the above-mentioned advantages, these formulations turned out to be considerably more efficient in the removal of polymer coatings than those based on anionic surfactants. Our results indicate that the cleaning process most likely consists of two steps: initially, the polymer film is swollen by the MEK dissolved in the continuous domain of the nanofluid; in the second stage, surfactant aggregates come into play by promoting the removal of the polymer film with a detergency-like mechanism. The efficiency can be tuned by the composition and nature of amphiphiles and is promoted by working as close as possible to the cloud point of the formulation, where the second step proceeds at maximum rate.

  9. Mechanisms of degradation in adhesive joint strength: Glassy polymer thermoset bond in a humid environment

    DOE PAGES

    Kropka, Jamie Michael; Adolf, Douglas Brian; Spangler, Scott Wilmer; ...

    2015-08-06

    The degradation in the strength of napkin-ring (NR) joints bonded with an epoxy thermoset is evaluated in a humid environment. While adherend composition (stainless steel and aluminum) and surface preparation (polished, grit blasted, primed, coupling agent coated) do not affect virgin (time=0) joint strength, they can significantly affect the role of moisture on the strength of the joint. Adherend surface abrasion and corrosion processes are found to be key factors in determining the reliability of joint strength in humid environments. In cases where surface specific joint strength degradation processes are not active, decreases in joint strength can be accounted formore » by the glass transition temperature, Tg, depression of the adhesive associated with water sorption. Under these conditions, joint strength can be rejuvenated to virgin strength by drying. In addition, the decrease in joint strength associated with water sorption can be predicted by the Simplified Potential Energy Clock (SPEC) model by shifting the adhesive reference temperature, Tref, by the same amount as the Tg depression. When surface specific degradation mechanisms are active, they can reduce joint strength below that associated with adhesive Tg depression, and joint strength is not recoverable by drying. Furthermore, a critical relative humidity (or, potentially, critical water sorption concentration), below which the surface specific degradation does not occur, appears to exist for the polished stainless steel joints.« less

  10. Mechanisms of degradation in adhesive joint strength: Glassy polymer thermoset bond in a humid environment

    SciTech Connect

    Kropka, Jamie Michael; Adolf, Douglas Brian; Spangler, Scott Wilmer; Austin, Kevin N.; Chambers, Robert S.

    2015-08-06

    The degradation in the strength of napkin-ring (NR) joints bonded with an epoxy thermoset is evaluated in a humid environment. While adherend composition (stainless steel and aluminum) and surface preparation (polished, grit blasted, primed, coupling agent coated) do not affect virgin (time=0) joint strength, they can significantly affect the role of moisture on the strength of the joint. Adherend surface abrasion and corrosion processes are found to be key factors in determining the reliability of joint strength in humid environments. In cases where surface specific joint strength degradation processes are not active, decreases in joint strength can be accounted for by the glass transition temperature, Tg, depression of the adhesive associated with water sorption. Under these conditions, joint strength can be rejuvenated to virgin strength by drying. In addition, the decrease in joint strength associated with water sorption can be predicted by the Simplified Potential Energy Clock (SPEC) model by shifting the adhesive reference temperature, Tref, by the same amount as the Tg depression. When surface specific degradation mechanisms are active, they can reduce joint strength below that associated with adhesive Tg depression, and joint strength is not recoverable by drying. Furthermore, a critical relative humidity (or, potentially, critical water sorption concentration), below which the surface specific degradation does not occur, appears to exist for the polished stainless steel joints.

  11. Regulation of coal polymer degradation by fungi. Fourth quarterly progress report, May 1995--June 1995

    SciTech Connect

    Irvine, R.L.

    1995-07-24

    To test the hypothesis that coal (leonardite) Solubilization and the subsequent depolymerization of the solubilized coal macromolecules are distinct events in lignin degrading fungi. In addition to T versicolor, Phanerochaete chrysosporium, another lignin degrading fungus that also has the ability to solubilize coal, will be studied. To test the hypothesis that the processes of coal (leonardite) solubilization and coal macro molecule depolymerization in lignin degrading fungi can be regulated by altering the nutritional status of the microorganism. Coal solubilization is expected to occur in nutrient rich media whereas depolymerization of solubilized coal macromolecules is expected to occur in nutrient limited media. To determine the role of extracellular enzymes (laccases, lignin peroxidases and Mn peroxidases) that are secreted by lignin degrading fungi during coal solubilization or coal macro molecule depolymerization. To assess the role of enzymatically generated oxygen radicals, non-radical active oxygen species, veratryl alcohol radicals and Mn{sup +++} complexes in coal macro molecule depolymerization. To characterize products of coal solubilization and coal macro molecule depolymerization that are formed by T. versicolor and P. chrysosporium and their respective extracellular enzymes. Solubilization products formed using oxalic acid and other metal chelators will also be characterized and compared.

  12. Relationships between structure and rheology in polymer nanocomposites probed via X-ray scattering

    NASA Astrophysics Data System (ADS)

    Pujari, Saswati

    Polymer nanocomposites have received intense attention due to their potential for significantly enhanced polymer properties like mechanical strength, thermal stability, electrical conductivity, etc. Melt state processing of these materials exposes the nanofillers to complex flow fields, which can induce changes in nanocomposite microstructure, including particle dispersion and the orientation of anisotropic nanoparticles in the polymer matrix. Since nanocomposite properties are strongly correlated with both these structural features, it is essential to develop methods to characterize such microstructural changes. This thesis reports extensive measurements of mechanical rheology and particle orientation during flow of nanocomposites based on multi-walled carbon nanotubes, clays, and graphene nanosheets. Changes in orientation of anisotropic nanoparticles are manifested in x-ray scattering images collected during shear. In-situ studies of orientation are enabled by custom designed x-ray adapted shear cells and high energy synchrotron radiation at the Advanced Photon Source in Argonne National Laboratory where these experiments were conducted. Studies of flow induced orientation in model nanotube dispersions revealed increasing sample anisotropy with increasing shear rate across concentrations and aspect ratios. In dilute dispersions the orientation dynamics was dominated by flow induced aggregation/disaggregation of MWNTs, with anisotropy primarily attributed to individually dispersed nanotubes. In concentrated suspensions, sample anisotropy resulted from flow induced elastic deformation within entangled MWNT clusters. Release of elastic energy upon flow cessation resulted in an unexpected relaxation of induced anisotropy. These studies were followed with study of more complex, but, industrially relevant nanocomposites made with polypropylene as the dispersing matrix. The high viscosity of polypropylene makes dispersion of nanoparticles difficult, and hence a careful

  13. Probing Nonlinear Viscoelasticity of Polymer Melts by Medium Amplitude Oscillatory Shear (MAOS)

    NASA Astrophysics Data System (ADS)

    Wagner, Manfred H.; Rolón-Garrido, Víctor Hugo

    2011-07-01

    MAOS is shown to be a powerful tool to investigate the inception of nonlinear viscoelasticity of polymer melts. A constitutive analysis based on a general single integral constitutive equation, which includes the Doi-Edwards model without (DE) and with independent alignment assumption (DE IA) as well as the molecular stress function (MSF) model, confirms two important scaling relations found experimentally by Hyun and Wilhelm: (1) The relative intensity of the 3rd harmonic compared to the 1st harmonic scales with the square of the strain amplitude according. Consequently, a new nonlinear coefficient, the so-called intrinsic nonlinearity was introduced. (2) In the terminal relaxation regime, the intrinsic nonlinearity scales with the square of the angular frequency, and was found to be a very sensitive measure regarding molecular topology by identifying and separating relaxation processes in model branched polymers. We show that the nonlinear viscoelastic moduli can be expressed as sums of their linear-viscolelastic counterparts at angular frequencies of ω, 2ω, and 3ω. The absolute value of the intrinsic nonlinearity depends on the difference (α-β) between the 3rd order orientational effect (parameter α) according to the DE or DE IA model and the 2nd order isotropic stretching effect (parameter β) according to the MSF model. The measured apparent values of the intrinsic nonlinearity measured in parallel-plate geometry are rescaled in order to take the non-uniform shear deformation into account, and are compared to constitutive models. While both the DE and DE IA model fail to describe the experimental data, the data of linear and comb-like PS melts are quantitatively described by the MSF model. However, the model predicts a plateau at the level of the maximum of the experimental data, while for comb polymers with entangled branches, a minimum in the intrinsic nonlinearity is observed, followed by a second increase of the intrinsic nonlinearity at higher

  14. Local Electronic Characterization of Conjugated Polymer Films using Conducting-Probe Atomic Force Microscopy

    NASA Astrophysics Data System (ADS)

    O'Brien, G.; Quinn, A. J.; Redmond, G.

    2004-03-01

    Correlation of local electronic properties with film morphology is a key challenge to be addressed in order to understand (and therefore control) charge injection, transport and recombination in organic electronic devices. We present a flexible method, Conducting-Probe Atomic Force Microscopy (CP-AFM), which can be used as a local probe of both film morphology and spectroscopy. MEH-PPV layers with thickness values comparable to films used in organic electronic devices (60 nm) are spun onto gold substrates under inert conditions. Tip-height vs bias voltage (z-V) sweeps taken at constant tunnel current (50 pA) show clear charge injection thresholds at both positive and negative bias (E_+,E_-). Statistical analysis of measured single-particle gap energies, E_gsp=E_+-E_-, reveals a distribution across the surface with peaks corresponding to (extracted) exciton binding energies of 100 meV and 400 meV respectively. Analysis of measured E_gsp values for films prepared under ambient conditions show a large density of mid-gap states confirming that the preparation route is critical for organic electronic devices.

  15. Probing proton dissociation in ionic polymers by means of in situ ATR-FTIR spectroscopy.

    PubMed

    Grosmaire, Lidwine; Castagnoni, Samuel; Huguet, Patrice; Sistat, Philippe; Boucher, Mario; Bouchard, Patrick; Bébin, Philippe; Deabate, Stefano

    2008-03-21

    The hydration process of cationic membrane protogenic groups was investigated using in situ ATR-FTIR spectroscopy. The aim of this study is to provide a relationship between the hydration degree of the membrane and the dissociation state of exchange sites inside the polymer material. IR spectra were recorded by means of an environmental device specifically manufactured to allow the control of water vapour pressure in equilibrium with the sample. The behaviour of Nafion 112 and sulfonated poly(ether ether ketone) (S-PEEK), in both proton and sodium forms, was compared. IR data, analyzed and fitted in the 800-1850 cm(-1) spectral range, gave precise information on the assignment of sulfonic group vibrational modes. The results of this study improve the understanding of the transition phenomena between dissociated and undissociated states of the grafted sites in protonic conductors.

  16. Probing the Mucoadhesive Interactions Between Porcine Gastric Mucin and Some Water-Soluble Polymers.

    PubMed

    Albarkah, Yasser A; Green, Rebecca J; Khutoryanskiy, Vitaliy V

    2015-11-01

    This study investigates the structural features of porcine gastric mucin (PGM) in aqueous dispersions and its interactions with water-soluble polymers (poly(acrylic acid) (PAA), poly(methacrylic acid) (PMAA), poly(ethylene oxide), and poly(ethylene glycol)) using isothermal titration calorimetry, turbidimetric titration, dynamic light scattering, and transmission electron microscopy. It is established that PAA (450 kDa) and PMAA (100 kDa) exhibit strong specific interactions with PGM causing further aggregation of its particles, while PAA (2 kDa), poly(ethylene oxide) (1 000 kDa), and poly(ethylene glycol) (10 kDa) do not show any detectable effects on mucin. Sonication of mucin dispersions prior to their mixing with PAA (450 kDa) and PMAA (100 kDa) leads to more pronounced intensity of interactions.

  17. Neutron scattering as a probe of liquid crystal polymer-reinforced composite materials

    SciTech Connect

    Hjelm, R.P.; Douglas, E.P.; Benicewicz, B.C.; Langlois, D.A.

    1995-12-31

    This is the final report of a three-year Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). This research project sought to obtain nanoscale and molecular level information on the mechanism of reinforcement in liquid crystal polymer (LCP)-reinforced composites, to realize molecular-reinforced LCP composites, and to test the validity of the concept of molecular reinforcement. Small-angle neutron scattering was used to study the structures in the ternary phase diagram of LCP with liquid crystal thermosets and solvent on length scales ranging from 1-100 nm. The goal of the scattering measurements is to understand the phase morphology and degree of segregation of the reinforcing and matrix components. This information helps elucidate the physics of self assembly in these systems. This work provides an experimental basis for a microengineering approach to composites of vastly improved properties.

  18. Environmentally Benign CO2-Based Copolymers: Degradable Polycarbonates Derived from Dihydroxybutyric Acid and Their Platinum-Polymer Conjugates.

    PubMed

    Tsai, Fu-Te; Wang, Yanyan; Darensbourg, Donald J

    2016-04-06

    (S)-3,4-Dihydroxybutyric acid ((S)-3,4-DHBA), an endogenous straight chain fatty acid, is a normal human urinary metabolite and can be obtained as a valuable chiral biomass for synthesizing statin-class drugs. Hence, its epoxide derivatives should serve as promising monomers for producing biocompatible polymers via alternating copolymerization with carbon dioxide. In this report, we demonstrate the production of poly(tert-butyl 3,4-dihydroxybutanoate carbonate) from racemic-tert-butyl 3,4-epoxybutanoate (rac-(t)Bu 3,4-EB) and CO2 using bifunctional cobalt(III) salen catalysts. The copolymer exhibited greater than 99% carbonate linkages, 100% head-to-tail regioselectivity, and a glass-transition temperature (Tg) of 37 °C. By way of comparison, the similarly derived polycarbonate from the sterically less congested monomer, methyl 3,4-epoxybutanoate, displayed 91.8% head-to-tail content and a lower Tg of 18 °C. The tert-butyl protecting group of the pendant carboxylate group was removed using trifluoroacetic acid to afford poly(3,4-dihydroxybutyric acid carbonate). Depolymerization of poly(tert-butyl 3,4-dihydroxybutanoate carbonate) in the presence of strong base results in a stepwise unzipping of the polymer chain to yield the corresponding cyclic carbonate. Furthermore, the full degradation of the acetyl-capped poly(potassium 3,4-dihydroxybutyrate carbonate) resulted in formation of the biomasses, β-hydroxy-γ-butyrolacetone and 3,4-dihydroxybutyrate, in water (pH = 8) at 37 °C. In addition, water-soluble platinum-polymer conjugates were synthesized with platinum loading of 21.3-29.5%, suggesting poly(3,4-dihydroxybutyric acid carbonate) and related derivatives may serve as platinum drug delivery carriers.

  19. In situ nanomechanical characterization of the early stages of swelling and degradation of a biodegradable polymer

    NASA Astrophysics Data System (ADS)

    Dumitru, A. C.; Espinosa, F. M.; Garcia, R.; Foschi, G.; Tortorella, S.; Valle, F.; Dallavalle, M.; Zerbetto, F.; Biscarini, F.

    2015-03-01

    The interactions of a biodegradable scaffold with cells or living tissues depend on the time-evolution of the nanoscale properties of the scaffold. We present an in situ quantitative study on the early-stage swelling and degradation of poly(lactic-co-glycolic acid) (PLGA). A novel metrology scheme based on force microscopy measurements of the patterns of PLGA nanostructures is developed to characterize the evolution of topography, volume and nanomechanical properties. The volume and nanoscale roughness show an oscillating behaviour during the first eight days of immersion; at a later stage, we observe a continuous decrease of the volume. The effective Young's modulus exhibits a monotonic decrease from an initial value of about 2.4 GPa down to 9 MPa at day 14. The oscillating behaviour of the volume before the onset of full degradation is explained by a coupled diffusion-swelling mechanism. The appearance of a second maximum in the volume evolution results from the competition between swelling and degradation.The interactions of a biodegradable scaffold with cells or living tissues depend on the time-evolution of the nanoscale properties of the scaffold. We present an in situ quantitative study on the early-stage swelling and degradation of poly(lactic-co-glycolic acid) (PLGA). A novel metrology scheme based on force microscopy measurements of the patterns of PLGA nanostructures is developed to characterize the evolution of topography, volume and nanomechanical properties. The volume and nanoscale roughness show an oscillating behaviour during the first eight days of immersion; at a later stage, we observe a continuous decrease of the volume. The effective Young's modulus exhibits a monotonic decrease from an initial value of about 2.4 GPa down to 9 MPa at day 14. The oscillating behaviour of the volume before the onset of full degradation is explained by a coupled diffusion-swelling mechanism. The appearance of a second maximum in the volume evolution results from

  20. Probing the viscoelastic response of glassy polymer films using atomic force microscopy.

    PubMed

    Yang, Guanwen; Rao, Nanxia; Yin, Zejie; Zhu, Da-Ming

    2006-05-01

    The mechanical properties of glassy films and glass surfaces have been studied using an atomic force microscope (AFM) through various imaging modes and measuring methods. In this paper, we discuss the viscoelastic response of a glassy surface probed using an AFM. We analyzed the force-distance curves measured on a glassy film or a glassy surface at temperatures near the glass transition temperature, Tg, using a Burgers model. We found that the material's characteristics of reversible anelastic response and viscous creep can be extracted from a force-distance curve. Anelastic response shifts the repulsive force-distance curve while viscous creep strongly affects the slope of the repulsive force-distance curve. When coupled with capillary force, due to the condensation of a thin layer of liquid film at the tip-surface joint, the anelasticity and viscous creep can alter the curve significantly in the attractive region.

  1. Evaluation of thermal degradation of polymer based electronic materials by non-destructive testing

    NASA Astrophysics Data System (ADS)

    Rafiee, P.; Khatibi, G.; Lederer, M.; Zehetbauer, M.

    2017-01-01

    Thermal degradation of polymeric materials used in microelectronic packages was studied by means of experimental modal analysis in combination with finite element methods. The devices were subjected to vibrational loads subsequent to various stages of high temperature storage and their modal response was recorded. Statistical methods and finite element analysis were applied to quantify and evaluate the alteration of the modal response of the packages due to the degradation / delamination of the silver filled epoxy adhesive and the glass filled epoxy resin molding compound. It was shown that changes in the material properties of the molding compound due to surface oxidation is the dominant cause for alteration of the modal response of encapsulated packages exposed to high temperatures.

  2. Probing polymer melt structure at the early stages of crystallization by in-situ rheo -SAXS and -WAXD techniques

    NASA Astrophysics Data System (ADS)

    Somani, R. H.; Yang, L.; Hsiao, B. S.; Agarwal, P.; Fruitwala, H.; Tsou, A.

    2002-03-01

    Flow fields strongly affect polymer crystallization, both in terms of phase transition and solid state morphology. Arguments, based on the average properties (such as entropy reduction and related elevation of melting point) of deformed melts does not fully account for high sensitivity of polymer crystallization kinetics to flow and deformation. Local orientation of macromolecular chains and its effect on the primary nucleation step is likely to be the determining phenomenon. In-situ rheo --SAXS (small angle x-ray scattering) and --WAXD (wide angle x-ray diffraction) techniques were used to probe the shear-induced precursor structures (primary nuclei) at the early stages of crystallization in isotactic polypropylene melt near its melting point. Initial SAXS patterns, immediately after shear (rate = 60 s ^--1, ts = 5 s), showed emergence of equatorial streaks due to oriented structures (precursors for microfibrils or shish) parallel to the flow direction and of meridional maxima due to growth of the oriented layer-like structures (precursors for kebabs) perpendicular to the flow; however, no crystal reflections were observed in corresponding WAXD patterns. SAXS and WAXD patterns at later times (t = 120 min after shear) indicated that the induced oriented structures were stable above the nominal melting point of iPP. DSC thermograms of sheared iPP samples confirmed the presence of two populations of crystalline fractions; one at 164 ^oC (corresponding to the normal melting point) and the other at 179 ^oC (corresponding to melting of oriented crystalline structures). \\underline Acknowledgements: We wish to acknowledge the assistance of Drs. Fengji Yeh, Lizhi Liu, Dufei Fang, and Shaofeng Ran of SUNY, Stony Brook for synchrotron SAXS and WAXD experimental setup. The financial support for this work was provided by NSF DMR-9732653 and by ExxonMobil.

  3. Self-reinforced composites of bioabsorbable polymer and bioactive glass with different bioactive glass contents. Part II: In vitro degradation.

    PubMed

    Niemelä, Tiiu; Niiranen, Henna; Kellomäki, Minna

    2008-01-01

    The in vitro degradation behavior of self-reinforced bioactive glass-containing composites was investigated comparatively with plain self-reinforced matrix polymer. The materials used were spherical bioactive glass 13-93 particles, with a particle size distribution of 50-125 microm, as a filler material and bioabsorbable poly-L,DL-lactide 70/30 as a matrix material. The composites containing 0, 20, 30, 40 and 50 wt.% of bioactive glass were manufactured using twin-screw extruder followed by self-reinforcing. The samples studied were characterized determining the changes in mechanical properties, thermal properties, molecular weight, mass loss and water absorption in phosphate-buffered saline at 37 degrees C for up to 104 weeks. The results showed that the bioactive glass addition modified the degradation kinetics and material morphology of the matrix material. It was concluded that the optimal bioactive glass content depends on the applications of the composites. The results of this study could be used as a guideline when estimating the best filler content of other self-reinforced osteoconductive filler containing composites which are manufactured in a similar way.

  4. Bacteria capable of degrading anthracene, phenanthrene, and fluoranthene as revealed by DNA based stable-isotope probing in a forest soil.

    PubMed

    Song, Mengke; Jiang, Longfei; Zhang, Dayi; Luo, Chunling; Wang, Yan; Yu, Zhiqiang; Yin, Hua; Zhang, Gan

    2016-05-05

    Information on microorganisms possessing the ability to metabolize different polycyclic aromatic hydrocarbons (PAHs) in complex environments helps in understanding PAHs behavior in natural environment and developing bioremediation strategies. In the present study, stable-isotope probing (SIP) was applied to investigate degraders of PAHs in a forest soil with the addition of individually (13)C-labeled phenanthrene, anthracene, and fluoranthene. Three distinct phylotypes were identified as the active phenanthrene-, anthracene- and fluoranthene-degrading bacteria. The putative phenanthrene degraders were classified as belonging to the genus Sphingomona. For anthracene, bacteria of the genus Rhodanobacter were the putative degraders, and in the microcosm amended with fluoranthene, the putative degraders were identified as belonging to the phylum Acidobacteria. Our results from DNA-SIP are the first to directly link Rhodanobacter- and Acidobacteria-related bacteria with anthracene and fluoranthene degradation, respectively. The results also illustrate the specificity and diversity of three- and four-ring PAHs degraders in forest soil, contributes to our understanding on natural PAHs biodegradation processes, and also proves the feasibility and practicality of DNA-based SIP for linking functions with identity especially uncultured microorganisms in complex microbial biota.

  5. Stability and Degradation Mechanisms of Radiation-Grafted Polymer Electrolyte Membranes for Water Electrolysis.

    PubMed

    Albert, Albert; Lochner, Tim; Schmidt, Thomas J; Gubler, L

    2016-06-22

    Radiation-grafted membranes are a promising alternative to commercial membranes for water electrolyzers, since they exhibit lower hydrogen crossover and area resistance, better mechanical properties, and are of potentially lower cost than perfluoroalkylsulfonic acid membranes, such as Nafion. Stability is an important factor in view of the expected lifetime of 40 000 h or more of an electrolyzer. In this study, combinations of styrene (St), α-methylstyrene (AMS), acrylonitrile (AN), and 1,3-diisopropenylbenzene (DiPB) are cografted into 50 μm preirradiated poly(ethylene-co-tetrafluoroethylene) (ETFE) base film, followed by sulfonation to produce radiation-grafted membranes. The stability of the membranes with different monomer combinations is compared under an accelerated stress test (AST), and the degradation mechanisms are investigated. To mimic the conditions in an electrolyzer, in which the membrane is always in contact with liquid water at elevated temperature, the membranes are immersed in water for 5 days at 90 °C, so-called thermal stress test (TST). In addition to testing in air atmosphere tests are also carried out under argon to investigate the effect of the absence of oxygen. The water is analyzed with UV-vis spectroscopy and ion chromatography. The ion exchange capacity (IEC), swelling degree, and Fourier transform infrared (FTIR) spectra of the membranes are compared before and after the test. Furthermore, energy-dispersive X-ray (EDX) spectroscopic analysis of the membrane cross-section is performed. Finally, the influence of the TST to the membrane area resistance and hydrogen crossover is measured. The stability increases along the sequence St/AN, St/AN/DiPB, AMS/AN, and AMS/AN/DiPB grafted membrane. The degradation at the weak-link, oxygen-induced degradation, and hydrothermal degradation are proposed in addition to the "swelling-induced detachment" reported in the literature. By mitigating the possible paths of degradation, the AMS

  6. Stabilization of nanosized titanium dioxide by cyclodextrin polymers and its photocatalytic effect on the degradation of wastewater pollutants

    PubMed Central

    Agócs, Tamás Zoltán; Puskás, István; Varga, Erzsébet; Molnár, Mónika

    2016-01-01

    Advanced oxidation processes (AOPs) are considered highly competitive water treatment technologies for the removal of organic pollutants. Among AOP techniques, photocatalysis has recently been the most widely studied. Our aims were to investigate how the dispersion of nanosized titanium dioxide (nanoTiO2) applied in photodegradation-based procedures can be stabilized with cyclodextrins in order to obtain a new, more efficient photocatalyst for the purification of waters polluted by xenobiotics applying UV irradiation. During our work, on the one hand, we studied the behavior and stability of nanoTiO2 in cyclodextrin solutions. On the other hand, we used various monomer and polymer cyclodextrin derivatives, and assessed the options for nanoTiO2 stabilization in the presence of various salts and tap water on the basis of turbidity tests. The physical stability of nanoTiO2 dispersions is diminished in the presence of the salts found in tap water (and occurring also in surface waters and ground water) and they are precipitated immediately. This colloidal instability can be improved by cyclodextrin derivatives. Based on the results of our studies we have selected carboxymethyl β-cyclodextrin polymer (CMBCD-P) for stabilization of nanoTiO2 dispersions. The photocatalytic degradation of methylene blue and ibuprofen as model organic pollutants in various media (distilled water, NaCl solution and tap water) has been studied using nanoTiO2 as catalyst stabilized by CMBCD-P. CMBCD-P itself showed a catalytic effect on the UV degradation of methylene blue. In addition to enhancing the colloid stability of nanoTiO2 CMBCD-P showed also synergistic effects in catalyzing the photodecomposition process of the dye. On the other hand, ibuprofen as a model pharmaceutical, a pollutant of emerging concern (EP), was protected by CMBCD-P against the photocatalytic degradation showing that inclusion complex formation can result in opposite effects depending on the structure of the host

  7. Balancing the Rates of New Bone Formation and Polymer Degradation Enhances Healing of Weight-Bearing Allograft/Polyurethane Composites in Rabbit Femoral Defects

    PubMed Central

    Dumas, Jerald E.; Prieto, Edna M.; Zienkiewicz, Katarzyna J.; Guda, Teja; Wenke, Joseph C.; Bible, Jesse; Holt, Ginger E.

    2014-01-01

    There is a compelling clinical need for bone grafts with initial bone-like mechanical properties that actively remodel for repair of weight-bearing bone defects, such as fractures of the tibial plateau and vertebrae. However, there is a paucity of studies investigating remodeling of weight-bearing bone grafts in preclinical models, and consequently there is limited understanding of the mechanisms by which these grafts remodel in vivo. In this study, we investigated the effects of the rates of new bone formation, matrix resorption, and polymer degradation on healing of settable weight-bearing polyurethane/allograft composites in a rabbit femoral condyle defect model. The grafts induced progressive healing in vivo, as evidenced by an increase in new bone formation, as well as a decrease in residual allograft and polymer from 6 to 12 weeks. However, the mismatch between the rates of autocatalytic polymer degradation and zero-order (independent of time) new bone formation resulted in incomplete healing in the interior of the composite. Augmentation of the grafts with recombinant human bone morphogenetic protein-2 not only increased the rate of new bone formation, but also altered the degradation mechanism of the polymer to approximate a zero-order process. The consequent matching of the rates of new bone formation and polymer degradation resulted in more extensive healing at later time points in all regions of the graft. These observations underscore the importance of balancing the rates of new bone formation and degradation to promote healing of settable weight-bearing bone grafts that maintain bone-like strength, while actively remodeling. PMID:23941405

  8. Use of stable isotope probing to assess the fate of emerging contaminants degraded by white-rot fungus.

    PubMed

    Badia-Fabregat, Marina; Rosell, Mònica; Caminal, Glòria; Vicent, Teresa; Marco-Urrea, Ernest

    2014-05-01

    The widespread of emerging contaminants in the environment and their potential impact on humans is a matter of concern. White-rot fungi are cosmopolitan organisms able to remove a wide range of pharmaceuticals and personal care products (PPCP) through cometabolism (i.e. laccases and peroxidases) or detoxification mechanisms (i.e. cytochrome P450 system). However, the use of PPCP as carbon source for these organisms is largely unexplored. Here, we used carbon stable isotope tracer experiments to assess the fate of anti-inflammatory diclofenac (DCF) and UV filter benzophenone-3 (BP3) during degradation by Trametes versicolor. The comparison between carbon isotopic composition of emitted carbon dioxide from 13C-labelled DCF ([acetophenyl ring-13C6]-DCF) and 13C-BP3 ([phenyl-13C6]-BP3) versus their 12C-homologue compounds showed mineralization of about 45% and 10% of the 13C contained in their respective molecules after 9 days of incubation. The carbon isotopic composition of the bulk biomass and the application of amino acid-stable isotope probing (SIP) allowed distinguishing between incorporation of 13C from BP3 into amino acids, which implies the use of this emerging contaminant as carbon source, and major intracellular accumulation of 13C from DCF without implying the transformation of its labelled phenyl ring into anabolic products. A mass balance of 13C in different compartments over time provided a comprehensive picture of the fate of DCF and BP3 across their different transformation processes. This is the first report assessing biodegradation of PPCP by SIP techniques and the use of emerging contaminants as carbon source for amino acid biosynthesis.

  9. Injectable, degradable, electroactive nanocomposite hydrogels containing conductive polymer nanoparticles for biomedical applications

    PubMed Central

    Wang, Qinmei; Wang, Qiong; Teng, Wei

    2016-01-01

    Injectable electroactive hydrogels (eGels) are promising in regenerative medicine and drug delivery, however, it is still a challenge to obtain such hydrogels simultaneously possessing other properties including uniform structure, degradability, robustness, and biocompatibility. An emerging strategy to endow hydrogels with desirable properties is to incorporate functional nanoparticles in their network. Herein, we report the synthesis and characterization of an injectable hydrogel based on oxidized alginate (OA) crosslinking gelatin reinforced by electroactive tetraaniline-graft-OA nanoparticles (nEOAs), where nEOAs are expected to impart electroactivity besides reinforcement without significantly degrading the other properties of hydrogels. Assays of transmission electron microscopy, 1H nuclear magnetic resonance, and dynamic light scattering reveal that EOA can spontaneously and quickly self-assemble into robust nanoparticles in water, and this nanoparticle structure can be kept at pH 3~9. Measurement of the gel time by rheometer and the stir bar method confirms the formation of the eGels, and their gel time is dependent on the weight content of nEOAs. As expected, adding nEOAs to hydrogels does not cause the phase separation (scanning electron microscopy observation), but it improves mechanical strength up to ~8 kPa and conductivity up to ~10−6 S/cm in our studied range. Incubating eGels in phosphate-buffered saline leads to their further swelling with an increase of water content <6% and gradual degradation. When growing mesenchymal stem cells on eGels with nEOA content ≤14%, the growth curves and morphology of cells were found to be similar to that on tissue culture plastic; when implanting these eGels on a chick chorioallantoic membrane for 1 week, mild inflammation response appeared without any other structural changes, indicating their good in vitro and in vivo biocompatibility. With injectability, uniformity, degradability, electroactivity, relative

  10. Degradable polymeric nanoparticles by aggregation of thermoresponsive polymers and ``click'' chemistry

    NASA Astrophysics Data System (ADS)

    Dworak, Andrzej; Lipowska, Daria; Szweda, Dawid; Suwinski, Jerzy; Trzebicka, Barbara; Szweda, Roza

    2015-10-01

    This study describes a novel approach to the preparation of crosslinked polymeric nanoparticles of controlled sizes that can be degraded under basic conditions. For this purpose thermoresponsive copolymers containing azide and alkyne functions were obtained by ATRP of di(ethylene glycol) monomethyl ether methacrylate (D) and 2-aminoethyl methacrylate (A) followed by post polymerization modification. The amino groups of A were reacted with propargyl chloroformate or 2-azido-1,3-dimethylimidazolinium hexafluorophosphate, which led to two types of copolymers. Increasing the temperature of aqueous solutions of the mixed copolymers caused their aggregation into spherical nanoparticles composed of both types of chains. Their dimensions could be controlled by changing the concentration and heating rate of the solutions. Covalent stabilization of aggregated chains was performed by a ``click'' reaction between the azide and alkyne groups. Due to the presence of a carbamate bond the nanoparticles undergo pH dependent degradation under mild basic conditions. The proposed procedure opens a route to new carriers for the controlled release of active species.This study describes a novel approach to the preparation of crosslinked polymeric nanoparticles of controlled sizes that can be degraded under basic conditions. For this purpose thermoresponsive copolymers containing azide and alkyne functions were obtained by ATRP of di(ethylene glycol) monomethyl ether methacrylate (D) and 2-aminoethyl methacrylate (A) followed by post polymerization modification. The amino groups of A were reacted with propargyl chloroformate or 2-azido-1,3-dimethylimidazolinium hexafluorophosphate, which led to two types of copolymers. Increasing the temperature of aqueous solutions of the mixed copolymers caused their aggregation into spherical nanoparticles composed of both types of chains. Their dimensions could be controlled by changing the concentration and heating rate of the solutions. Covalent

  11. Injectable, degradable, electroactive nanocomposite hydrogels containing conductive polymer nanoparticles for biomedical applications.

    PubMed

    Wang, Qinmei; Wang, Qiong; Teng, Wei

    2016-01-01

    Injectable electroactive hydrogels (eGels) are promising in regenerative medicine and drug delivery, however, it is still a challenge to obtain such hydrogels simultaneously possessing other properties including uniform structure, degradability, robustness, and biocompatibility. An emerging strategy to endow hydrogels with desirable properties is to incorporate functional nanoparticles in their network. Herein, we report the synthesis and characterization of an injectable hydrogel based on oxidized alginate (OA) crosslinking gelatin reinforced by electroactive tetraaniline-graft-OA nanoparticles (nEOAs), where nEOAs are expected to impart electroactivity besides reinforcement without significantly degrading the other properties of hydrogels. Assays of transmission electron microscopy, (1)H nuclear magnetic resonance, and dynamic light scattering reveal that EOA can spontaneously and quickly self-assemble into robust nanoparticles in water, and this nanoparticle structure can be kept at pH 3~9. Measurement of the gel time by rheometer and the stir bar method confirms the formation of the eGels, and their gel time is dependent on the weight content of nEOAs. As expected, adding nEOAs to hydrogels does not cause the phase separation (scanning electron microscopy observation), but it improves mechanical strength up to ~8 kPa and conductivity up to ~10(-6) S/cm in our studied range. Incubating eGels in phosphate-buffered saline leads to their further swelling with an increase of water content <6% and gradual degradation. When growing mesenchymal stem cells on eGels with nEOA content ≤14%, the growth curves and morphology of cells were found to be similar to that on tissue culture plastic; when implanting these eGels on a chick chorioallantoic membrane for 1 week, mild inflammation response appeared without any other structural changes, indicating their good in vitro and in vivo biocompatibility. With injectability, uniformity, degradability, electroactivity, relative

  12. Probing the subglass relaxation behavior in model heterocyclic polymer networks by dielectric spectroscopy

    NASA Astrophysics Data System (ADS)

    Kramarenko, V. Yu.; Ezquerra, T. A.; Privalko, V. P.

    2001-11-01

    The subglass relaxation (β) in model heterocyclic polymer networks (HPNs) with a controlled ratio of trimerized mono- and diisocyanates was characterized by dielectric spectroscopy in the frequency domain. The β relaxation in the investigated HPNs follows the Arrhenius law with unusually low values of the preexponential factor (10-17<τβ0<10-15 s). However, little influence of the local environment, as characterized by the network density, on the apparent activation energies ΔEβ is observed. This fact, combined with their fairly low absolute values (50.4-58.3 kJ/mol), were considered as typical of a noncooperative relaxation in loosely packed regions of a glassy quasilattice. Both the intensity and dielectric strength of the β relaxation in HPNs increase with increasing apparent network density (i.e., with lower ratios of linear and network structures in the system, L/N). This effect was explained by a model assuming that the total, composition-invariant, free volume available was distributed between densely packed domains comprising linear, two-arm isocyanurate heterocycles (ISHs) and loosely packed, three-arm ISHs, which form continuous, three-dimensional network structures. The experimental data for HPNs confirm Ngai's correlation between the logarithm of the secondary β-relaxation time and the Kohlrausch-Williams-Watts stretching exponent for the primary α relaxation. It is suggested that the absence of conjugated bonds within isocyanurate heterocycles makes them sufficiently flexible to allow for specific conformational transitions, like the ``chair-boat-chair'' transition in the structurally similar cyclohexyl ring.

  13. Degradation of greenhouse twines derived from natural fibers and biodegradable polymer during composting.

    PubMed

    Lau, A K; Cheuk, W W; Lo, K V

    2009-01-01

    Commercial composting operations generally do not accept organic wastes with plastic twines from the greenhouse vegetable industry and the bulk of the waste materials ends up in landfills. The objectives of this paper are to identify environmentally compatible substitutes that could replace the current use of petrochemically derived plastic twines in greenhouse vegetable production, thus diverting them from landfills, and to assess the extent of their degradation via composting. Physical properties of the twines, including linear density, percent weight loss and tensile strength were monitored for the biodegradation tests. A pilot-scale composting trial was conducted in an in-vessel composting system. Results showed that the three biodegradable twine materials (cotton, jute and EcoPLA) could degrade readily in a composting environment within a reasonable time frame. Specifically, at the end of 105 days of composting, 85.3%, 84.8% and 81.1% of weight loss was observed for cotton, jute and EcoPLA, respectively. Furthermore, EcoPLA exhibited a slower decline in tensile strength with time, when compared to jute and cotton.

  14. Regulation of coal polymer degradation by fungi. Quarterly report, 31 July 1997--30 September 1997

    SciTech Connect

    Not Available

    1997-12-31

    During this reporting period the authors continued their investigations of how low rank coals are degraded by wood rotting fungi. Previous investigations showed that ligninolytic cultures of P. chrysosporium could decolorize soluble low rank coal macromolecule. The authors continue to investigate this phenomenon. Consistent with earlier observations they conclude that soluble coal macromolecule is decolorized in ligninolytic cultures of P. chrysosporium. To determine if this fungus can depolymerize coal macromolecule, samples were analyzed by GPC-HPLC. These analyses suggested that when coal macromolecules were incubated with ligninolytic cultures of P. chrysosporium a slight decrease in the average peak molecular weight of this mixture had occurred. During this reporting period they also discovered that changes in buffer composition can alter the peak retention times of coal macromolecules during GPC-HPLC probably by causing dissociation and reassociation of individual macromolecules. In other experiments it has been shown that lignin peroxidases that are secreted by ligninolytic cultures of P. chrysosporium are responsible, at least in part, for decolorization of coal macromolecules. Taken together, these studies show that the lignin degrading system of P. chrysosporium is able to enzymatically attack macromolecules solubilized from low rank coal. The ability of nonacclimated bacteria from sewage sludge to used leonardite and soluble coal macromolecule as a substrate for methanogenesis was also investigated. To date, the bacterial consortium studied was unable to use these substrates for this purpose.

  15. Concentration Effects of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Activity for Three Platinum Catalysts

    DOE PAGES

    Christ, J. M.; Neyerlin, K. C.; Richards, R.; ...

    2014-10-04

    A rotating disk electrode (RDE) along with cyclic voltammetry (CV) and linear sweep voltammetry (LSV), were used to investigate the impact of two model compounds representing degradation products of Nafion and 3M perfluorinated sulfonic acid membranes on the electrochemical surface area (ECA) and oxygen reduction reaction (ORR) activity of polycrystalline Pt, nano-structured thin film (NSTF) Pt (3M), and Pt/Vulcan carbon (Pt/Vu) (TKK) electrodes. ORR kinetic currents (measured at 0.9 V and transport corrected) were found to decrease linearly with the log of concentration for both model compounds on all Pt surfaces studied. Ultimately, model compound adsorption effects on ECA weremore » more abstruse due to competitive organic anion adsorption on Pt surfaces superimposing with the hydrogen underpotential deposition (HUPD) region.« less

  16. Gold nanoworms immobilized graphene oxide polymer brush nanohybrid for catalytic degradation studies of organic dyes

    NASA Astrophysics Data System (ADS)

    Mogha, Navin Kumar; Gosain, Saransh; Masram, Dhanraj T.

    2017-02-01

    In the present work, we report gold nanoparticles (AuNPs) on poly (dimethylaminoethyl methacrylate) (PDMAEMA) brushes immobilized reduced graphene oxide (Au/PDMAEMA/RGO) as catalyst for degradation kinetic studies of Rhodamine B (RB), Methyl Orange (MO) and Eosine Y (EY) dyes, having an excellent catalytic activity, as evident by the apparent rate constant (kapp), which is found to be 21.8, 26.2, and 8.7 (×10-3 s-1), for RB, MO and EY respectively. Au/PDMAEMA/RGO catalyst is easy to use, highly efficient, recyclable, which make it suitable for applications in waste water management. Foremost, synthesis of PDMAEMA brushes on graphene oxide is accomplished by Atom transfer radical polymerization method (ATRP), whereas AuNPs are synthesized by simple chemical reduction method.

  17. Concentration Effects of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Activity for Three Platinum Catalysts

    SciTech Connect

    Christ, J. M.; Neyerlin, K. C.; Richards, R.; Dinh, H. N.

    2014-10-04

    A rotating disk electrode (RDE) along with cyclic voltammetry (CV) and linear sweep voltammetry (LSV), were used to investigate the impact of two model compounds representing degradation products of Nafion and 3M perfluorinated sulfonic acid membranes on the electrochemical surface area (ECA) and oxygen reduction reaction (ORR) activity of polycrystalline Pt, nano-structured thin film (NSTF) Pt (3M), and Pt/Vulcan carbon (Pt/Vu) (TKK) electrodes. ORR kinetic currents (measured at 0.9 V and transport corrected) were found to decrease linearly with the log of concentration for both model compounds on all Pt surfaces studied. Ultimately, model compound adsorption effects on ECA were more abstruse due to competitive organic anion adsorption on Pt surfaces superimposing with the hydrogen underpotential deposition (HUPD) region.

  18. The effect of the oxidation state of a terthiophene-conducting polymer and of the presence of a redox probe on its gene-sensing properties.

    PubMed

    Spires, John B; Peng, Hui; Williams, David E; Wright, Bryon E; Soeller, Christian; Travas-Sejdic, Jadranka

    2008-12-01

    The gene-sensing properties of sensor films made of a terthiophene-conducting polymer, poly(3-((2':2'', 5'':2'''-terthiophene)-3''-yl)acrylic acid) (PTAA), were evaluated using electrochemical impedance spectroscopy for films in their reduced and oxidised states with and without the Fe(CN)(6)(3-/4-) redox probe (RP) in dilute tris-EDTA buffer. Porous films of PTAA were prepared and attached to an oligonucleotide sequence specific to the Salmonella virulence gene InvA. These films could be described with a dual transmission line model in which the polymer conductivity was increased as a consequence of surface binding of complementary DNA. The effect is analogous to that reported for silicon nanowires and field-effect transistors in dilute electrolyte modified by charge exchange across the polymer-electrolyte interface. As a result, gene sensing could be conveniently observed as a change in the impedance phase angle at a fixed frequency.

  19. Nucleophilic Polymers and Gels in Hydrolytic Degradation of Chemical Warfare Agents.

    PubMed

    Bromberg, Lev; Creasy, William R; McGarvey, David J; Wilusz, Eugene; Hatton, T Alan

    2015-10-07

    Water- and solvent-soluble polymeric materials based on polyalkylamines modified with nucleophilic groups are introduced as catalysts of chemical warfare agent (CWA) hydrolysis. A comparative study conducted at constant pH and based on the criteria of the synthetic route simplicity, aqueous solubility, and rate of hydrolysis of CWA mimic, diisopropylfluorophosphate (DFP), indicated that 4-aminopyridine-substituted polyallylamine (PAAm-APy) and polyvinylamine substituted with 4-aminopyridine (PVAm-APy) were advantageous over 4-pyridinealdoxime-modified PVAm and PAAm, poly(butadiene-co-pyrrolidinopyridine), and PAAm modified with bipyridine and its complex with Cu(II). The synthesis of PVAm-APy and PAAm-APy involved generation of a betaine derivative of acrylamide and its covalent attachment onto the polyalkylamine chain followed by basic hydrolysis. Hydrogel particles of PAAm-APy and PVAm-APy cross-linked by epichlorohydrin exhibited pH-dependent swelling and ionization patterns that affected the rate constants of DFP nucleophilic hydrolysis. Deprotonation of the aminopyridine and amine groups increased the rates of the nucleophilic hydrolysis. The second-order rate of nucleophilic hydrolysis was 5.5- to 10-fold higher with the nucleophile-modified gels compared to those obtained by cross-linking of unmodified PAAm, throughout the pH range. Testing of VX and soman (GD) was conducted in 2.5-3.7 wt % PVAm-APy suspensions or gels swollen in water or DMSO/water mixtures. The half-lives of GD in aqueous PVAm-APy were 12 and 770 min at pH 8.5 and 5, respectively. Addition of VX into 3.5-3.7 wt % suspensions of PVAm-APy in DMSO-d6 and D2O at initial VX concentration of 0.2 vol % resulted in 100% VX degradation in less than 20 min. The unmodified PVAm and PAAm were 2 orders of magnitude less active than PVAm-APy and PAAm-APy, with VX half-lives in the range of 24 h. Furthermore, the PVAm-APy and PAAm-APy gels facilitated the dehydrochlorination reaction of sulfur mustard

  20. Interface for direct and continuous sample-matrix deposition onto a MALDI probe for polymer analysis by thermal field flow fractionation and off-line MALDI-MS.

    PubMed

    Basile, Franco; Kassalainen, Galina E; Ratanathanawongs Williams, S Kim

    2005-05-01

    A simple interface based on an oscillating capillary nebulizer (OCN) is described for direct deposition of eluate from a thermal field-flow fractionation (ThFFF) system onto a matrix-assisted laser desorption/ionization (MALDI) probe. In this study, the polymer-containing eluent from the ThFFF system was mixed on-line with MALDI matrix solution and deposited directly onto a moving MALDI probe. The result was a continuous sample track representative of the fractionation process. Subsequent off-line MALDI-mass spectrometry analysis was performed in automated and manual modes. Polystyrene samples of broad polydispersity were used to characterize the overall system performance. The OCN interface is easy to build and operate without the use of heaters or high voltages and is compatible with any MALDI probe format.

  1. Fatigue degradation and life prediction of glass fabric polymer composites under tension/torsion biaxial loadings

    SciTech Connect

    Kawakami, H.; Fujii, T.J.; Morita, Y.

    1995-10-01

    Fatigue degradation and life prediction for a plain woven glass fabric reinforced polyester under tension/torsion biaxial loadings were investigated. Typical S-N diagrams were given at several biaxial ratios when the biaxial cyclic loads were proportionally applied to the specimens. A fatigue damage accumulation model based on the continuum damage mechanics theory was developed, where modulus decay ratios in tension and shear were used as indicators for damage variables (D). In the model, the damage variables are considered to be second-order tensors. Then, the maximum principal damage variable, D* is introduced. According to the similarity to the principal stress, D* is obtained as the maximum eigen value of damage tensor [D{prime}]. Under proportional tension/torsion loadings, fatigue lives were satisfactorily predicted at any biaxial stress ratios using the present model in which the fatigue characteristics only under uniaxial tension and pure torsion loadings were needed. For a certain biaxial stress ratio, the effect of loading path on the fatigue strength was examined. The experimental result does not show a strong effect of loading path on the fatigue life.

  2. Plasticized drug-loaded melt electrospun polymer mats: characterization, thermal degradation, and release kinetics.

    PubMed

    Balogh, Attila; Drávavölgyi, Gábor; Faragó, Kornél; Farkas, Attila; Vigh, Tamás; Sóti, Péter Lajos; Wagner, István; Madarász, János; Pataki, Hajnalka; Marosi, György; Nagy, Zsombor Kristóf

    2014-04-01

    Melt electrospinning (MES) was used to prepare fast dissolving fibrous drug delivery systems in the presence of plasticizers. This new method was found promising in the field of pharmaceutical formulation because it combines the advantages of melt extrusion and solvent-based electrospinning. Lowering of the process temperature was performed using plasticizers in order to avoid undesired thermal degradation. Carvedilol (CAR), a poorly water-soluble and thermal-sensitive model drug, was introduced into an amorphous methacrylate terpolymer matrix, Eudragit® E, suitable for fiber formation. Three plasticizers (triacetin, Tween® 80, and polyethylene glycol 1500) were tested, all of which lowered the process temperature effectively. Scanning electron microscopy, X-ray diffraction, differential scanning calorimetry, and Raman microspectrometry investigations showed that crystalline CAR turned into an amorphous form during processing and preserved it for longer time. In vitro dissolution studies revealed ultrafast drug dissolution of the fibrous samples. According to the HPLC impurity tests, the reduced stability of CAR under conditions applied without plasticizer could be avoided using plasticizers, whereas storage tests also indicated the importance of optimizing the process parameters during MES.

  3. Investigation of degradation mechanisms of a high-temperature polymer-electrolyte-membrane fuel cell stack by electrochemical impedance spectroscopy

    NASA Astrophysics Data System (ADS)

    Kim, Ji-Rae; Yi, Jung S.; Song, Tae-Won

    2012-12-01

    Retaining optimum acid-contents in membranes and electrodes is critical to maintaining the performance and durability of acid-doped high-temperature (HT) polymer-electrolyte-membrane fuel cells (PEMFCs). Since the distribution of acids is influenced by the operating and compression conditions of the stack, there is great demand for understanding the behavior of individual membrane-electrode-assemblies (MEAs) while operating the cells in a stack. In this study, an in-situ diagnosis method using electrochemical impedance spectroscopy (EIS) is implemented during the durability test of an HT-PEMFC stack. Adopting a lumped equivalent-circuit model, the specific parameters are obtained from EIS results, and the changes of the values are compared with the performance loss of individual MEA. From this analysis it can be concluded that the main cause of performance degradation of the stack is due to the loss of electrolytes in the cathode, which leads to an increase in the proton transport resistance of cathode catalyst layers. In addition to the proton transport loss in the cathode, the charge transfer resistance of the oxygen reduction reaction has contributed to the performance decay of the stack. The causes of the increase in the cathode charge transfer resistance for each cell of the stack are discussed.

  4. The effect of degradable polymer surfaces on co-cultures of monocytes and smooth muscle cells.

    PubMed

    McBane, Joanne E; Battiston, Kyle G; Wadhwani, Aman; Sharifpoor, Soroor; Labow, Rosalind S; Santerre, J Paul

    2011-05-01

    Strategies to optimize biomaterial chemistry for applications in vascular tissue engineering attempt to promote endothelial and smooth muscle cell recruitment into porous material constructs. The primary objective is to facilitate relevant tissue formation in a wound healing versus pro-inflammatory manner. The present work investigated the interactive co-cellular response of human monocytes and human vascular smooth muscle cells (VSMCs) with a novel degradable, polar/hydrophobic/ionic (D-PHI) polyurethane and compared it to a commercially available biomaterial, poly-lactic-glycolic acid (PLGA) as well as tissue culture polystyrene (TCPS). D-PHI triggered a smaller pro-inflammatory response (acid phosphatase, esterase, tumor necrosis factor-α) at later time points (>14 d) than PLGA suggesting that monocytes may be transitioning to a more wound-healing phenotype on the D-PHI surface. When D-PHI was coated with collagen, monocyte cell attachment did not differ with the native D-PHI; however, PLGA showed significant differences between collagen coated versus uncoated surfaces. There were more VSMCs and monocytes attached in co-culture to D-PHI when compared to PLGA. Co-cultures on D-PHI released more IL-10 (anti-inflammatory) than monocytes cultured alone, while the VSMCs retained the expression of its marker protein calponin. Together the above data suggest that co-culturing monocytes with VSMCs may aid in stimulating the attachment of VSMCs to D-PHI while eliciting the desired functional phenotypes for both monocytes (i.e. low inflammation based on IL-10 values) and VSMCs (expressing calponin, a marker of contractility). Moreover, the results of this study demonstrated that D-PHI performed equally or better to PLGA in terms of the assayed biological parameters.

  5. Bioresorbable Ca-phosphate-polymer/metal and Fe-Ag nanocomposites for macro-porous scaffolds with tunable degradation and drug release

    NASA Astrophysics Data System (ADS)

    Gotman, I.; Swain, S. K.; Sharipova, A.; Gutmanas, E. Y.

    2016-11-01

    Bioresorbable implants are increasingly gaining popularity as an attractive alternative to traditional permanent bone healing devices. The advantage of bioresorbable implantable devices is that they slowly degrade over time and disappear once their "mission" is accomplished. Thus, no foreign material is left behind that can cause adverse effects on the host, such as long term local or systemic immune response and stress-shielding related bone atrophy. Resorbable materials considered for surgical implant applications include degradable polymers, Ca phosphate ceramics (CaP) and corrodible metals. Degradable polymers, such as polycaprolactone and lactic acid are weak, lack osteoconductivity and degrade to acidic products that can cause late inflammation. Resorbable CaP ceramics (e.g., β-TCP) are attractive materials for bone regeneration bear close resemblance to the bone mineral, however they are intrinsically brittle and thus unsuitable for use in load-bearing sites. Moreover, introducing high porosity required to encourage better cellular ingrowth into bone regeneration scaffolds is detrimental to the mechanical strength of the material. In present work we review and discuss our results on development of strong bioresorbable Ca-phosphate-polymer/metal nanonocomposites and highly porous scaffolds from them. By introduction of nanoscale ductile polymer or metal phase into CaP ceramic an attempt was made to mimic structure of natural bone, where nanocrystallites of CaP ceramic are bonded by thin collagen layers. Recent results on development of high strength scaffolds from Fe-Ag nanocomposites are also reported. High energy milling of powders followed by cold sintering—high pressure consolidation at ambient temperature in combination with modified porogen leaching method was employed for processing. The developed nanocomposites and scaffolds exhibited high mechanical strength coupled with measurable ductility, gradual lost weight and strength during immersion in

  6. Photothermal Gene Delivery: Stimuli-Regulated Enzymatically Degradable Smart Graphene-Oxide-Polymer Nanocarrier Facilitating Photothermal Gene Delivery (Adv. Healthcare Mater. 15/2016).

    PubMed

    Kim, Hyunwoo; Kim, Jinhwan; Lee, Minkyung; Choi, Hee Cheul; Kim, Won Jong

    2016-08-01

    On page 1918, Won Jong Kim and co-workers use disulfide bonding for the rational design of graphene oxide (GO) based nanocarriers. In the lower left side, photothermally triggered gene release is illustrated in cancer cell. Polymer-detached GOis exocytosed, and subsequently gets into the macrophage (middle right). In the macrophage, peroxidase binds to GO, thus degrades it to small fragments which are fluorescent.

  7. The guanidinium group as a key part of water-soluble polymer carriers for siRNA complexation and protection against degradation.

    PubMed

    Tabujew, Ilja; Freidel, Christoph; Krieg, Bettina; Helm, Mark; Koynov, Kaloian; Müllen, Klaus; Peneva, Kalina

    2014-07-01

    Here, the preparation of a novel block copolymer consisting of a statistical copolymer N-(2-hydroxypropyl) methacrylamide-s-N-(3-aminopropyl) methacrylamide and a short terminal 3-guanidinopropyl methacrylamide block is reported. This polymer structure forms neutral but water-soluble nanosized complexes with siRNA. The siRNA block copolymer complexes are first analyzed using agarose gel electrophoresis and their size is determined with fluorescence correlation spectroscopy. The protective properties of the polymer against RNA degradation are investigated by treating the siRNA block copolymer complexes with RNase V1. Heparin competition assays confirm the efficient release of the cargo in vitro. In addition, the utilization of microscale thermophoresis is demonstrated for the determination of the binding strength between a fluorescently labeled polyanion and a polymer molecule.

  8. Matrix-assisted laser desorption/ionization mass spectrometry imaging: a powerful tool for probing the molecular topology of plant cutin polymer.

    PubMed

    Veličković, Dušan; Herdier, Hélène; Philippe, Glenn; Marion, Didier; Rogniaux, Hélène; Bakan, Bénédicte

    2014-12-01

    The cutin polymers of different fruit cuticles (tomato, apple, nectarine) were examined using matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI MSI) after in situ release of the lipid monomers by alkaline hydrolysis. The mass spectra were acquired from each coordinate with a lateral spatial resolution of approximately 100 μm. Specific monomers were released at their original location in the tissue, suggesting that post-hydrolysis diffusion can be neglected. Relative quantification of the species was achieved by introducing an internal standard, and the collection of data was subjected to non-supervised and supervised statistical treatments. The molecular images obtained showed a specific distribution of ions that could unambiguously be ascribed to cutinized and suberized regions observed at the surface of fruit cuticles, thus demonstrating that the method is able to probe some structural changes that affect hydrophobic cuticle polymers. Subsequent chemical assignment of the differentiating ions was performed, and all of these ions could be matched to cutin and suberin molecular markers. Therefore, this MALDI-MSI procedure provides a powerful tool for probing the surface heterogeneity of plant lipid polymers. This method should facilitate rapid investigation of the relationships between cuticle phenotypes and the structure of cutin within a large population of mutants.

  9. Role of oxygen active species in the photocatalytic degradation of phenol using polymer sensitized TiO2 under visible light irradiation.

    PubMed

    Zhang, Dongdong; Qiu, Rongliang; Song, Lin; Eric, Brewer; Mo, Yueqi; Huang, Xiongfei

    2009-04-30

    The role of dissolved oxygen, and of active species generated by photo-induced reactions with oxygen, in the photocatalytic degradation of phenol was investigated using polymer [poly-(fluorene-co-thiophene) with thiophene content of 30%, so-called PFT30] sensitized TiO2 (PFT30/TiO2) under visible light irradiation. The photoluminescent (PL) quantum yield of PFT30/TiO2 was about 30% of that of PFT30/Al(2)O(3), proving that electron transfer took place between the polymer and TiO2. The result that photocatalytic degradation of phenol was almost stopped when the solution was saturated with N(2) proved the importance of O(2). Addition of NaN(3), an effective quencher of singlet oxygen ((1)O(2)), caused about a 40% decrease in the phenol degradation ratio. Addition of alcohols caused about a 60% decrease in the phenol photodegradation ratio, indicating that the hydroxyl radicals (OH), whose presence was confirmed by electron spin resonance (ESR) spectroscopy, was the predominant active species in aqueous solution. In anhydrous solution, singlet oxygen ((1)O(2)) was the predominant species. These results indicate that oxygen plays a very important role in the photocatalytic degradation of phenol.

  10. APPLICATION OF FLUORESCENCE SPECTROSCOPIC TECHNIQUES AND PROBES TO THE DETECTION OF BIOPOLYMER DEGRADATION IN NATURAL ENVIRONMENTS. (R825159)

    EPA Science Inventory

    The activities and substrate specificities of extracellular enzymes in natural systems are not well understood, despite their critical role in microbial remineralization of organic carbon. These enzymes initiate organic carbon degradation by selectively hydrolyzing high molecular...

  11. Probing the structure and nano-scale mechanical properties of polymer surfaces with scanning force microscopy and sum frequency vibrational spectroscopy

    SciTech Connect

    Gracias, David Hugo

    1999-05-01

    Scanning Force Microscopy (SFM) has been used to quantitatively measure the elastic modulus, friction and hardness of polymer surfaces with special emphasis on polyethylene and polypropylene. In the experiments, tips of different radii of curvature ranging from 20 nm to 1000 nm have been used and the high pressure applied by the SFM have been observed to affect the values obtained in the measurements. The contact of the SFM tip with the polymer surface is explained by fitting the experimental curves to theoretical predictions of contact mechanics. Sum Frequency Generation (SFG) Vibrational Spectroscopy has been used to measure vibrational spectra of polymer surfaces in the vibrational range of 2700 to 3100 cm-1. Strong correlations are established between surface chemistry and surface structure as probed by SFG and mechanical properties measured by SFM on the surfaces. In these studies segregation of low surface energy moieties, from the bulk of the polymer to the surface have been studied. It was found that surface segregation occurs in miscible polymer blends and a small concentration of surface active polymer can be used to totally modify the surface properties of the blend. A novel high vacuum SFM was built to do temperature dependent measurements of mechanical changes occurring at the surface of polypropylene during the glass transition of the polymer. Using this instrument the modulus and friction of polypropylene was measured in the range of room temperature to ˜-60°C. An increase in the ordering of the backbone of the polymer chains below the glass transition measured by SFG correlates well with the increase in modulus measured on the same surface with SFM. Friction measurements have been done on polyethylene with three different instruments by applying loads ranging from nN to sub newton i.e. over eight orders of magnitude. Pressure and contact area effects were observed to play a significant role in determining the frictional response of the polymer

  12. In vitro study of drug-eluting stent coatings based on poly(L-lactide) incorporating cyclosporine A - drug release, polymer degradation and mechanical integrity.

    PubMed

    Sternberg, Katrin; Kramer, Sven; Nischan, Claudia; Grabow, Niels; Langer, Thomas; Hennighausen, Gerhard; Schmitz, Klaus-Peter

    2007-07-01

    In this study, absorbable polymer stent coatings for localized drug delivery based on poly(L-lactide) (PLLA) and cyclosporine A (CsA) were developed and tested in vitro. Metallic stents were coated with different compositions of PLLA/CsA (70/30, 60/40, 50/50% w/w) and beta-sterilized. The specimens were used to assess the drug release kinetics with HPLC. Sterilization influenced polymer degradation was measured with GPC. Mechanical integrity of the stent coatings was studied with SEM. The interconnection of the coated stents with a balloon-catheter was characterized by the measurement of stent dislodgment force. A migration assay was used to determine the inhibitory effect of the model drug CsA on smooth muscle cell (SMC) migration. The release of CsA was established over time periods up to 24 days in sodium chloride solution and in porcine blood plasma. An inhibition of SMC migration (max. 26-33%) was found for CsA concentrations of 4 x 10(-5) to 4 x 10(-7) mol/l. Marked molecular weight reduction (70-80%) of the PLLA matrix occurred after beta-sterilization. We also observed a substantial decrease of in vitro degradation time. The maintenance of the mechanical integrity of the polymer coating during crimping and dilation of the specimens could be verified, and a sufficient stent dislodgment force of 0.8-0.9 N was measured.

  13. Hydrothermal synthesis of Bismuth(III) coordination polymer and its transformation to nano α-Bi{sub 2}O{sub 3} for photocatalytic degradation

    SciTech Connect

    Huang, Ya-Jing; Zheng, Yue-Qing Zhu, Hong-Lin; Wang, Jin-Jian

    2016-07-15

    A new Bi(III) coordination polymer Bi{sub 2}(Hpdc){sub 2}(pdc){sub 2}·2H{sub 2}O (H{sub 2}pdc=pyridine-2,6-dicarboxylic acid) was synthesized by hydrothermal method. Solid state thermal decomposition of this complex under 500 °C for 1 h led to the foliated Bi{sub 2}O{sub 3} nanoparticles, which were then characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Comparative study on their photocatalytic activity toward the degradation of rhodamine B (RhB), methylene blue (MB) and methyl orange (MO) in polluted water was explored, and the mechanism of these photocatalytic degradation was discussed. These results provided some interesting insights into their photocatalytic applications. - Graphical abstract: We regard Bi{sub 2}(Hpdc){sub 2}(pdc){sub 2}·2H{sub 2}O with 1D chain structures as the precursor, then calcinate the complex to prepare nano-powder α-Bi{sub 2}O{sub 3}. The photochemical experiment indicates that Bi{sub 2}(Hpdc){sub 2}(pdc){sub 2}·2H{sub 2}O can be used as an efficient photocatalyst for the degradation of RhB and MB. Interestingly, nano α-Bi{sub 2}O{sub 3} shows higher activity than the commercial Bi{sub 2}O{sub 3} for the degradation of RhB, MB or MO. Display Omitted - Highlights: • A novel dinuclear Bi(III) coordination polymer is hydrothermally synthesized. • Calcinating the precursor Bi-CP will result in the nano Bi{sub 2}O{sub 3} with foliated morphology. • Nano Bi{sub 2}O{sub 3} shows higher activity than the commercial Bi{sub 2}O{sub 3} for the degradation of dyes.

  14. Probing the self-assembled nanostructures of functional polymers with synchrotron grazing incidence X-ray scattering.

    PubMed

    Ree, Moonhor

    2014-05-01

    For advanced functional polymers such as biopolymers, biomimic polymers, brush polymers, star polymers, dendritic polymers, and block copolymers, information about their surface structures, morphologies, and atomic structures is essential for understanding their properties and investigating their potential applications. Grazing incidence X-ray scattering (GIXS) is established for the last 15 years as the most powerful, versatile, and nondestructive tool for determining these structural details when performed with the aid of an advanced third-generation synchrotron radiation source with high flux, high energy resolution, energy tunability, and small beam size. One particular merit of this technique is that GIXS data can be obtained facilely for material specimens of any size, type, or shape. However, GIXS data analysis requires an understanding of GIXS theory and of refraction and reflection effects, and for any given material specimen, the best methods for extracting the form factor and the structure factor from the data need to be established. GIXS theory is reviewed here from the perspective of practical GIXS measurements and quantitative data analysis. In addition, schemes are discussed for the detailed analysis of GIXS data for the various self-assembled nanostructures of functional homopolymers, brush, star, and dendritic polymers, and block copolymers. Moreover, enhancements to the GIXS technique are discussed that can significantly improve its structure analysis by using the new synchrotron radiation sources such as third-generation X-ray sources with picosecond pulses and partial coherence and fourth-generation X-ray laser sources with femtosecond pulses and full coherence.

  15. The influence of the electrochemical stressing (potential step and potential-static holding) on the degradation of polymer electrolyte membrane fuel cell electrocatalysts

    NASA Astrophysics Data System (ADS)

    Shao, Yuyan; Kou, Rong; Wang, Jun; Viswanathan, Vilayanur V.; Kwak, Ja Hun; Liu, Jun; Wang, Yong; Lin, Yuehe

    The understanding of the degradation mechanisms of electrocatalysts is very important for developing durable electrocatalysts for polymer electrolyte membrane (PEM) fuel cells. The degradation of Pt/C electrocatalysts under potential-static holding conditions (at 1.2 V and 1.4 V vs. RHE) and potential step conditions with the upper potential of 1.4 V for 150 s and lower potential limits (0.85 V and 0.60 V) for 30 s in each period [denoted as Pstep(1.4V_150s-0.85V_30s) and Pstep(1.4V_150s-0.60V_30s), respectively] were investigated. The electrocatalysts and support were characterized with electrochemical voltammetry, transmission electron microscope (TEM) and X-ray photoelectron spectroscopy (XPS). Pt/C degrades much faster under Pstep conditions than that under potential-static holding conditions. Pt/C degrades under the Pstep(1.4V_150s-0.85V_30s) condition mainly through the coalescence process of Pt nanoparticles due to the corrosion of carbon support, which is similar to that under the conditions of 1.2 V- and 1.4 V-potential-static holding; however, Pt/C degrades mainly through the dissolution/loss and dissolution/redeposition process if stressed under Pstep(1.4V_150s-0.60V_30s). The difference in the degradation mechanisms is attributed to the chemical states of Pt nanoparticles: Pt dissolution can be alleviated by the protective oxide layer under the Pstep(1.4V_150s-0.85V_30s) condition and the potential-static holding conditions. These findings are very important for understanding PEM fuel cell electrode degradation and are also useful for developing fast test protocol for screening durable catalyst support materials.

  16. Polymer dynamics near the surface and in the bulk of poly(tetrafluoroethylene) probed by zero-field muon-spin-relaxation spectroscopy.

    PubMed

    McKenzie, Iain; Salman, Zaher; Giblin, Sean R; Han, Yun Yu; Leach, Gary W; Morenzoni, Elvezio; Prokscha, Thomas; Suter, Andreas

    2014-02-01

    The results of many experiments on polymers such as polystyrene indicate that the polymer chains near a free surface exhibit enhanced dynamics when compared with the bulk. We have investigated whether this is the case for poly(tetrafluoroethylene) (PTFE) by using zero-field muon-spin-relaxation spectroscopy to characterize a local probe, the F-Mu(+)-F state, which forms when spin-polarized positive muons are implanted in PTFE. Low-energy muons (implantation energies from 2.0 to 23.0 keV) were used to study the F-Mu(+)-F state between ∼ 23 and 191 nm from the free surface of PTFE. Measurements were also made with surface muons (4.1 MeV) where the mean implantation depth is on the order of ∼ 0.6 mm. The relaxation rate of the F-Mu(+)-F state up to ∼ 150 K was found to be significantly higher for muons implanted at 2.0 keV than for higher implantation energies, which suggests that the polymer chains in a region on the order of a few tens of nanometers from the free surface are more mobile than those in the bulk.

  17. High Resolution DNA Stable Isotope Probing Reveals that Root Exudate Addition to Soil Changes the Identity of the Microbes that Degrade Cellulose but not the Rate of Degradation

    NASA Astrophysics Data System (ADS)

    Campbell, A.; Pepe-Ranney, C. P.; Nguyen, A. V. T.; Buckley, D. H.

    2015-12-01

    Plant roots release compounds, such as root exudates, which can alter soil organic matter (SOM) decomposition and have large impacts on soil carbon (C) retention. The changes in SOM turnover resulting from the addition of organic and/or inorganic substrates are termed 'priming effects'. In this study we examine the effects of root exudates on the priming of cellulose added as particulate organic matter. We amended soil microcosms with 13C-cellulose in the presence or absence of artificial root exudate additions and incubated over time for 45 days. Soils receiving the root exudate (RE) were given either one large dose or multiple, small doses of RE. In each treatment we tracked operational taxonomic units (OTUs) assimilating 13C from cellulose (herein, known as a 'responder') over time using DNA stable isotope probing coupled with next generation sequencing. In all treatments the same amount of cellulose-13C was respired indicating the addition of RE did not result in the priming of cellulose decomposition. However, cellulose responders were different depending on treatment and time of sampling (days 14, 28 and 45). We identified a total of 10,361 OTUs, of which there were 369 cellulose responders in the cellulose only treatment, 273 in the repeated, small dose RE treatment, and 358 in the RE single, large dose treatment. Most of the cellulose responders found in all treatments belonged to phyla Bacteroidetes, Planctomycetes, Proteobacteria, Verrucomicrobia, and Chloroflexi. The response time of phyla varies; for instance, more OTUs in Bacteroidetes were observed on day 14 and diminish with each subsequent sampling time. On the other hand, OTUs in Verrucomicrobia increased in response over time. Our study shows no priming effect resulting from the addition of root exudates, although the identity of the microbial mediators of cellulose decomposition varies in each treatment.

  18. An extended micromechanics method for probing interphase properties in polymer nanocomposites [An extended micromechanics method for overlapping geometries with application to polymer nanocomposites

    SciTech Connect

    Liu, Zeliang; Moore, John A.; Liu, Wing Kam

    2016-05-03

    Inclusions comprised on filler particles and interphase regions commonly form complex morphologies in polymer nanocomposites. Addressing these morphologies as systems of overlapping simple shapes allows for the study of dilute particles, clustered particles, and interacting interphases all in one general modeling framework. To account for the material properties in these overlapping geometries, weighted-mean and additive overlapping conditions are introduced and the corresponding inclusion-wise integral equations are formulated. An extended micromechanics method based on these overlapping conditions for linear elastic and viscoelastic heterogeneous material is then developed. An important feature of the proposed approach is that the effect of both the geometric overlapping (clustered particles) and physical overlapping (interacting interphases) on the effective properties can be distinguished. Lastly, we apply the extended micromechanics method to a viscoelastic polymer nanocomposite with interphase regions, and estimate the properties and thickness of the interphase region based on experimental data for carbon-black filled styrene butadiene rubbers.

  19. Innovative Protocols for in SITU MTBE Degradation by Using Molecular Probes-An Enhanced Chemical-Bio Oxidation Technique

    SciTech Connect

    Paul Fallgren

    2009-02-20

    In situ chemical oxidation (ISCO) is a common technology to cleanup petroleum hydrocarbon-contaminated soils and groundwater. Sodium percarbonate (SPC) is an oxidant which is activated by iron (Fe) to produce Fenton-like reactions. Western Research Institute, in conjunction with Regenesis and the U.S. Department of Energy, conducted a study that investigated the performance of a 'safe' oxidant, SPC, to cleanup groundwater and soils contaminated with petroleum hydrocarbons and associated contaminants (e.g., MTBE). Results from a field pilot test in Frenchglen, Oregon showed VOC concentrations in groundwater decreased substantially within 2 weeks after injecting activated SPC (RegenOx). A protocol was established for determining RegenOx TOD in soils and groundwater. Total oxidant demand tests were necessary to determine the correct dosage of RegenOx to apply in the field and sufficiently degrade the contaminants of concern. Bench studies with RegenOx showed this technology was effective in degrading diesel fuel and 1,4-dioxane. The Fe-silica activator (RegenOx Part B) was tested with another oxidant, sodium persulfate. Bench tests results showed the combination of sodium persulfate and RegenOx Part B was effective in reducing PCE, MTBE, benzene, and n-heptane concentrations in water. Overall, the results of this project indicated that most petroleum contaminants in soil and groundwater can be sufficiently degraded using the RegenOx technology.

  20. Hydrothermal synthesis of Bismuth(III) coordination polymer and its transformation to nano α-Bi2O3 for photocatalytic degradation

    NASA Astrophysics Data System (ADS)

    Huang, Ya-Jing; Zheng, Yue-Qing; Zhu, Hong-Lin; Wang, Jin-Jian

    2016-07-01

    A new Bi(III) coordination polymer Bi2(Hpdc)2(pdc)2·2H2O (H2pdc=pyridine-2,6-dicarboxylic acid) was synthesized by hydrothermal method. Solid state thermal decomposition of this complex under 500 °C for 1 h led to the foliated Bi2O3 nanoparticles, which were then characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Comparative study on their photocatalytic activity toward the degradation of rhodamine B (RhB), methylene blue (MB) and methyl orange (MO) in polluted water was explored, and the mechanism of these photocatalytic degradation was discussed. These results provided some interesting insights into their photocatalytic applications.

  1. Positively charged polymer brush-functionalized filter paper for DNA sequence determination following Dot blot hybridization employing a pyrrolidinyl peptide nucleic acid probe.

    PubMed

    Laopa, Praethong S; Vilaivan, Tirayut; Hoven, Voravee P

    2013-01-07

    As inspired by the Dot blot analysis, a well known technique in molecular biology and genetics for detecting biomolecules, a new paper-based platform for colorimetric detection of specific DNA sequences employing peptide nucleic acid (PNA) as a probe has been developed. In this particular study, a pyrrolidinyl PNA bearing a conformationally rigid d-prolyl-2-aminocyclopentanecarboxylic acid backbone (acpcPNA) was used as a probe. The filter paper was modified to be positively charged with grafted polymer brushes of quaternized poly(dimethylamino)ethyl methacrylate (QPDMAEMA) prepared by surface-initiated polymerization of 2-(dimethylamino)ethyl methacrylate from the filter paper via ARGET ATRP followed by quaternization with methyl iodide. Following the Dot blot format, a DNA target was first immobilized via electrostatic interactions between the positive charges of the QPDMAEMA brushes and negative charges of the phosphate backbone of DNA. Upon hybridization with the biotinylated pyrrolidinyl peptide nucleic acid (b-PNA) probe, the immobilized DNA can be detected by naked eye observation of the yellow product generated by the enzymatic reaction employing HRP-labeled streptavidin. It has been demonstrated that this newly developed assay was capable of discriminating between complementary and single base mismatch targets at a detection limit of at least 10 fmol. In addition, the QPDMAEMA-grafted filter paper exhibited a superior performance to the commercial membranes, namely Nylon 66 and nitrocellulose.

  2. Adjustable degradation and drug release of a thermosensitive hydrogel based on a pendant cyclic ether modified poly(ε-caprolactone) and poly(ethylene glycol)co-polymer.

    PubMed

    Wang, Weiwei; Deng, Liandong; Liu, Shasha; Li, Xu; Zhao, Xiumei; Hu, Renjie; Zhang, Jianhua; Han, Haijie; Dong, Anjie

    2012-11-01

    The convenient and precise fabrication of drug-hydrogel formulations with satisfactory degradability and a well-controlled drug release profile are crucial factors for injectable hydrogel formulations in clinical applications. Here a new injectable thermosensitive hydrogel formed from poly(ε-caprolactone) (PCL)-poly(ethylene glycol)-poly(ε-caprolactone) amphiphilicco-polymers with 1,4,8-trioxa[4.6]spiro-9-undecanone (TOSUO) moieties incorporated in the poly(ε-caprolactone) (PCL)block (PECT) was constructed to provide a route to tailor the degradation and drug release behavior. The effect of hydrophilic cyclic ether moieties on the degradation of and drug release by PECT hydrogels were evaluated in vitro and in vivo. The results indicated that a freeze-dried powder of paclitaxel-loaded PECT nanoparticles rapidly dissolved in water at ambient temperature with slightly shaking and formed a stable injectable in situ drug-hydrogel formulation at body temperature, which is convenient for clinical operations because it avoids the need for pre-quenching or long-term incubation. The paclitaxel distribution was also more quantitative and homogeneous on entrapping paclitaxel in PECT nanoparticles. Further, the small number of pendant cyclic ether groups in PCL could decrease the cystallinity and hydrophobicity and, as a result, the in vitro and in vivo retention time of PECT hydrogels and the release of entrapped paclitaxel could be tuned from a few weeks to months by varying the amount of PTOSUO in the hydrophobic block. Significantly, paclitaxel-loaded PECT nanoparticles and free paclitaxel could be simultaneously released during the in vitro paclitaxel release from PECT hydrogels. A histopathological evaluation indicated that in vivo injected PECT hydrogels produced only a modest inflammatory response. Thus pendant cyclic ether modification of PCL could be an effective way to achieve the desired degradation and drug release profiles of amphiphilicco-polymer

  3. Electroanalytical measurements without electrolytes: conducting polymers as probes for redox titration in non-conductive organic media.

    PubMed

    Lange, Ulrich; Mirsky, Vladimir M

    2012-09-26

    Electroanalytical methods have been applied only in conducting media. An application of conducting polymers allows to overcome this limitation. If such material is in electrochemical equilibrium with dissolved redox active species, its electrical conductivity depends on the redox potential of these species. Therefore, conductometric measurements with conducting polymers can provide about the same information as classical redox electrodes. The approach was applied for redox titration. Equivalent points obtained by this titration in aqueous and organic electrolytes were identical. Then the approach was applied for determination of bromine number by redox titration in non-conducting organic phase.

  4. Probing the Biomimetic Ice Nucleation Inhibition Activity of Poly(vinyl alcohol) and Comparison to Synthetic and Biological Polymers

    PubMed Central

    2015-01-01

    Nature has evolved many elegant solutions to enable life to flourish at low temperatures by either allowing (tolerance) or preventing (avoidance) ice formation. These processes are typically controlled by ice nucleating proteins or antifreeze proteins, which act to either promote nucleation, prevent nucleation or inhibit ice growth depending on the specific need, respectively. These proteins can be expensive and their mechanisms of action are not understood, limiting their translation, especially into biomedical cryopreservation applications. Here well-defined poly(vinyl alcohol), synthesized by RAFT/MADIX polymerization, is investigated for its ice nucleation inhibition (INI) activity, in contrast to its established ice growth inhibitory properties and compared to other synthetic polymers. It is shown that ice nucleation inhibition activity of PVA has a strong molecular weight dependence; polymers with a degree of polymerization below 200 being an effective inhibitor at just 1 mg.mL–1. Other synthetic and natural polymers, both with and without hydroxyl-functional side chains, showed negligible activity, highlighting the unique ice/water interacting properties of PVA. These findings both aid our understanding of ice nucleation but demonstrate the potential of engineering synthetic polymers as new biomimetics to control ice formation/growth processes PMID:26258729

  5. Microbial degradation of lignin: how a bulky recalcitrant polymer is efficiently recycled in nature and how we can take advantage of this

    PubMed Central

    Ruiz‐Dueñas, Francisco J.; Martínez, Ángel T.

    2009-01-01

    Summary Lignin is the second most abundant constituent of the cell wall of vascular plants, where it protects cellulose towards hydrolytic attack by saprophytic and pathogenic microbes. Its removal represents a key step for carbon recycling in land ecosystems, as well as a central issue for industrial utilization of plant biomass. The lignin polymer is highly recalcitrant towards chemical and biological degradation due to its molecular architecture, where different non‐phenolic phenylpropanoid units form a complex three‐dimensional network linked by a variety of ether and carbon–carbon bonds. Ligninolytic microbes have developed a unique strategy to handle lignin degradation based on unspecific one‐electron oxidation of the benzenic rings in the different lignin substructures by extracellular haemperoxidases acting synergistically with peroxide‐generating oxidases. These peroxidases posses two outstanding characteristics: (i) they have unusually high redox potential due to haem pocket architecture that enables oxidation of non‐phenolic aromatic rings, and (ii) they are able to generate a protein oxidizer by electron transfer to the haem cofactor forming a catalytic tryptophanyl‐free radical at the protein surface, where it can interact with the bulky lignin polymer. The structure–function information currently available is being used to build tailor‐made peroxidases and other oxidoreductases as industrial biocatalysts. PMID:21261911

  6. Ultrafast carrier photogeneration dynamics in polymer: fullerene solar cells probed by photocurrent-detected two-dimensional coherence spectroscopy (Presentation Recording)

    NASA Astrophysics Data System (ADS)

    Silva, Carlos

    2015-08-01

    In solar cells that incorporate semiconductor polymers as electron donors and fullerene derivatives as acceptors, a number of reports based on ultrafast optical probes reveal that charges can be generated on timescales significantly faster than ~100 fs in certain solid-state microstructures. Techniques that have been applied in these studies include variants of visible transient absorption and photoluminescence spectroscopy, terahertz spectroscopy, time-resolved infrared spectroscopy, and femtosecond stimulated Raman spectroscopy. These probes allow measurement of population dynamics of relevant photoexcitations (excitons, polarons) but do not reveal directly how these interact to produce photocarriers. Here, we present a non-linear coherent spectroscopy, photocurrent-detected two-dimensional spectroscopy (2DPC), which is an ultrafast optical thechnique belonging to a family of 2D Fourier- domain spectroscopies that allows measurement of correlations between optical transitions induced by short optical pulses. In our implementation, spectral correlations are detected via the time-integrated photocurrent produced in a photovoltaic diode. Four collinear ultrashort laser pulses (10 fs, centered at 600 nm in our experimental setup) excite the semiconductor polymer in the solar cell, with a variable delay that is independently controlled between each pulse in the sequence. Each pulse separately excites a quantum wavepacket with spectral phase and amplitude imparted by that pulse, while the effect of the pulse sequence is to collectively excite multiple quantum coherences. Interferences between the various combinations of the wavepackets determine linear and non-linear contributions to the material optical response. The fourth-order signal terms of the detected photocurrent are read using phase-sensitive detection schemes with reference waveforms corresponding to a modulation of specific phase combinations of the four femtosecond excitation pulses. By scanning the time

  7. DNA stable-isotope probing of oil sands tailings pond enrichment cultures reveals different key players for toluene degradation under methanogenic and sulfidogenic conditions.

    PubMed

    Laban, Nidal Abu; Dao, Anh; Foght, Julia

    2015-05-01

    Oil sands tailings ponds are anaerobic repositories of fluid wastes produced by extraction of bitumen from oil sands ores. Diverse indigenous microbiota biodegrade hydrocarbons (including toluene) in situ, producing methane, carbon dioxide and/or hydrogen sulfide, depending on electron acceptor availability. Stable-isotope probing of cultures enriched from tailings associated specific taxa and functional genes to (13)C6- and (12)C7-toluene degradation under methanogenic and sulfate-reducing conditions. Total DNA was subjected to isopycnic ultracentrifugation followed by gradient fraction analysis using terminal restriction fragment length polymorphism (T-RFLP) and construction of 16S rRNA, benzylsuccinate synthase (bssA) and dissimilatory sulfite reductase (dsrB) gene clone libraries. T-RFLP analysis plus sequencing and in silico digestion of cloned taxonomic and functional genes revealed that Clostridiales, particularly Desulfosporosinus (136 bp T-RF) contained bssA genes and were key toluene degraders during methanogenesis dominated by Methanosaeta. Deltaproteobacterial Desulfobulbaceae (157 bp T-RF) became dominant under sulfidogenic conditions, likely because the Desulfosporosinus T-RF 136 apparently lacks dsrB and therefore, unlike its close relatives, is presumed incapable of dissimilatory sulfate reduction. We infer incomplete oxidation of toluene by Desulfosporosinus in syntrophic association with Methanosaeta under methanogenic conditions, and complete toluene oxidation by Desulfobulbaceae during sulfate reduction.

  8. Metabolic versatility of toluene-degrading, iron-reducing bacteria in tidal flat sediment, characterized by stable isotope probing-based metagenomic analysis.

    PubMed

    Kim, So-Jeong; Park, Soo-Je; Cha, In-Tae; Min, Deullae; Kim, Jin-Seog; Chung, Won-Hyung; Chae, Jong-Chan; Jeon, Che Ok; Rhee, Sung-Keun

    2014-01-01

    DNA stable isotope probing and metagenomic sequencing were used to assess the metabolic potential of iron-reducing bacteria involved in anaerobic aromatic hydrocarbon degradation in oil spill-affected tidal flats. In a microcosm experiment, (13) C-toluene was degraded with the simultaneous reduction of Fe(III)-NTA, which was also verified by quasi-stoichiometric (13) C-CO2 release. The metabolic potential of the dominant member affiliated with the genus Desulfuromonas in the heavy DNA fraction was inferred using assembled scaffolds (designated TF genome, 4.40 Mbp with 58.8 GC mol%), which were obtained by Illumina sequencing. The gene clusters with peripheral pathways for toluene and benzoate conversion possessed the features of strict and facultative anaerobes. In addition to the class II-type benzoyl-CoA reductase (Bam) of strict anaerobes, the class I-type (Bcr) of facultative anaerobes was encoded. Genes related to the utilization of various anaerobic electron acceptors, including iron, nitrate (to ammonia), sulfur and fumarate, were identified. Furthermore, genes encoding terminal oxidases (caa3 , cbb3 and bd) and a diverse array of genes for oxidative stress responses were detected in the TF genome. This metabolic versatility may be an adaptation to the fluctuating availability of electron acceptors and donors in tidal flats.

  9. An extended micromechanics method for probing interphase properties in polymer nanocomposites [An extended micromechanics method for overlapping geometries with application to polymer nanocomposites

    DOE PAGES

    Liu, Zeliang; Moore, John A.; Liu, Wing Kam

    2016-05-03

    Inclusions comprised on filler particles and interphase regions commonly form complex morphologies in polymer nanocomposites. Addressing these morphologies as systems of overlapping simple shapes allows for the study of dilute particles, clustered particles, and interacting interphases all in one general modeling framework. To account for the material properties in these overlapping geometries, weighted-mean and additive overlapping conditions are introduced and the corresponding inclusion-wise integral equations are formulated. An extended micromechanics method based on these overlapping conditions for linear elastic and viscoelastic heterogeneous material is then developed. An important feature of the proposed approach is that the effect of both themore » geometric overlapping (clustered particles) and physical overlapping (interacting interphases) on the effective properties can be distinguished. Lastly, we apply the extended micromechanics method to a viscoelastic polymer nanocomposite with interphase regions, and estimate the properties and thickness of the interphase region based on experimental data for carbon-black filled styrene butadiene rubbers.« less

  10. Effect of incubation conditions on the enrichment of pyrene-degrading bacteria identified by stable-isotope probing in an aged, PAH-contaminated soil.

    PubMed

    Jones, Maiysha D; Singleton, David R; Carstensen, Darryl P; Powell, Sabrina N; Swanson, Julie S; Pfaender, Frederic K; Aitken, Michael D

    2008-08-01

    To determine whether the diversity of pyrene-degrading bacteria in an aged polycyclic aromatic hydrocarbon-contaminated soil is affected by the addition of inorganic nutrients or by slurrying the soil, various incubation conditions (all including phosphate buffer) were examined by mineralization studies and stable-isotope probing (SIP). The addition of nitrogen to either continuously mixed slurry or static field-wet soil incubations increased the rate and extent of mineralization of [(14)C]pyrene, with the most rapid mineralization observed in slurried, nitrogen-amended soil. Microcosms of slurry and static field-wet soil amended with nitrogen were also examined by SIP with [U-(13)C]pyrene. Recovered (13)C-enriched deoxyribonucleic acid (DNA) was analyzed by denaturing-gradient gel electrophoresis (DGGE) and 16S ribosomal ribonucleic acid (rRNA) gene clone libraries. DGGE profiles of (13)C-enriched DNA fractions from both incubation conditions were similar, suggesting that pyrene-degrading bacterial community diversity may be independent of treatment method. The vast majority (67 of 71) of the partial sequences recovered from clone libraries were greater than or equal to 97% similar to one another, 98% similar to sequences of pyrene-degrading bacteria previously detected by SIP with pyrene in different soil, and only 89% similar to the closest cultivated genus. All of the sequences recovered from the field-wet incubation and most of the sequences recovered from the slurry incubation were in this clade. Of the four sequences from slurry incubations not within this clade, three possessed greater than 99% similarity to the 16S rRNA gene sequences of phylogenetically dissimilar Caulobacter spp.

  11. Statistical optimization and artificial neural network modeling for acridine orange dye degradation using in-situ synthesized polymer capped ZnO nanoparticles.

    PubMed

    Dhiman, Nitesh; Markandeya; Singh, Amrita; Verma, Neeraj K; Ajaria, Nidhi; Patnaik, Satyakam

    2017-05-01

    ZnO NPs were synthesized by a prudent green chemistry approach in presence of polyacrylamide grafted guar gum polymer (pAAm-g-GG) to ensure uniform morphology, and functionality and appraised for their ability to degrade photocatalytically Acridine Orange (AO) dye. These ZnO@pAAm-g-GG NPs were thoroughly characterized by various spectroscopic, XRD and electron microscopic techniques. The relative quantity of ZnO NPs in polymeric matrix has been estimated by spectro-analytical procedure; AAS and TGA analysis. The impact of process parameters viz. NP's dose, contact time and AO dye concentration on percentage photocatalytic degradation of AO dyes were evaluated using multivariate optimizing tools, Response Surface Methodology (RSM) involving Box-Behnken Design (BBD) and Artificial Neural Network (ANN). Congruity of the BBD statistical model was implied by R(2) value 0.9786 and F-value 35.48. At RSM predicted optimal condition viz. ZnO@pAAm-g-GG NP's dose of 0.2g/L, contact time of 210min and AO dye concentration 10mg/L, a maximum of 98% dye degradation was obtained. ANOVA indicated appropriateness of the model for dye degradation owing to "Prob.>F" less than 0.05 for variable parameters. We further, employed three layers feed forward ANN model for validating the BBD process parameters and suitability of our chosen model. The evaluation of Levenberg-Marquardt algorithm (ANN1) and Gradient Descent with adaptive learning rate (ANN2) model employed to scrutinize the best method and found experimental values of AO dye degradation were in close to those with predicated value of ANN 2 modeling with minimum error.

  12. Polymer Soft-Landing Isolation of Acetylene on Polystyrene and Poly(vinylpyridine): A Novel Approach to Probing Hydrogen Bonding in Polymers.

    PubMed

    Li, Yike; Samet, Cindy

    2015-09-17

    Hydrogen-bonded complexes of acetylene (Ac) with the polymers polystyrene (PS), poly(4-vinylpyridine) (P4VP), and poly(2-vinylpyridine) (P2VP) have been characterized for the first time at 16 K in a "polymer soft-landing isolation" experiment which is being pioneered in our research laboratory. In particular, changes in vibrational modes of Ac provide ample evidence for hydrogen-bonded complexes between Ac and the phenyl groups of PS or the pyridyl groups of P4VP and P2VP. With PS, the proton on the top Ac molecule of the classic T-shaped Ac dimer interacts with the π cloud of the benzene (Bz) ring to form a C-H---π interaction, while the π cloud of the lower Ac forms a second C-H---π interaction with a proton on the Bz ring. An analogous (ring)1-(Ac)2 double interaction occurs between an Ac dimer and the pyridine (Pyr) rings on both P2VP and P4VP, yielding a C-H---N and C-H---π interaction. With P4VP and P2VP a second bridged (ring)2-(Ac)2 product is formed, with the Ac dimer forming nearly collinear C-H---N hydrogen bonds to adjacent Pyr rings. On P2VP this bridged product is the only one after extensive annealing. These complexes in which Ac acts as both proton donor and acceptor have not previously been observed in conventional matrix isolation experiments. This study is the second from our laboratory employing this method, which represents a slight modification of the traditional matrix isolation technique.

  13. Evaluation of reversible and irreversible degradation rates of polymer electrolyte membrane fuel cells tested in automotive conditions

    NASA Astrophysics Data System (ADS)

    Gazdzick, Pawel; Mitzel, Jens; Garcia Sanchez, Daniel; Schulze, Mathias; Friedrich, K. Andreas

    2016-09-01

    This work provides single cell durability tests of membrane electrode assemblies in dynamic operation regularly interrupted by recovery procedures for the removal of reversible voltage losses. Degradation rates at different loads in one single test can be determined from these tests. Hence, it is possible to report degradation rates versus current density instead of a single degradation rate value. A clear discrimination between reversible and irreversible voltage loss rates is provided. The irreversible degradation rate can be described by a linear regression of voltage values after the recovery steps. Using voltage values before refresh is less adequate due to possible impacts of reversible effects. The reversible contribution to the voltage decay is dominated by an exponential decay after restart, eventually turning into a linear one. A linear-exponential function is proposed to fit the reversible voltage degradation. Due to this function, the degradation behavior of an automotive fuel cell can be described correctly during the first hours after restart. The fit parameters decay constant, exponential amplitude and linear slope are evaluated. Eventually, the reasons for the voltage recovery during shutdown are analyzed showing that ionomer effects in the catalyst layer and/or membrane seem to be the key factor in this process.

  14. Imidazolium-Based Porous Organic Polymers: Anion Exchange-Driven Capture and Luminescent Probe of Cr2O7(2.).

    PubMed

    Su, Yanqing; Wang, Yangxin; Li, Xiaoju; Li, Xinxiong; Wang, Ruihu

    2016-07-27

    A series of imidazolium-based porous organic polymers (POP-Ims) was synthesized through Yamamoto reaction of 1,3-bis(4-bromophenyl)imidazolium bromide and tetrakis(4-bromophenyl)ethylene. Porosities and hydrophilicity of such polymers may be well tuned by varying the ratios of two monomers. POP-Im with the highest density of imidazolium moiety (POP-Im1) exhibits the best dispersity in water and the highest efficiency in removing Cr2O7(2-). The capture capacity of 171.99 mg g(-1) and the removal efficiency of 87.9% were achieved using an equivalent amount of POP-Im1 within 5 min. However, no Cr2O7(2-) capture was observed using nonionic analogue despite its large surface area and abundant pores, suggesting that anion exchange is the driving force for the removal of Cr2O7(2-). POP-Im1 also displays excellent enrichment ability and remarkable selectivity in capturing Cr2O7(2-). Cr(VI) in acid electroplating wastewater can be removed completely using excess POP-Im1. In addition, POP-Im1 can serve as a luminescent probe for Cr2O7(2-) due to the incorporation of luminescent tetraphenylethene moiety.

  15. Probing the degradation mechanisms in electrolyte solutions for Li-ion batteries by in situ transmission electron microscopy.

    PubMed

    Abellan, Patricia; Mehdi, B Layla; Parent, Lucas R; Gu, Meng; Park, Chiwoo; Xu, Wu; Zhang, Yaohui; Arslan, Ilke; Zhang, Ji-Guang; Wang, Chong-Min; Evans, James E; Browning, Nigel D

    2014-03-12

    Development of novel electrolytes with increased electrochemical stability is critical for the next generation battery technologies. In situ electrochemical fluid cells provide the ability to rapidly and directly characterize electrode/electrolyte interfacial reactions under conditions directly relevant to the operation of practical batteries. In this paper, we have studied the breakdown of a range of inorganic/salt complexes relevant to state-of-the-art Li-ion battery systems by in situ (scanning) transmission electron microscopy ((S)TEM). In these experiments, the electron beam itself caused the localized electrochemical reaction that allowed us to observe electrolyte breakdown in real-time. The results of the in situ (S)TEM experiments matches with previous stability tests performed during battery operation and the breakdown products and mechanisms are also consistent with known mechanisms. This analysis indicates that in situ liquid stage (S)TEM observations could be used to directly test new electrolyte designs and identify a smaller library of candidate solutions deserving of more detailed characterization. A systematic study of electrolyte degradation is also a necessary first step for any future controlled in operando liquid (S)TEM experiments intent on visualizing working batteries at the nanoscale.

  16. Degradation of methyl bromide and methyl chloride in soil microcosms: Use of stable C isotope fractionation and stable isotope probing to identify reactions and the responsible microorganisms

    USGS Publications Warehouse

    Miller, L.G.; Warner, K.L.; Baesman, S.M.; Oremland, R.S.; McDonald, I.R.; Radajewski, S.; Murrell, J.C.

    2004-01-01

    Bacteria in soil microcosm experiments oxidized elevated levels of methyl chloride (MeCl) and methyl bromide (MeBr), the former compound more rapidly than the latter. MeBr was also removed by chemical reactions while MeCl was not. Chemical degradation dominated the early removal of MeBr and accounted for more than half of its total loss. Fractionation of stable carbon isotopes during chemical degradation of MeBr resulted in a kinetic isotope effect (KIE) of 59 ?? 7???. Soil bacterial oxidation dominated the later removal of MeBr and MeCl and was characterized by different KIEs for each compound. The KIE for MeBr oxidation was 69 ?? 9??? and the KIE for MeCl oxidation was 49 ?? 3???. Stable isotope probing revealed that different populations of soil bacteria assimilated added 13C-labeled MeBr and MeCl. The identity of the active MeBr and MeCl degrading bacteria in soil was determined by analysis of 16S rRNA gene sequences amplified from 13C-DNA fractions, which identified a number of sequences from organisms not previously thought to be involved in methyl halide degradation. These included Burkholderia , the major clone type in the 13C-MeBr fraction, and Rhodobacter, Lysobacter and Nocardioides the major clone types in the 13C-MeCl fraction. None of the 16S rRNA gene sequences for methyl halide oxidizing bacteria currently in culture (including Aminobacter strain IMB-1 isolated from fumigated soil) were identified. Functional gene clone types closely related to Aminobacter spp. were identified in libraries containing the sequences for the cmuA gene, which codes for the enzyme known to catalyze the initial step in the oxidation of MeBr and MeCl. The cmuA gene was limited to members of the alpha-Proteobacteria whereas the greater diversity demonstrated by the 16S rRNA gene may indicate that other enzymes catalyze methyl halide oxidation in different groups of bacteria. Copyright ?? 2004 Elsevier Ltd.

  17. Simultaneous electrochemical immunoassay using graphene-Au grafted recombinant apoferritin-encoded metallic labels as signal tags and dual-template magnetic molecular imprinted polymer as capture probes.

    PubMed

    Wang, De; Gan, Ning; Zhang, Huairong; Li, Tianhua; Qiao, Li; Cao, Yuting; Su, Xiurong; Jiang, Shan

    2015-03-15

    A novel electrochemical multiplexed immunoassay was designed for simultaneous determination of alpha-fetoprotein (AFP) and carcinoembryonic antigen (CEA) using recombinant apoferritin-encoded metallic nanoparticles (rApo-M) as labels and dual-template magnetic molecularly imprinted polymers (MMIPs) as capture probes. The labels were prepared by loading recombinant apoferritin (r-Apo) and separately immobilize primary antibodies (anti-AFP and anti-CEA) via Au nanoparticles of in site growth on graphene (G). The capture probes were synthesized by self-polymerization of dopamine (DA) on the Fe3O4 nanoparticles (Fe3O4 NPs) and using AFP and CEA as the template proteins, which were used to enrich the targets simultaneously. After a sandwich-type immunoreaction, the labels were captured to the surface of MMIPs. The subsequent electrochemical stripping analysis of the metal components from the immunocomplex provide a means for quantification of targets based on the peak currents of Cd and Pb. Experimental results showed the immunoassay enabled the simultaneous determination of AFP and CEA in a single run with wide dynamic ranges of 0.001-5ngmL(-1). And the detection limits of AFP and CEA were 0.3 and 0.35pgmL(-1) (S/N=3), respectively. These results suggested that the proposed multiplexed immunoassay would be applied for clinical screening of other biomarkers.

  18. A novel bio-degradable polymer stabilized Ag/TiO2 nanocomposites and their catalytic activity on reduction of methylene blue under natural sun light.

    PubMed

    Geetha, D; Kavitha, S; Ramesh, P S

    2015-11-01

    In the present work we defined a novel method of TiO2 doped silver nanocomposite synthesis and stabilization using bio-degradable polymers viz., chitosan (Cts) and polyethylene glycol (PEG). These polymers are used as reducing agents. The instant formation of AgNPs was analyzed by visual observation and UV-visible spectrophotometer. TiO2 nanoparticles doped at different concentrations viz., 0.03, 0.06 and 0.09mM on PEG/Cts stabilized silver (0.04wt%) were successfully synthesized. This study presents a simple route for the in situ synthesis of both metal and polymer confined within the nanomaterial, producing ternary hybrid inorganic-organic nanomaterials. The results reveal that they have higher photocatalytic efficiencies under natural sun light. The synthesized TiO2 doped Ag nanocomposites (NCs) were characterized by SEM/EDS, TEM, XRD, FTIR and DLS with zeta potential. The stability of Ag/TiO2 nanocomposite is due to the high negative values of zeta potential and capping of constituents present in the biodegradable polymer which is evident from zeta potential and FT-IR studies. The XRD and EDS pattern of synthesized Ag/TiO2 NCs showed their crystalline structure, with face centered cubic geometry oriented in (111) plane. AFM and DLS studies revealed that the diameter of stable Ag/TiO2 NCs was approximately 35nm. Moreover the catalytic activity of synthesize Ag/TiO2 NCs in the reduction of methylene blue was studied by UV-visible spectrophotometer. The synthesized Ag/TiO2 NCs are observed to have a good catalytic activity on the reduction of methylene blue by bio-degradable which is confirmed by the decrease in absorbance maximum value of methylene blue with respect to time using UV-vis spectrophotometer. The significant enhancement in the photocatalytic activity of Ag/TiO2 nanocomposites under sun light irradiation can be ascribed to the effect of noble metal Ag by acting as electron traps in TiO2 band gap.

  19. Anomalous Diffusion in Polymer Solution as Probed by Fluorescence Correlation Spectroscopy and Its Universal Importance in Biological Systems

    NASA Astrophysics Data System (ADS)

    Ushida, Kiminori

    2008-02-01

    Experimental evidence of anomalous diffusion occurring in an inhomogeneous media (hyaluronan aquous solution) was obtained by use of fluorescence correlation spectroscopy (FCS) combined with other techniques (PFG-NMR and Photochemical reactions). The diffusion coefficient was obtained as a function of diffusion time or diffusion distance. Since this polymer solution can be regarded as a model system of extracellular matrices (ECMs), intercellular communication, which takes part in ECM, is greatly influenced by this anomalous diffusion mode. Therefore universal importance of anomalous diffusion in biological activity is identified in this series of independent experiments to measure diffusion coefficients.

  20. Poly(Beta-Hydroxybutyrate) Stereoisomers: A Model Study of the Effects of Stereochemical and Morphological Variables on Polymer Biological Degradability

    DTIC Science & Technology

    1992-01-01

    sole source of carbon. The bacterial ybutyrate), (R)-PHB, which is a highly crystalline bio- strains Pseudomonas ?remoignei (ATCC 17989)15-18 and...degradable thermoplastic.8 Alcaligenes faecalis T1,1s9A isolated from soil and activated Several researchers have studied the depolymerization sewage sludge

  1. Identification of Unsaturated and 2H Polyfluorocarboxylate Homologous Series and Their Detection in Environmental Samples and as Polymer Degradation Products

    EPA Science Inventory

    A pair of homologous series of polyfluorinated degradation products have been identified, both having structures similar to perfluorocarboxylic acids but (i) having a H substitution for F on the α carbon for 2H polyfluorocarboxylic acids (2HPFCAs) and (ii) bearing a double ...

  2. Radiation induced structural and motional changes occurring in silica filled silicone polymer foams as probed by multinuclear NMR

    SciTech Connect

    Maxwell, R.S.; Balazs, B.; Chien, A.; LeMay, J.

    1999-10-14

    The aging of polymeric composite materials through factors such as thermal and mechanical stresses, environment, radiation, and chemical attack can affect the length of time for which a given material can maintain its engineering performance. Iterative interactions and cumulative reactions may result in the material or device reaching a critical age where its properties fail unexpectedly and catastrophically. The mechanical poperty changes associated with multi-mechanism aging may be subtle, and may not necessarily change linearly as a function of time in service. Since such linear relationships are often used in lifetime predictions, there is a fundamental need to develop and employ spectroscopic methods to investigate the structural and motional changes that occur in these organic-inorganic materials as a result of aging in chemically, thermally, or radioactively harsh environments. Silica filled polydimethylsiloxane (PDMS) composite systems are of technological interest due to their chemical and environmental resilience. Silica is usually chosen as the filler phase due to the significant reinforcement of the composite material through hydrogen bonding between the polymer chains and the surface groups on the filler. Unfilled PDMS is known to crosslink when exposed to high-energy radiation. The presence of a silica filler phase, which has a higher electron density than the polymer matrix, has been proposed to result in an increased incidence of crosslinking or scission due to backscatter of the incident radiation. Cohen-Addad has used {sup 1}H relaxation times to characterized cross-link density in unirradiated filled PDMS and Charlesby has reported {sup 1}H relaxation studies of irradiation induced changes in unfilled PDMS systems of average molccular weights up to 1 MDalton. However, no specific studies have been reported on aging of silica-filled PDMS based polymers systems. To this end the authors have applied Nuclear Magnetic Resonance (NMR) methods to gain

  3. Temperature Dependence of the Viscoelastic Properties of a Confined Liquid Polymer Measured by Using an Oscillating Optical Fiber Probe

    NASA Astrophysics Data System (ADS)

    Itoh, Shintaro; Fukuzawa, Kenji; Hamamoto, Yuya; Zhang, Hedong

    2010-08-01

    We measured the temperature dependence of the viscoelastic properties of a liquid polymer confined and sheared within a nanometer-sized gap. In the viscoelastic measurements, we used the fiber wobbling method, a highly sensitive method that we have developed for measuring shear forces. As a liquid sample, we used the fluoropolyether lubricant Fomblin Zdol4000. Our experimental results showed that the temperature dependence of the viscosity was well expressed by the well-known Andrade equation, even in the confined state. The activation enthalpy was calculated by assuming that Eyring's theory of viscosity holds for gaps of a width ranging from 100 nm down to a few nanometers. We observed a significant decrease in the activation enthalpy for gaps smaller than 10 nm. Elasticity, which only appeared for confinement in gaps smaller than 10 nm, roughly decreased with increasing temperature.

  4. Synthesis and In Vivo Pharmacokinetic Evaluation of Degradable Shell Crosslinked Polymer Nanoparticles with Poly(carboxybetaine) vs. Poly(ethylene glycol) Surface-grafted Coatings

    PubMed Central

    Li, Ang; Luehmann, Hannah P.; Sun, Guorong; Samarajeewa, Sandani; Zou, Jiong; Zhang, Shiyi; Zhang, Fuwu; Welch, Michael J.; Liu, Yongjian; Wooley, Karen L.

    2012-01-01

    Nanoparticles with tunable pharmacokinetics are desirable for various biomedical applications. Poly(ethylene glycol) (PEG) is well known to create “stealth” effects to stabilize and extend the blood circulation of nanoparticles. In this work, poly(carboxybetaine) (PCB), a new non-fouling polymer material, was incorporated as surface-grafted coatings, conjugated onto degradable shell crosslinked knedel-like nanoparticles (dSCKs) composed of poly(acrylic acid)- based shells and poly(lactic acid) (PLA) cores, to compare the in vivo pharmacokinetics to their PEG-functionalized analogs. A series of five dSCKs was prepared from amphiphilic block copolymers, having different numbers and lengths of either PEG or PCB grafts, by supramolecular assembly in water followed by shell crosslinking, and then studied by a lactate assay to confirm their core hydrolytic degradabilities. Each dSCK was also conjugated with 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) macrocyclic chelators and tyramine moieties to provide for 64Cu and/or radiohalogen labeling. The high specific activity of 64Cu radiolabeling ensured nanogram administration of dSCKs for in vivo evaluation of their pharmacokinetics. Biodistribution studies demonstrated comparable in vivo pharmacokinetic profiles of PCB-grafted dSCKs to their PEG-conjugated counterparts. These results indicated that PCB-functionalized dSCKs have great potential as a theranostic platform for translational research. PMID:23043240

  5. A hydrated phospholipid polymer-grafted layer prevents lipid-related oxidative degradation of cross-linked polyethylene.

    PubMed

    Kyomoto, Masayuki; Moro, Toru; Yamane, Shihori; Takatori, Yoshio; Tanaka, Sakae; Ishihara, Kazuhiko

    2017-01-01

    The surface and substrate of a cross-linked polyethylene (CLPE) liner are designed to achieve resistance against oxidative degradation in the construction of hip joint replacements. In this study, we aimed to evaluate the oxidative degradation caused by lipid absorption of a highly hydrophilic nanometer-scaled thickness layer prepared by grafting a poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) layer and a high-dose gamma-ray irradiated CLPE with vitamin E blending (HD-CLPE[VE]). The HD-CLPE(VE) and PMPC-grafted HD-CLPE(VE) exhibited extremely high oxidation resistance regardless of lipid absorption, even though residual-free radical levels were detectable. The water wettability of the PMPC-grafted CLPE and PMPC-grafted HD-CLPE(VE) surfaces was considerably greater than that of untreated surfaces. The hydrated PMPC-grafted layer also exhibited extremely low solubility for squalene. Lipids such as squalene and cholesterol esters diminished the oxidation resistance of CLPE despite the vitamin E improvement. Notably, the PMPC-grafted surface was resistant to lipid absorption and diffusion as well as subsequent lipid-related oxidative degradation, likely because of the presence of the hydrated PMPC-grafted layer. Together, these results provide preliminary evidence that the resistance against lipid absorption and diffusion of a hydrated PMPC-grafted layer might positively affect the extent of resistance to the in vivo oxidation of orthopedic implants.

  6. A cost-effective sandwich electrochemiluminescence immunosensor for ultrasensitive detection of HIV-1 antibody using magnetic molecularly imprinted polymers as capture probes.

    PubMed

    Zhou, Jing; Gan, Ning; Li, Tianhua; Hu, Futao; Li, Xing; Wang, Lihong; Zheng, Lei

    2014-04-15

    In this report, a rapid and cost-effective sandwich electrochemiluminescence (ECL) immunosensor was constructed for the ultrasensitive detection of human immunodeficiency virus type 1 antibody (anti-HIV-1) using magnetic molecularly imprinted polymers (MMIPs) as capture probes by combining surface and epitope imprinting techniques and antigen conjugated with horseradish peroxidase (HRP-HIV-1) as labels. First, 3-aminobenzeneboronic acid (APBA) was used as the functional monomer and cross-linking reagent, which was polymerized on the surface of silicate-coated magnetic iron oxide nanoparticles (Fe3O4@SiO2 NPs) in the presence of human immunoglobulin G (HIgG), as the template exhibiting the same Fc region but different Fab region to anti-HIV-1 after the addition of the initiator, ammonium persulfate. This process resulted in grafting a hydrophilic molecularly imprinted polymer (MIP) film on the Fe3O4@SiO2 NPs. Thus, MMIPs, which could be reused after eluting the template, were used to recognize and enrich ultra-trace levels of anti-HIV-1. Subsequently, a novel sandwich ECL immunosensor was formed through the immunoreaction between MMIPs conjugated with varied concentrations of anti-HIV-1 and HRP-HIV-1. By the catalysis of HRP immobilized onto HRP-HIV-1 on the ECL system of Luminol-H2O2, a linear response range of the anti-HIV-1 dilution ratio (standard positive serum) was achieved from 1:20,000 to 1:50, with a detection limit of 1:60,000 (S/N=3). The developed method provides a low-cost, simple, and sensitive way for the early diagnosis of HIV infected patients.

  7. Operational electrochemical stability of thiophene-thiazole copolymers probed by resonant Raman spectroscopy

    SciTech Connect

    Wade, Jessica; Wood, Sebastian; Kim, Ji-Seon; Beatrup, Daniel; Hurhangee, Michael; McCulloch, Iain; Durrant, James R.; Bronstein, Hugo

    2015-06-28

    We report on the electrochemical stability of hole polarons in three conjugated polymers probed by resonant Raman spectroscopy. The materials considered are all isostructural to poly(3-hexyl)thiophene, where thiazole units have been included to systematically deepen the energy level of the highest occupied molecular orbital (HOMO). We demonstrate that increasing the thiazole content planarizes the main conjugated backbone of the polymer and improves the electrochemical stability in the ground state. However, these more planar thiazole containing polymers are increasingly susceptible to electrochemical degradation in the polaronic excited state. We identify the degradation mechanism, which targets the C=N bond in the thiazole units and results in disruption of the main polymer backbone conjugation. The introduction of thiazole units to deepen the HOMO energy level and increase the conjugated backbone planarity can be beneficial for the performance of certain optoelectronic devices, but the reduced electrochemical stability of the hole polaron may compromise their operational stability.

  8. Applicability of new degradable hypericin-polymer-conjugates as photosensitizers: principal mode of action demonstrated by in vitro models.

    PubMed

    Feinweber, Daniela; Verwanger, Thomas; Brüggemann, Oliver; Teasdale, Ian; Krammer, Barbara

    2014-11-01

    Two series of water soluble novel conjugates of the photosensitizer hypericin were prepared and evaluated for their use as agents for photodynamic therapy, with covalently and non-covalently loaded hypericin on functionalised, hydrolytically degradable inorganic-organic hybrid polyphosphazenes. The conjugates showed excellent aqueous solubility and similar fluorescence spectra to pristine hypericin. Detailed in vitro investigations revealed that the substances were non-toxic in the dark over a wide concentration range, but displayed phototoxicity upon irradiation. Cell uptake studies showed rapid uptake with localization of hypericin observed in endoplasmic reticulum, Golgi complex and particularly in the lysosomes. Furthermore, a DNA fragmentation assay revealed that the photosensitizer conjugates are efficient inducers of apoptosis with some tumor cell selectivity caused by faster and enhanced accumulation in A431 than in HaCaT cells, and thus a moderately higher phototoxicity of A431 compared to HaCaT cells. These novel photosensitizer conjugates hence represent viable hydrolytically degradable alternatives for the advanced delivery of hypericin.

  9. Degradation effects in polymer electrolyte membrane fuel cell stacks by sub-zero operation-An in situ and ex situ analysis

    NASA Astrophysics Data System (ADS)

    Alink, R.; Gerteisen, D.; Oszcipok, M.

    The effect of low temperatures down to -40 °C on the performance and component properties of a polymer electrolyte membrane (PEM) fuel cell stack was investigated. By analyzing the temperature-dependent high-frequency resistance, the mechanism of ice formation within the stack was investigated during freeze/thaw (F/T) cycling while the stack was not operating and during a cold start-up. A step-like change in conductivity at 0 °C indicates that the membranes are dehydrated at sub-zero temperatures due to a change in capillary pressure at the interface membrane/catalyst. Furthermore, it was found that the stack shows little degradation when it is dried out before cooling down. Freezing in a wet state and additional cold start-ups resulted in performance degradation which was mainly attributed to changes in wetting properties. Ex situ environmental scanning electron microscope (ESEM) investigations showed distinct damage and increasing porosity of the electrode in the wet frozen stack, which was most likely the reason for the change in wetting properties. Inductively coupled plasma (ICP) mass spectroscopy showed distinct concentrations of platinum in the exhaust gas of the dry cycled stack, but no additional platinum was found when the stack was cycled in a wet state. Additional ex situ F/T investigations of gas diffusion layers (GDLs) and membrane electrode assemblies (MEAs) within an ESEM confirmed the results, found by in situ investigations of the fuel cell stacks. Serious detachment of electrode material was found without the compressive force applied to an assembly.

  10. PEG-b-AGE Polymer Coated Magnetic Nanoparticle Probes with Facile Functionalization and Anti-fouling Properties for Reducing Non-specific Uptake and Improving Biomarker Targeting

    PubMed Central

    Wang, Liya; Huang, Jing; Wu, Hui; Cheng, Guojun; Zhou, Zhengyang; MacDonald, Tobey; Yang, Lily; Mao, Hui

    2015-01-01

    Non-specific surface adsorption of bio-macromolecules (e.g. proteins) on nanoparticles, known as biofouling, and the uptake of nanoparticles by the mononuclear phagocyte system (MPS) and reticuloendothelial system (RES) lead to substantial reduction in the efficiency of target-directed imaging and delivery in biomedical applications of engineered nanomaterials in vitro and in vivo. In this work, a novel copolymer consisting of blocks of poly ethylene glycol and allyl glycidyl ether (PEG-b-AGE) was developed for coating magnetic iron oxide nanoparticles (IONPs) to reduce non-specific protein adhesion that leads to formation of “protein corona” and uptake by macrophages. The facile surface functionalization was demonstrated by using targeting ligands of a small peptide of RGD or a whole protein of transferrin (Tf). The PEG-b-AGE coated IONPs exhibited anti-biofouling properties with significantly reduced protein corona formation and non-specific uptake by macrophages before and after the surface functionalization, thus improving targeting of RGD-conjugated PEG-b-AGE coated IONPs to integrins in U87MG glioblastoma and MDA-MB-231 breast cancer cells that overexpress αvβ3 integrins, and Tf-conjugated PEG-b-AGE coated IONPs to transferrin receptor (TfR) in D556 and Daoy medulloblastoma cancer cells with high overexpression of transferrin receptor, compared to respective control cell lines. Magnetic resonance imaging (MRI) of cancer cells treated with targeted IONPs with or without anti-biofouling PEG-b-AGE coating polymers demonstrated the target specific MRI contrast change using anti-biofouling PEG-b-AGE coated IONP with minimal off-targeted background compared to the IONPs without anti-biofouling coating, promising the highly efficient active targeting of nanoparticle imaging probes and drug delivery systems and potential applications of imaging quantification of targeted biomarkers. PMID:26594360

  11. PEG-b-AGE Polymer Coated Magnetic Nanoparticle Probes with Facile Functionalization and Anti-fouling Properties for Reducing Non-specific Uptake and Improving Biomarker Targeting.

    PubMed

    Li, Yuancheng; Lin, Run; Wang, Liya; Huang, Jing; Wu, Hui; Cheng, Guojun; Zhou, Zhengyang; MacDonald, Tobey; Yang, Lily; Mao, Hui

    2015-05-07

    Non-specific surface adsorption of bio-macromolecules (e.g. proteins) on nanoparticles, known as biofouling, and the uptake of nanoparticles by the mononuclear phagocyte system (MPS) and reticuloendothelial system (RES) lead to substantial reduction in the efficiency of target-directed imaging and delivery in biomedical applications of engineered nanomaterials in vitro and in vivo. In this work, a novel copolymer consisting of blocks of poly ethylene glycol and allyl glycidyl ether (PEG-b-AGE) was developed for coating magnetic iron oxide nanoparticles (IONPs) to reduce non-specific protein adhesion that leads to formation of "protein corona" and uptake by macrophages. The facile surface functionalization was demonstrated by using targeting ligands of a small peptide of RGD or a whole protein of transferrin (Tf). The PEG-b-AGE coated IONPs exhibited anti-biofouling properties with significantly reduced protein corona formation and non-specific uptake by macrophages before and after the surface functionalization, thus improving targeting of RGD-conjugated PEG-b-AGE coated IONPs to integrins in U87MG glioblastoma and MDA-MB-231 breast cancer cells that overexpress αvβ3 integrins, and Tf-conjugated PEG-b-AGE coated IONPs to transferrin receptor (TfR) in D556 and Daoy medulloblastoma cancer cells with high overexpression of transferrin receptor, compared to respective control cell lines. Magnetic resonance imaging (MRI) of cancer cells treated with targeted IONPs with or without anti-biofouling PEG-b-AGE coating polymers demonstrated the target specific MRI contrast change using anti-biofouling PEG-b-AGE coated IONP with minimal off-targeted background compared to the IONPs without anti-biofouling coating, promising the highly efficient active targeting of nanoparticle imaging probes and drug delivery systems and potential applications of imaging quantification of targeted biomarkers.

  12. A statistical design of experiments for optimizing the MALDI-TOF-MS sample preparation of polymers. An application in the assessment of the thermo-mechanical degradation mechanisms of poly (ethylene terephthalate).

    PubMed

    Badía, J D; Strömberg, E; Ribes-Greus, A; Karlsson, S

    2011-04-29

    The sample preparation procedure for MALDI-TOF MS of polymers is addressed in this study by the application of a statistical Design of Experiments (DoE). Industrial poly (ethylene terephthalate) (PET) was chosen as model polymer. Different experimental settings (levels) for matrixes, analyte/matrix proportions and concentrations of cationization agent were considered. The quality parameters used for the analysis were signal-to-noise ratio and resolution. A closer inspection of the statistical results provided the study not only with the best combination of factors for the MALDI sample preparation, but also with a better understanding of the influence of the different factors, individually or in combination, to the signal. The application of DoE for the improvement of the MALDI measure of PET stated that the best combination of factors and levels was the following: matrix (dithranol), proportion analyte/matrix/cationization agent (1/15/1, V/V/V), and concentration of cationization agent (2 g L(-1)). In a second part, multiple processing by means of successive injection cycles was used to simulate the thermo-mechanical degradation effects on the oligomeric distribution of PET under mechanical recycling. The application of MALDI-TOF-MS showed that thermo-mechanical degradation primarily affected initially predominant cyclic species. Several degradation mechanisms were proposed, remarking intramolecular transesterification and hydrolysis. The ether links of the glycol unit in PET were shown to act as potential reaction sites, driving the main reactions of degradation.

  13. Structural characterization of synthetic polymers and copolymers using multidimensional mass spectrometry interfaced with thermal degradation, liquid chromatography and/or ion mobility separation

    NASA Astrophysics Data System (ADS)

    Alawani, Nadrah

    This dissertation focuses on coupling mass spectrometry (MS) and tandem mass spectrometry (MS/MS) to thermal degradation, liquid chromatography (LC) and/or ion mobility (IM) spectrometry for the characterization of complex mixtures. In chapter II, an introduction of the history and the principles of MS and LC are discussed. Chapter III illustrates the materials and instrumentation used to complete this dissertation. Polyethers have been characterized utilizing MS/MS, as presented in Chapter IV and Chapter VI. Diblock copolymers of polyethylene oxide and polycaprolactone, PEO-b-PCL, have been characterized by matrix-assisted laser desorption/ionization quadrupole/time-of-flight mass spectrometry (MALDI-Q/ToF) and LC-MS/MS (Chapter V). Thermoplastic elastomers have been characterized by thermal degradation using an atmospheric solids analysis probe (ASAP) and ion mobility mass spectrometry (IM-MS), as discussed in Chapter VII. Interfacing separation techniques with mass spectrometry permitted the detection of species present with low concentration in complex materials and improved the sensitivity of MS. In chapter IV, the fragmentation mechanisms in MS/MS experiments of cyclic and linear poly(ethylene oxide) macroinitiators are discussed. This study aimed at determining the influence of end groups on the fragmentation pathways. In the study reported in Chapter V, ultra high performance liquid chromatography (UHPLC) was interfaced with MS and MS/MS to achieve the separation and in-depth characterization and separation of amphiphilic diblock copolymers (PEO- b-PCL) in which the architecture of the PEO block is linear or cyclic. Applying UPLC-MS and UPLC-MS/MS provides fast accurate information about the number and type of the blocks in the copolymers. Chapter VI reports MS/MS and IM-MS analyses which were performed to elucidate the influence of molecular size and collision energy on the fragmentation pathways of polyethers subjected to collisionally activated

  14. In situ analysis of plant tissue underivatized carbohydrates and on-probe enzymatic degraded starch by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry by using carbon nanotubes as matrix.

    PubMed

    Gholipour, Yousef; Nonami, Hiroshi; Erra-Balsells, Rosa

    2008-12-15

    Underivatized carbohydrates of tulip bulb and leaf tissues were characterized in situ by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) by using carbon nanotubes (CNTs) as matrix. Two sample preparation methods--(i) depositing CNTs on the fresh tissue slices placed on the probe and (ii) locating semitransparent tissues on a dried layer of CNTs on the probe--were examined. Furthermore, practicability of in situ starch analysis by MALDI-TOF MS was examined by detection of glucose originated from on-probe amyloglucosidase-catalyzed degradation of starch on the tissue surface. Besides, CNTs could efficiently desorb/ionize natural mono-, di-, and oligosaccharides extracted from tulip bulb tissues as well as glucose resulting from starch enzymatic degradation in vitro. These results were compared with those obtained by in situ MALDI-TOF MS analysis of similar tissues. Positive ion mode showed superior signal reproducibility. CNTs deposited under semitransparent tissue could also desorb/ionize neutral carbohydrates, leading to nearly complete elimination of matrix cluster signals but with an increase in tissue-originated signals. Furthermore, several experiments were carried out to compare the efficiency of 2,5-dihydroxybenzoic acid, nor-harmane, alpha-cyano-4-hydroxycinnamic acid, and CNTs as matrices for MALDI of neutral carbohydrates from the intact plant tissue surface and for enzymatic tissue starch degradation; these results are discussed in brief. Among matrices studied, the lowest laser power was needed to acquire carbohydrate signals with high signal-to-noise ratio and resolution when CNTs were used.

  15. Effect of Glucose on the Fatty Acid Composition of Cupriavidus necator JMP134 during 2,4-Dichlorophenoxyacetic Acid Degradation: Implications for Lipid-Based Stable Isotope Probing Methods▿†

    PubMed Central

    Lerch, Thomas Z.; Dignac, Marie-France; Barriuso, Enrique; Mariotti, André

    2011-01-01

    Combining lipid biomarker profiling with stable isotope probing (SIP) is a powerful technique for studying specific microbial populations responsible for the degradation of organic pollutants in various natural environments. However, the presence of other easily degradable substrates may induce significant physiological changes by altering both the rate of incorporation of the target compound into the biomass and the microbial lipid profiles. In order to test this hypothesis, Cupriavidus necator JMP134, a 2,4-dichlorophenoxyacetic acid (2,4-D)-degrading bacterium, was incubated with [13C]2,4-D, [13C]glucose, or mixtures of both substrates alternatively labeled with 13C. C. necator JMP134 exhibited a preferential use of 2,4-D over glucose. The isotopic analysis showed that glucose had only a small effect on the incorporation of the acetic chain of 2,4-D into the biomass (at days 2 and 3) and no effect on that of the benzenic ring. The addition of glucose did change the fatty acid methyl ester (FAME) composition. However, the overall FAME isotopic signature reflected that of the entire biomass. Compound-specific individual isotopic analyses of FAME composition showed that the 13C-enriched FAME profiles were slightly or not affected when tracing the 2,4-D acetic chain or 2,4-D benzenic ring, respectively. This batch study is a necessary step for validating the use of lipid-based SIP methods in complex environments. PMID:21856833

  16. Characterizing Fluorotelomer and Polyfluoroalkyl Substances in New and Aged Fluorotelomer-Based Polymers for Degradation Studies with GC/MS and LC/MS/MS

    EPA Science Inventory

    Fluorotelomer-based polymers (FTPs), the dominant product of the fluorotelomer industry, are antistaining and antiwetting agents that permeate the products and surfaces of modern society. However, the degree to which these materials expose humans and the environment to fluorotelo...

  17. Electrical condition monitoring method for polymers

    DOEpatents

    Watkins, Jr. Kenneth S.; Morris, Shelby J.; Masakowski, Daniel D.; Wong, Ching Ping; Luo, Shijian

    2010-02-16

    An electrical condition monitoring method utilizes measurement of electrical resistivity of a conductive composite degradation sensor to monitor environmentally induced degradation of a polymeric product such as insulated wire and cable. The degradation sensor comprises a polymeric matrix and conductive filler. The polymeric matrix may be a polymer used in the product, or it may be a polymer with degradation properties similar to that of a polymer used in the product. The method comprises a means for communicating the resistivity to a measuring instrument and a means to correlate resistivity of the degradation sensor with environmentally induced degradation of the product.

  18. Use of a sub-gasket and soft gas diffusion layer to mitigate mechanical degradation of a hydrocarbon membrane for polymer electrolyte fuel cells in wet-dry cycling

    NASA Astrophysics Data System (ADS)

    Ishikawa, Hiroshi; Teramoto, Takeshi; Ueyama, Yasuhiro; Sugawara, Yasushi; Sakiyama, Yoko; Kusakabe, Masato; Miyatake, Kenji; Uchida, Makoto

    2016-09-01

    The mechanical durability of hydrocarbon (HC) membranes, used for polymer electrolyte fuel cells (PEFCs), was evaluated by the United States Department of Energy (USDOE) stress protocol involving wet-dry cycling, and the degradation mechanism is discussed. The HC membrane ruptured in the edge region of the membrane electrode assembly (MEA) after 300 cycles due to a concentration of the mechanical stress. Post-test analysis of stress-strain measurements revealed that the membrane mechanical strain decreased more than 80% in the edge region of the MEA and about 50% in the electrode region, compared with the pristine condition. Size exclusion chromatography (SEC) indicated that the average molecular weight of the HC polymer increased slightly, indicating some cross-linking, while the IEC decreased slightly, indicating ionomer degradation. As a result of two types of modifications, a sub-gasket (SG) and a soft gas diffusion layer (GDL) in the MEA edge region, the mechanical stress decreased, and the durability increased, the membrane lasting more than 30,000 cycles without mechanical failure.

  19. Field solar degradation of pesticides and emerging water contaminants mediated by polymer films containing titanium and iron oxide with synergistic heterogeneous photocatalytic activity at neutral pH.

    PubMed

    Mazille, F; Schoettl, T; Klamerth, N; Malato, S; Pulgarin, C

    2010-05-01

    Photocatalytic degradation of phenol, nalidixic acid, mixture of pesticides, and another of emerging contaminants in water was mediated by TiO(2) and iron oxide immobilized on functionalized polyvinyl fluoride films (PVF(f)-TiO(2)-Fe oxide) in a compound parabolic collector (CPC) solar photoreactor. During degradation, little iron leaching (<0.2mgL(-1)) was observed. Phenol was efficiently degraded and mineralized at operational pH<5 and nalidixic acid degradation was complete even at pH 7, but mineralization stopped at 35%. Pesticide mixture was slowly degraded (50%) after 150min of irradiation. Degradation of the emergent contaminant mixture was successful for eight compounds and less efficient for six other compounds. The significant reactivity differences between tested compounds were assigned to the differences in structure namely that the presence of complexing or chelating groups enhanced the rates. PVF(f)-TiO(2)-Fe oxide photoactivity gradually increased during 20 days of experiments. X-ray photoelectron spectroscopy (XPS) measurements revealed significant changes on the catalyst surface. These analyses confirm that during photocatalysis mediated by PVF(f)-TiO(2)-Fe oxide, some iron leaching led to enlargement of the TiO(2) surface exposed to light, increasing its synergy with iron oxides and leading to enhanced pollutant degradation.

  20. Polyanhydride degradation and erosion.

    PubMed

    Göpferich, A; Tessmar, J

    2002-10-16

    It was the intention of this paper to give a survey on the degradation and erosion of polyanhydrides. Due to the multitude of polymers that have been synthesized in this class of material in recent years, it was not possible to discuss all polyanhydrides that have gained in significance based on their application. It was rather the intention to provide a broad picture on polyanhydride degradation and erosion based on the knowledge that we have from those polymers that have been intensively investigated. To reach this goal this review contains several sections. First, the foundation for an understanding of the nomenclature are laid by defining degradation and erosion which was deemed necessary because many different definitions exist in the current literature. Next, the properties of major classes of anhydrides are reviewed and the impact of geometry on degradation and erosion is discussed. A complicated issue is the control of drug release from degradable polymers. Therefore, the aspect of erosion-controlled release and drug stability inside polyanhydrides are discussed. Towards the end of the paper models are briefly reviewed that describe the erosion of polyanhydrides. Empirical models as well as Monte-Carlo-based approaches are described. Finally it is outlined how theoretical models can help to answer the question why polyanhydrides are surface eroding. A look at the microstructure and the results from these models lead to the conclusion that polyanhydrides are surface eroding due to their fast degradation. However they switch to bulk erosion once the device dimensions drop below a critical limit.

  1. Ex situ remediation of polluted soils by absorptive polymers, and a comparison of slurry and two-phase partitioning bioreactors for ultimate contaminant degradation.

    PubMed

    Tomei, M Concetta; Mosca Angelucci, Domenica; Annesini, M Cristina; Daugulis, Andrew J

    2013-11-15

    The present study has provided a comparison between a conventional ex situ method for the treatment of contaminated soil, a soil slurry bioreactor, with a novel technology in which a contaminant is rapidly and effectively removed from the soil by means of absorptive polymer beads, which are then added to a two-phase partitioning bioreactor (TPPB) for biodegradation of the target molecule. 4-nitrophenol (4NP) was selected as a model contaminant, being representative of a large class of xenobiotics, and the DuPont thermoplastic Hytrel™ 8206 was utilized for its extraction from soil over ranges of soil contamination level, soil moisture content, and polymer:soil ratios. Since the polymers were able to rapidly (up to 77% and 85% in 4 and 24h respectively) and selectively remove the contaminant, the soil retained its nutrient and microflora content, which is in contrast to soil washing which can remove these valuable soil resources. After 4h of reaction time, the TPPB system demonstrated removal efficiency four times higher (77% vs 20%) than the slurry system, with expected concomitant savings in time and energy. A volumetric removal rate of 75 mg4NPh(-1) L(-1) was obtained in the TPPB, significantly greater than the value of 1.7 obtained in the slurry bioreactor. The polymers were readily regenerated for subsequent reuse, demonstrating the versatility of the polymer-based soil treatment technology.

  2. 08-ERD-071 Final Report: New Molecular Probes and Catalysts for Bioenergy Research

    SciTech Connect

    Thelen, M P; Rowe, A A; Siebers, A K; Jiao, Y

    2011-03-07

    A major thrust in bioenergy research is to develop innovative methods for deconstructing plant cell wall polymers, such as cellulose and lignin, into simple monomers that can be biologically converted to ethanol and other fuels. Current techniques for monitoring a broad array of cell wall materials and specific degradation products are expensive and time consuming. To monitor various polymers and assay their breakdown products, molecular probes for detecting specific carbohydrates and lignins are urgently needed. These new probes would extend the limited biochemical techniques available, and enable realtime imaging of ultrastructural changes in plant cells. Furthermore, degradation of plant biomass could be greatly accelerated by the development of catalysts that can hydrolyze key cell wall polysaccharides and lignin. The objective of this project was to develop cheap and efficient DNA reagents (aptamers) used to detect and quantify polysaccharides, lignin, and relevant products of their breakdown. A practical goal of the research was to develop electrochemical aptamer biosensors, which could be integrated into microfluidic devices and used for high-throughput screening of enzymes or biological systems that degrade biomass. Several important model plant cell wall polymers and compounds were targeted for specific binding and purification of aptamers, which were then tested by microscopic imaging, circular dichroism, surface plasmon resonance, fluorescence anisotropy, and electrochemical biosensors. Using this approach, it was anticiated that we could provide a basis for more efficient and economically viable biofuels, and the technologies established could be used to design molecular tools that recognize targets sought in medicine or chemical and biological defense projects.

  3. Chemical State Mapping of Degraded B4C Control Rod Investigated with Soft X-ray Emission Spectrometer in Electron Probe Micro-analysis.

    PubMed

    Kasada, R; Ha, Y; Higuchi, T; Sakamoto, K

    2016-05-10

    B4C is widely used as control rods in light water reactors, such as the Fukushima Daiichi nuclear power plant, because it shows excellent neutron absorption and has a high melting point. However, B4C can melt at lower temperatures owing to eutectic interactions with stainless steel and can even evaporate by reacting with high-temperature steam under severe accident conditions. To reduce the risk of recriticality, a precise understanding of the location and chemical state of B in the melt core is necessary. Here we show that a novel soft X-ray emission spectrometer in electron probe microanalysis can help to obtain a chemical state map of B in a modeled control rod after a high-temperature steam oxidation test.

  4. Chemical State Mapping of Degraded B4C Control Rod Investigated with Soft X-ray Emission Spectrometer in Electron Probe Micro-analysis

    NASA Astrophysics Data System (ADS)

    Kasada, R.; Ha, Y.; Higuchi, T.; Sakamoto, K.

    2016-05-01

    B4C is widely used as control rods in light water reactors, such as the Fukushima Daiichi nuclear power plant, because it shows excellent neutron absorption and has a high melting point. However, B4C can melt at lower temperatures owing to eutectic interactions with stainless steel and can even evaporate by reacting with high-temperature steam under severe accident conditions. To reduce the risk of recriticality, a precise understanding of the location and chemical state of B in the melt core is necessary. Here we show that a novel soft X-ray emission spectrometer in electron probe microanalysis can help to obtain a chemical state map of B in a modeled control rod after a high-temperature steam oxidation test.

  5. Probing Reactions in Monolayers Using Normal Incidence Cavity Ring-down Spectroscopy

    NASA Astrophysics Data System (ADS)

    Murray, Alissa C.

    This dissertation describes a study that was conducted on a two-dimensional (2-D) polymer system to help characterize the formation and dissociation of the polymer. Normal incidence cavity ring-down spectroscopy (NICRDS) was used to probe the monolayer system. Cavity ring-down spectroscopy (CRDS) is an ultra-sensitive absorption technique which has been extensively used for detection of gas-phase species and has recently been extended to studies in condensed phases. To date, this technique had not been used to study reactions in monolayers and, more specifically, 2D polymers. The newly emerging field of 2D polymers is predicted to impact several areas of technological importance, one of which includes membrane separations. These materials are rationally synthesized and are crystalline in two dimensions forming a covalently linked sheet of molecules. This new class of materials has yet to be fully understood since characterization is difficult due to their delicacy and size. The carboxy fantrip 2D polymer system is an anthracene-based analog and was used in our studies since it is known to be photo and thermally activated. Photo polymerization and depolymerization and thermal depolymerization were monitored using NICRDS to help characterize the poly(carboxy fantrip) 2-D polymer. Relative absorbance values occurring from changes in the CRDS signal during the polymer formation or dissociation reactions are in good agreement with known absorbance values and the predicted monolayer film thickness. In addition to using NICRDS, we developed a new method of CRDS which is comprised of a dual cavity where two wavelengths of light are simultaneously used as probes. A probe at normal incidence geometry and a probe at the Brewster angle for fused silica overlap on the sample of interest. For our experiments, the Brewster angle probe served as an indicator for changes in the ring-down times for the thin film/optical flat system unrelated to the photochemistry of the 2-D polymer

  6. Time-resolved probes and oxidase-based biosensors using terbium(III)-guanosine monophosphate-mercury(II) coordination polymer nanoparticles.

    PubMed

    Zhang, Min; Qu, Zhi-bei; Han, Chun-Min; Lu, Ling-Fei; Li, Yan-Yun; Zhou, Tianshu; Shi, Guoyue

    2014-11-04

    A novel lanthanide coordination polymer nanoparticle (LCPN)-based ternary complex was synthesized via the self-assembly of a terbium ion (Tb(3+)) with a nucleotide (GMP) and a mercury ion (Hg(2+)) in aqueous solution. The as-prepared LCPN-based ternary complex (Tb-GMP-Hg) can be applied to the development of time-resolved luminescence assays and oxidase-based biosensors.

  7. Probing the tails of the ground-state energy distribution for the directed polymer in a random medium of dimension d=1,2,3 via a Monte Carlo procedure in the disorder.

    PubMed

    Monthus, Cécile; Garel, Thomas

    2006-11-01

    In order to probe with high precision the tails of the ground-state energy distribution of disordered spin systems, Körner, Katzgraber, and Hartmann have recently proposed an importance-sampling Monte Carlo Markov chain in the disorder. In this paper, we combine their Monte Carlo procedure in the disorder with exact transfer matrix calculations in each sample to measure the negative tail of ground-state energy distribution Pd(E0) for the directed polymer in a random medium of dimension d=1,2,3. In d=1, we check the validity of the algorithm by a direct comparison with the exact result, namely, the Tracy-Widom distribution. In dimensions d=2 and d=3, we measure the negative tail up to ten standard deviations, which correspond to probabilities of order Pd(E0) approximately 10(-22). Our results are in agreement with Zhang's argument, stating that the negative tail exponent eta(d) of the asymptotic behavior lnPd(E0) approximately -|E0|eta(d) as E0-->-infinity is directly related to the fluctuation exponent theta(d) [which governs the fluctuations DeltaE0(L) approximately Ltheta(d) of the ground-state energy E0 for polymers of length L] via the simple formula eta(d)=1/[1-theta(d)]. Throughout the paper, we comment on the similarities and differences with spin glasses.

  8. Physical organic chemistry of supramolecular polymers.

    PubMed

    Serpe, Michael J; Craig, Stephen L

    2007-02-13

    Unlike the case of traditional covalent polymers, the entanglements that determine properties of supramolecular polymers are defined by very specific, intermolecular interactions. Recent work using modular molecular platforms to probe the mechanisms underlying mechanical response of supramolecular polymers is reviewed. The contributions of supramolecular kinetics, thermodynamics, and conformational flexibility to supramolecular polymer properties in solutions of discrete polymers, in networks, and at interfaces, are described. Molecule-to-material relationships are established through methods reminiscent of classic physical organic chemistry.

  9. Ultrafast photo-induced nuclear relaxation of a conformationally disordered conjugated polymer probed with transient absorption and femtosecond stimulated Raman spectroscopies.

    PubMed

    Yu, Wenjian; Donohoo-Vallett, Paul J; Zhou, Jiawang; Bragg, Arthur E

    2014-07-28

    A combination of transient absorption (TAS) and femtosecond stimulated Raman (FSRS) spectroscopies were used to interrogate the photo-induced nuclear relaxation dynamics of poly(3-cyclohexyl,4-methylthiophene) (PCMT). The large difference in inter-ring dihedral angles of ground and excited-state PCMT make it an ideal candidate for studying large-amplitude vibrational relaxation associated with exciton trapping. Spectral shifting in the S1 TA spectra on sub-ps timescales (110 ± 20 and 800 ± 100 fs) is similar to spectroscopic signatures of excited-state relaxation observed with related photoexcited conjugated polymers and which have been attributed to exciton localization and a combination of resonant energy transfer and torsional relaxation, respectively. Measurements made with both techniques reveal fast PCMT S1 decay and triplet formation (τS1 = 25-32 ps), which is similar to the excited-state dynamics of short oligothiophenes and highly twisted polyconjugated molecules. On ultrafast timescales FSRS of S1 PCMT offers a new perspective on the nuclear dynamics that underlie localization of excitons in photoexcited conjugated polymers: Spectral dynamics in the C=C stretching region (1400-1600 cm(-1)) include a red-shift of the in-phase C=C stretching frequency, as well as a change in the relative intensity of in-phase and out-of-phase stretch intensities on a timescale of ∼100 fs. Both changes indicate an ultrafast vibrational distortion that increases the conjugation length in the region of the localized excitation and are consistent with exciton self-localization or trapping. Wavelength-dependent excited-state FSRS measurements further demonstrate that the C=C stretching frequency provides a useful spectroscopic handle for interrogating the degree of delocalization in excited conjugated polymers given the selectivity achieved via resonance enhancement.

  10. Ultrafast photo-induced nuclear relaxation of a conformationally disordered conjugated polymer probed with transient absorption and femtosecond stimulated Raman spectroscopies

    SciTech Connect

    Yu, Wenjian; Donohoo-Vallett, Paul J.; Zhou, Jiawang; Bragg, Arthur E.

    2014-07-28

    A combination of transient absorption (TAS) and femtosecond stimulated Raman (FSRS) spectroscopies were used to interrogate the photo-induced nuclear relaxation dynamics of poly(3-cyclohexyl,4-methylthiophene) (PCMT). The large difference in inter-ring dihedral angles of ground and excited-state PCMT make it an ideal candidate for studying large-amplitude vibrational relaxation associated with exciton trapping. Spectral shifting in the S{sub 1} TA spectra on sub-ps timescales (110 ± 20 and 800 ± 100 fs) is similar to spectroscopic signatures of excited-state relaxation observed with related photoexcited conjugated polymers and which have been attributed to exciton localization and a combination of resonant energy transfer and torsional relaxation, respectively. Measurements made with both techniques reveal fast PCMT S{sub 1} decay and triplet formation (τ{sub S1} = 25–32 ps), which is similar to the excited-state dynamics of short oligothiophenes and highly twisted polyconjugated molecules. On ultrafast timescales FSRS of S{sub 1} PCMT offers a new perspective on the nuclear dynamics that underlie localization of excitons in photoexcited conjugated polymers: Spectral dynamics in the C=C stretching region (1400–1600 cm{sup −1}) include a red-shift of the in-phase C=C stretching frequency, as well as a change in the relative intensity of in-phase and out-of-phase stretch intensities on a timescale of ∼100 fs. Both changes indicate an ultrafast vibrational distortion that increases the conjugation length in the region of the localized excitation and are consistent with exciton self-localization or trapping. Wavelength-dependent excited-state FSRS measurements further demonstrate that the C=C stretching frequency provides a useful spectroscopic handle for interrogating the degree of delocalization in excited conjugated polymers given the selectivity achieved via resonance enhancement.

  11. Chloromethane Utilization Gene Cluster from Hyphomicrobium chloromethanicum Strain CM2T and Development of Functional Gene Probes To Detect Halomethane-Degrading Bacteria

    PubMed Central

    McAnulla, Craig; Woodall, Claire A.; McDonald, Ian R.; Studer, Alex; Vuilleumier, Stephane; Leisinger, Thomas; Murrell, J. Colin

    2001-01-01

    Hyphomicrobium chloromethanicum CM2T, an aerobic methylotrophic member of the α subclass of the class proteobacteria, can grow with chloromethane as the sole carbon and energy source. H. chloromethanicum possesses an inducible enzyme system for utilization of chloromethane, in which two polypeptides (67-kDa CmuA and 35-kDa CmuB) are expressed. Previously, four genes, cmuA, cmuB, cmuC, and purU, were shown to be essential for growth of Methylobacterium chloromethanicum on chloromethane. The cmuA and cmuB genes were used as probes to identify homologs in H. chloromethanicum. A cmu gene cluster (9.5 kb) in H. chloromethanicum contained 10 open reading frames: folD (partial), pduX, orf153, orf207, orf225, cmuB, cmuC, cmuA, fmdB, and paaE (partial). CmuA from H. chloromethanicum (67 kDa) showed high identity to CmuA from M. chloromethanicum and contains an N-terminal methyltransferase domain and a C-terminal corrinoid-binding domain. CmuB from H. chloromethanicum is related to a family of methyl transfer proteins and to the CmuB methyltransferase from M. chloromethanicum. CmuC from H. chloromethanicum shows identity to CmuC from M. chloromethanicum and is a putative methyltransferase. folD codes for a methylene-tetrahydrofolate cyclohydrolase, which may be involved in the C1 transfer pathway for carbon assimilation and CO2 production, and paaE codes for a putative redox active protein. Molecular analyses and some preliminary biochemical data indicated that the chloromethane utilization pathway in H. chloromethanicum is similar to the corrinoid-dependent methyl transfer system in M. chloromethanicum. PCR primers were developed for successful amplification of cmuA genes from newly isolated chloromethane utilizers and enrichment cultures. PMID:11133460

  12. Three dimensional nano-assemblies of noble metal nanoparticle-infinite coordination polymers as specific oxidase mimetics for degradation of methylene blue without adding any cosubstrate.

    PubMed

    Wang, Lihua; Zeng, Yi; Shen, Aiguo; Zhou, Xiaodong; Hu, Jiming

    2015-02-07

    Novel three-dimensional (3D) nano-assemblies of noble metal nanoparticle (NP)-infinite coordination polymers (ICPs) are conveniently fabricated through the infiltration of HAuCl4 into hollow Au@Ag@ICPs core-shell nanostructures and its replacement reaction with Au@Ag NPs. The present 3D nano-assemblies exhibit highly efficient and specific intrinsic oxidase-like activity even without adding any cosubstrate.

  13. Conjugated polymer with carboxylate groups-Hg2 + system as a turn-on fluorescence probe for label-free detection of cysteine-containing compounds

    NASA Astrophysics Data System (ADS)

    Mi, Hongyu; Guan, Mingming; Liu, Jilin; Shan, Hongyan; Fei, Qiang; Huan, Yanfu; Feng, Guodong

    2017-04-01

    In this work, a turn on fluorescent sensor, based on Hg2 + coordination conjugated polymer, was developed to detect cysteine-containing compounds. The fluorescence of conjugated polymer (poly(2,5-bis (sodium 4-oxybutyrate) -1,4 - phenylethynylene-alt-1,4-phenyleneethynylene; PPE-OBS) would be quenched by Hg2 + because of the coordination-induced aggregation and electron transfers of PPE-OBS toward Hg2 +. When there were some cysteine-containing compounds in PPE-OBS-Hg2 + system, the fluorescence of PPE-OBS would be recovered. It indicated that the PPE-OBS-Hg2 + system could be used to detect cysteine-containing compounds. Under the optimized conditions, the experiment results showed that there were particularly linear range, high sensitivity and selectivity over other amino acids. The limit of detection (LOD) of cysteine (Cys), homocysteine (Hcy) and glutathione (GSH) were 0.725 μmol L- 1, 0.982 μmol L- 1 and 1.21 μmol L- 1 by using this sensor. In addition, Cys standard recovery in several green tea drink and honey samples was also demonstrated. The recovery of Cys was range from 96.3 to 105.0% and RSD was less than 3.25%. The satisfactory results demonstrated that the proposed method could be as a potential fluorescent method for determining cysteine-containing compounds in real samples.

  14. Ex situ testing method to characterize cathode catalysts degradation under simulated start-up/shut-down conditions - A contribution to polymer electrolyte membrane fuel cell benchmarking

    NASA Astrophysics Data System (ADS)

    Marcu, A.; Toth, G.; Kundu, S.; Colmenares, L. C.; Behm, R. J.

    2012-10-01

    The paper introduces a novel ex situ test procedure that was developed to quantify the ageing of catalyst layers under critical automotive fuel cell conditions during start-up/shut-down phases. It is based on liquid electrolyte measurements, using a thin film catalyst electrode. The overall degradation under start-up/shut-down conditions is assessed by the decay in electrochemically active surface area. Furthermore, contributions from different processes leading to catalyst degradation such as Pt dissolution and Pt particle growth/agglomeration can be separated. Finally, using a differential electrochemical mass spectrometry (DEMS) set-up, also the extent and role of carbon corrosion under these conditions is accessible. The potential of this, compared to in situ fuel cell stack tests, rather fast and less costly ex situ test procedure is demonstrated in measurements using a commercial, graphitized carbon-supported Pt catalyst. The results of the degradation test and in particular the contributions from different degradation processes such as Pt dissolution, Pt particle growth/agglomeration and carbon corrosion during different stages of catalyst ageing are discussed.

  15. Hydroxyapatite degradation and biocompatibility

    NASA Astrophysics Data System (ADS)

    Wang, Haibo

    Hydroxyapatite (HA) is widely used as a bioactive ceramics since it forms a chemical bonding to bone. The disadvantage of this material is its poor mechanical properties. HA can be degraded in body, which is the reason for its bioactivity, but too fast degradation rate could cause negative effects, such as macrophage present, particle generation, and even implant clinical failure. HA degradation rate will be greatly changed under many conditions: purity, HA form (i.e. bulk form, porous form, coating, or HA/polymer composites), microstructure, implant site, body conditions, etc. Although much work has been done in HA properties and application areas, the HA degradation behavior and mechanism under these different conditions are still not clear. In this research, three aspects of HA degradation have been studied: (1) Two very common impurities---Tri-Calcium Phosphate (TCP) and Calcium Oxide and their influences on HA degradation in vitro and in vivo, (2) influence of HA/polymer composite form on HA degradation, (3) HA material particle generation and related mechanism. From the in vitro and in vivo tests on bulk HA disks with various Ca/P ratios, HA degradation can clearly be found. The degradation level is different in different Ca/P ratio samples as well as in different test environments. In same test environment, non-stoichiometric HA samples have higher degradation rate than stoichiometric HA. HA/PMMA composite design successfully intensifies HA degradation both in vitro and in vivo. Grain boundary damage can be found on in vivo test samples, which has not been clearly seen on bulk HA degraded surface. HA particle generation is found in in vitro and in vivo HA/PMMA composite surface and in vivo bulk HA surface. Sintering temperature and time does affect HA grain size, and this affect HA degradation rate. Intergranular fracture is found in a several micron zone close to the Ca/P ratio 1.62 and 1.67 sample degraded surfaces. At Ca/P ratio greater than 1.667, after

  16. In-situ characterization of free-volume holes in polymer thin films under controlled humidity conditions with an atmospheric positron probe microanalyzer

    SciTech Connect

    Zhou Wei; Oshima, Nagayasu; O'Rourke, Brian E.; Kuroda, Ryunosuke; Suzuki, Ryoichi; Chen Zhe; Ito, Kenji; Yanagishita, Hiroshi; Tsutsui, Takuro; Uedono, Akira; Hayashizaki, Noriyosu

    2012-07-02

    A pulsed, slow positron beam, with a diameter of 200 {mu}m, was extracted into air through a thin SiN window of an atmospheric positron probe microanalyzer (PPMA), and used to measure the ortho-positronium lifetimes {tau} in polyvinyl alcohol and polycaprolactam sub-{mu}m-thick films. By measuring the variation of {tau} as a function of relative humidity, the effect of water molecules on the hole sizes, deduced from {tau}, was examined for the films with consideration to the chain mobility. The results demonstrate the usefulness of the atmospheric PPMA to the in-situ characterization of nanoscopic holes in thin films under practical conditions.

  17. Enzymatic degradation of polycaprolactone-gelatin blend

    NASA Astrophysics Data System (ADS)

    Banerjee, Aditi; Chatterjee, Kaushik; Madras, Giridhar

    2015-04-01

    Blends of polycaprolactone (PCL), a synthetic polymer and gelatin, natural polymer offer a optimal combination of strength, water wettability and cytocompatibility for use as a resorbable biomaterial. The enzymatic degradation of PCL, gelatin and PCL-gelatin blended films was studied in the presence of lipase (Novozym 435, immobilized) and lysozyme. Novozym 435 degraded the PCL films whereas lysozyme degraded the gelatin. Though Novozym 435 and lysozyme individually could degrade PCL-gelatin blended films, the combination of these enzymes showed the highest degradation of these blended films. Moreover, the enzymatic degradation was much faster when fresh enzymes were added at regular intervals. The changes in physico-chemical properties of polymer films due to degradation were studied by scanning electron microscopy, Fourier transform infrared spectroscopy and differential scanning calorimetry. These results have important implications for designing resorbable biomedical implants.

  18. Polymer films

    DOEpatents

    Granick, Steve; Sukhishvili, Svetlana A.

    2004-05-25

    A film contains a first polymer having a plurality of hydrogen bond donating moieties, and a second polymer having a plurality of hydrogen bond accepting moieties. The second polymer is hydrogen bonded to the first polymer.

  19. Polymer films

    DOEpatents

    Granick, Steve; Sukhishvili, Svetlana A.

    2008-12-30

    A film contains a first polymer having a plurality of hydrogen bond donating moieties, and a second polymer having a plurality of hydrogen bond accepting moieties. The second polymer is hydrogen bonded to the first polymer.

  20. Changes In Cell Wall Polymers And Degradability In Maize Mutants Lacking 3'- And 5'-O-Methyltransferases Involved In Lignin Biosynthesis.

    PubMed

    Fornalé, Silvia; Rencoret, Jorge; García-Calvo, Laura; Encina, Antonio; Rigau, Joan; Gutiérrez, Ana; Del Río, José Carlos; Caparros-Ruiz, David

    2016-12-23

    Caffeoyl Coenzyme A 3-O-Methyltransferase (CCoAOMT) and Caffeic acid-O-Methyltransferase (COMT) are key enzymes in the biosynthesis of coniferyl and sinapyl alcohols, the precursors of guaiacyl (G) and syringyl (S) lignin subunits. The function of these enzymes was characterised in single and double mutant maize plants. In this work, we determined that the comt (brown-midrib 3) mutant plants display a reduction of the flavonolignin unit derived from tricin (a dimethylated flavone), demonstrating that COMT is a key enzyme involved in the synthesis of this compound. In contrast, the ccoaomt1 mutants displays wild type amount of tricin, suggesting that CCoAOMT1 is not essential for the synthesis of this compound. Based on our data, we suggest that CCoAOMT1 is involved in lignin biosynthesis at least in midribs. The phenotype of ccoaomt1 mutant plants displays no alterations, and their lignin content and composition remain unchanged. On the other hand, the ccoaomt1 comt mutant displays phenotypic and lignin alterations similar to the ones already described for the comt mutant. Although stems from the three mutants display a similar increase of hemicelluloses, the effect on cell wall degradability varies, being the cell walls of the ccoaomt1 the most degradable. This suggests that the positive effect of lignin reduction on cell wall degradability of comt and ccoaomt1 comt mutants is counteracted by changes occurring in lignin composition, such as the decreased S/G ratio. In addition, the role of the flavonolignin unit derived from tricin in cell wall degradability is also discussed.

  1. Tools for fluorescent molecularly imprinted polymers.

    PubMed

    Rathbone, Daniel L; Bains, Ajeet

    2005-01-15

    A linear co-polymer of hexyl acrylate and quinine acrylate was prepared anchored to cellulose filtration membranes. These were used to probe quenching of the tethered fluorophore by test compounds in solution for the validation of imprinted polymer fluorescence studies. The results are compared with simple solution phase quenching studies and also for two membrane-bound imprinted polymers containing the same fluorophore.

  2. Spectrophotometric probe

    DOEpatents

    Prather, W.S.; O'Rourke, P.E.

    1994-08-02

    A support structure is described bearing at least one probe for making spectrophotometric measurements of a fluid using a source of light and a spectrophotometer. The probe includes a housing with two optical fibers and a planoconvex lens. A sleeve bearing a mirror surrounds the housing. The lens is separated from the mirror by a fixed distance, defining an interior space for receiving a volume of the fluid sample. A plurality of throughholes extending through the sleeve communicate between the sample volume and the exterior of the probe, all but one hole bearing a screen. A protective jacket surrounds the probe. A hollow conduit bearing a tube is formed in the wall of the probe for venting any air in the interior space when fluid enters. The probe is held at an acute angle so the optic fibers carrying the light to and from the probe are not bent severely on emergence from the probe. 3 figs.

  3. Spectrophotometric probe

    DOEpatents

    Prather, William S.; O'Rourke, Patrick E.

    1994-01-01

    A support structure bearing at least one probe for making spectrophotometric measurements of a fluid using a source of light and a spectrophotometer. The probe includes a housing with two optical fibers and a planoconvex lens. A sleeve bearing a mirror surrounds the housing. The lens is separated from the mirror by a fixed distance, defining an interior space for receiving a volume of the fluid sample. A plurality of throughholes extending through the sleeve communicate between the sample volume and the exterior of the probe, all but one hole bearing a screen. A protective jacket surrounds the probe. A hollow conduit bearing a tube is formed in the wall of the probe for venting any air in the interior space when fluid enters. The probe is held at an acute angle so the optic fibers carrying the light to and from the probe are not bent severely on emergence from the probe.

  4. Starch-filled polymer composites

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This report describes the development of degradable polymer composites that can be made at room temperature without special equipments. The developed composites are made from ethyl cyanoacrylate and starch. The polymer composites produced by this procedure contain 60 wt% of starch with compressive s...

  5. Charge collection kinetics on ferroelectric polymer surface using charge gradient microscopy

    PubMed Central

    Choi, Yoon-Young; Tong, Sheng; Ducharme, Stephen; Roelofs, Andreas; Hong, Seungbum

    2016-01-01

    A charge gradient microscopy (CGM) probe was used to collect surface screening charges on poly(vinylidene fluoride-trifluoroethylene) [P(VDF-TrFE)] thin films. These charges are naturally formed on unscreened ferroelectric domains in ambient condition. The CGM data were used to map the local electric current originating from the collected surface charges on the poled ferroelectric domains in the P(VDF-TrFE) thin films. Both the direction and amount of the collected current were controlled by changing the polarity and area of the poled domains. The endurance of charge collection by rubbing the CGM tip on the polymer film was limited to 20 scan cycles, after which the current reduced to almost zero. This degradation was attributed to the increase of the chemical bonding strength between the external screening charges and the polarization charges. Once this degradation mechanism is mitigated, the CGM technique can be applied to efficient energy harvesting devices using polymer ferroelectrics. PMID:27138943

  6. Charge collection kinetics on ferroelectric polymer surface using charge gradient microscopy

    SciTech Connect

    Choi, Yoon-Young; Tong, Sheng; Ducharme, Stephen P.; Roelofs, Andreas; Hong, Seungbum

    2016-05-03

    Here, a charge gradient microscopy (CGM) probe was used to collect surface screening charges on poly(vinylidene fluoride-trifluoroethylene) [P(VDF-TrFE)] thin films. These charges are naturally formed on unscreened ferroelectric domains in ambient condition. The CGM data were used to map the local electric current originating from the collected surface charges on the poled ferroelectric domains in the P(VDF-TrFE) thin films. Both the direction and amount of the collected current were controlled by changing the polarity and area of the poled domains. The endurance of charge collection by rubbing the CGM tip on the polymer film was limited to 20 scan cycles, after which the current reduced to almost zero. This degradation was attributed to the increase of the chemical bonding strength between the external screening charges and the polarization charges. Once this degradation mechanism is mitigated, the CGM technique can be applied to efficient energy harvesting devices using polymer ferroelectrics.

  7. Charge collection kinetics on ferroelectric polymer surface using charge gradient microscopy

    NASA Astrophysics Data System (ADS)

    Choi, Yoon-Young; Tong, Sheng; Ducharme, Stephen; Roelofs, Andreas; Hong, Seungbum

    2016-05-01

    A charge gradient microscopy (CGM) probe was used to collect surface screening charges on poly(vinylidene fluoride-trifluoroethylene) [P(VDF-TrFE)] thin films. These charges are naturally formed on unscreened ferroelectric domains in ambient condition. The CGM data were used to map the local electric current originating from the collected surface charges on the poled ferroelectric domains in the P(VDF-TrFE) thin films. Both the direction and amount of the collected current were controlled by changing the polarity and area of the poled domains. The endurance of charge collection by rubbing the CGM tip on the polymer film was limited to 20 scan cycles, after which the current reduced to almost zero. This degradation was attributed to the increase of the chemical bonding strength between the external screening charges and the polarization charges. Once this degradation mechanism is mitigated, the CGM technique can be applied to efficient energy harvesting devices using polymer ferroelectrics.

  8. Degradable PEGylated Protein Conjugates Utilizing RAFT Polymerization.

    PubMed

    Decker, Caitlin G; Maynard, Heather D

    2015-04-01

    Poly(ethylene glycol) (PEG)-protein therapeutics exhibit enhanced pharmacokinetics, but have drawbacks including decreased protein activities and polymer accumulation in the body. Therefore a major aim for second-generation polymer therapeutics is to introduce degradability into the backbone. Herein we describe the synthesis of poly(poly(ethylene glycol methyl ether methacrylate)) (pPEGMA) degradable polymers with protein-reactive end-groups via reversible addition-fragmentation chain transfer (RAFT) polymerization, and the subsequent covalent attachment to lysozyme through a reducible disulfide linkage. RAFT copolymerization of cyclic ketene acetal (CKA) monomer 5,6-benzo-2-methylene-1,3-dioxepane (BMDO) with PEGMA yielded two polymers with number-average molecular weight (Mn ) (GPC) of 10.9 and 20.9 kDa and molecular weight dispersities (Ð) of 1.34 and 1.71, respectively. Hydrolytic degradation of the polymers was analyzed by (1)H-NMR and GPC under basic and acidic conditions. The reversible covalent attachment of these polymers to lysozyme, as well as the hydrolytic and reductive cleavage of the polymer from the protein, was analyzed by gel electrophoresis and mass spectrometry. Following reductive cleavage of the polymer, an increase in activity was observed for both conjugates, with the released protein having full activity. This represents a method to prepare PEGylated proteins, where the polymer is readily cleaved from the protein and the main chain of the polymer is degradable.

  9. A novel fluorescent probe for copper ions based on polymer-modified CdSe/CdS core/shell quantum dots.

    PubMed

    Cao, Zhong; Gu, Zheng; Zeng, Ju-Lan; Liu, Jin-Hua; Deng, Qin; Fan, Jun-Bing; Xiang, Jian-Nan

    2011-01-01

    Quantum dots (QDs) have become one of the most attractive fields of current research because of their unique optical properties. Novel copper-sensitive fluorescent fluoroionophores based on CdSe/CdS core/shell QDs modified with a polymer of MAO-mPEG were synthesized and characterized in the present work. A pH of 6.47 was optimally selected for measurements. By modifying QDs with MAO-mPEG, significant aqueous fluorescence quenching was observed upon binding with copper ions involving both reduced and oxidized environments, indicating great sensitivity and specificity for copper-ion sensing. No significant interfering effects from other metal ions, such as Ag(+), Al(3+), Ba(2+), Ca(2+), Cd(2+), Co(2+), Cr(3+), Fe(2+), Fe(3+), Hg(2+), K(+), Mg(2+), Mn(2+), Na(+), Ni(2+), Pb(2+), Sn(2+), and Zn(2+), were observed. The linear response range for Cu(2+) was found to be 0.01-0.50 µM, and the limit of detection was evaluated to be 16 nM. The proposed method demonstrated improved sensitivity and selectivity characteristics for Cu(II) determinations based on CdSe/CdS core/shell QDs modified with MAO-mPEG by using a typical liquid-phase quenching assay, showing its potential application to multiplex sensing of different analytes through distinct ligand conjugation and functionalization of individual fluorophores.

  10. Scanning Probe Microscopy of Organic Solar Cells

    NASA Astrophysics Data System (ADS)

    Reid, Obadiah G.

    Nanostructured composites of organic semiconductors are a promising class of materials for the manufacture of low-cost solar cells. Understanding how the nanoscale morphology of these materials affects their efficiency as solar energy harvesters is crucial to their eventual potential for large-scale deployment for primary power generation. In this thesis we describe the use of optoelectronic scanning-probe based microscopy methods to study this efficiency-structure relationship with nanoscale resolution. In particular, our objective is to make spatially resolved measurements of each step in the power conversion process from photons to an electric current, including charge generation, transport, and recombination processes, and correlate them with local device structure. We have achieved two aims in this work: first, to develop and apply novel electrically sensitive scanning probe microscopy experiments to study the optoelectronic materials and processes discussed above; and second, to deepen our understanding of the physics underpinning our experimental techniques. In the first case, we have applied conductive-, and photoconductive atomic force (cAFM & pcAFM) microscopy to measure both local photocurrent collection and dark charge transport properties in a variety of model and novel organic solar cell composites, including polymer/fullerene blends, and polymer-nanowire/fullerene blends, finding that local heterogeneity is the rule, and that improvements in the uniformity of specific beneficial nanostructures could lead to large increases in efficiency. We have used scanning Kelvin probe microscopy (SKPM) and time resolved-electrostatic force microscopy (trEFM) to characterize all-polymer blends, quantifying their sensitivity to photochemical degradation and the subsequent formation of local charge traps. We find that while trEFM provides a sensitive measure of local quantum efficiency, SKPM is generally unsuited to measurements of efficiency, less sensitive than tr

  11. Green polymer chemistry: biocatalysis and biomaterials

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This overview briefly surveys the practice of green chemistry in polymer science. Eight related themes can be discerned from the current research activities: 1) biocatalysis, 2) bio-based building blocks and agricultural products, 3) degradable polymers, 4) recycling of polymer products and catalys...

  12. Green polymer chemistry: a brief review

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This review briefly surveys the research done on green polymer chemistry in the past few years. For convenience, these research activities can be grouped into 8 themes: 1) greener catalysis, 2) diverse feedstock base, 3) degradable polymers and waste minimization, 4) recycling of polymer products a...

  13. Preparation of a photo-degradation- resistant quantum dot-polymer composite plate for use in the fabrication of a high-stability white-light-emitting diode

    NASA Astrophysics Data System (ADS)

    Jang, Eun-Pyo; Song, Woo-Seuk; Lee, Ki-Heon; Yang, Heesun

    2013-02-01

    We report on the synthesis of highly fluorescent double-ZnS-shell-capped, yellow-emitting Cu-In-S quantum dots (QDs) with a surprisingly high quantum yield of 92%, the preparation of a free-standing QD-polymethylmethacrylate composite plate, and the application of the QD plate in the fabrication of QD-based white-light-emitting diodes (WLEDs). A free-standing QD plate with QDs embedded uniformly inside a polymeric matrix is used to fabricate a remote-type, resin-free WLED. The QD plate-based WLED displays a high luminous efficiency; however, it suffers from a significantly unstable device performance due to QD degradation upon prolonged photo-excitation. An exceptional operational stability of the QD plate-based WLED is realized by generating hybrid double layers of an organic adhesion layer and a gas barrier layer of sol-gel-derived silica, rendering the QD plate impermeable to oxygen. Our success in achieving a color converter robust against photo-degradation and applying it in the fabrication of a reliable QD-based LED is greatly encouraging as regards the development of next-generation QD-based LED lighting sources.

  14. Study of nitrile-containing proton exchange membranes prepared by radiation grafting: Performance and degradation in the polymer electrolyte fuel cell

    NASA Astrophysics Data System (ADS)

    Zhang, Zhuoxiang; Jetsrisuparb, Kaewta; Wokaun, Alexander; Gubler, Lorenz

    2013-12-01

    The fuel cell performance and durability of three kinds of styrene based radiation grafted membranes are investigated and compared in the single cell. The styrene/methacrylonitrile (MAN) co-grafted membrane exhibits the best performance among the tested radiation grafted membranes. The accelerated tests under open circuit voltage (OCV) conditions and post-mortem analysis demonstrate that the nitrile-containing membranes exhibit significantly enhanced durability compared to the pure styrene grafted membrane, which is associated with the reduced gas crossover rates and attributed to the improved gases barrier properties due to the polarity of the nitrile group. To understand the influence of each functional group in the co-monomer units, both styrene/MAN and styrene/acrylonitrile (AN) co-grafted membranes are evaluated in a set of tests at OCV. The degrees of loss of the graft components are subsequently quantitatively analyzed based on FTIR spectra, showing a comparable decomposition rate of grafted styrene units, but more loss of nitrile in case of the styrene/AN co-grafted membrane. The styrene/AN co-grafted membrane, with AN lacking protection at the α-position in contrast to MAN, is found to be susceptible to significant hydrolysis, directly leading to an accelerated degradation in the late stages of the 130 h OCV test and inhomogeneous in-plane degradation.

  15. Part I: In-situ fluorometric quantification of microalgal neutral lipids. Part II: Thermal degradation behavior of investment casting polymer patterns

    NASA Astrophysics Data System (ADS)

    Zhao, Hongfang

    Research described in this dissertation covers two topics. Part-I is focused on in-situ determination of neutral lipid content of microalgae using a lipophilic fluorescent dye. The traditional Nile red stain-based method for detecting microalgal intracellular lipids is limited due to varying composition and thickness of rigid cell walls. In this study, the addition of dilute acid and heating of solution, were found to greatly enhance staining efficiency of Nile red for microalgal species evaluated. Oil-in-water (O/W) microemulsion stabilized by a non-ionic surfactant was employed as a pseudo-standard that mimics lipid-bearing microalgal cells suspended in water. The average neutral lipid contents determined were very close to the results obtained by traditional gravimetric method and solid phase extraction. Part II of the dissertation explores thermo-physico-chemical properties of polymeric pattern materials, including expanded polystyrene (EPS) foam, polyurethane foam, and epoxy stereolithography (SLA) patterns, that are used in investment casting. Density, elastic modulus, expansion coefficient, thermal degradation behavior, etc. were experimentally investigated for their effects on metal casting quality. The reduction in toxic hydrogen cyanide (HCN) generated during thermal decomposition of polyurethane pattern was achieved by increasing either oxidant level or residence time in heated zone. Thermal degradation kinetics of the pattern materials were examined with a thermogravimetric analysis and activation energies were determined by Kissinger and Flynn-Wall-Ozawa methods.

  16. Mechanochemical and Conventional Synthesis of Zn(II)/Cd(II) Luminescent Coordination Polymers: Dual Sensing Probe for Selective Detection of Chromate Anions and TNP in Aqueous Phase.

    PubMed

    Parmar, Bhavesh; Rachuri, Yadagiri; Bisht, Kamal Kumar; Laiya, Ridhdhi; Suresh, Eringathodi

    2017-03-06

    Isostructural Zn(II)/Cd(II) mixed ligand coordination polymers (CPs) {[M(IPA)(L)]}n (CP1 and CP2) built from isophthalic acid (H2IPA) and 3-pyridylcarboxaldehyde nicotinoylhydrazone (L) were prepared using versatile synthetic routes: viz., diffusion of precursor solutions, conventional reflux methods, and green mechanochemical (grinding) reactions. Both robust CPs synthesized by different routes were characterized by various analytical methods, and their thermal and chemical stability as well as the phase purity was established. Crystallographic studies revealed that CP1 and CP2 are isostructural frameworks and feature a double-lined two-dimensional network composed of Zn(2+)/Cd(2+) nodes connected through IPA and pillared by the Schiff base ligand L with a double-walled edge. The photoluminescent (PL) properties of CP1 and CP2 have been exploited as dual detection fluorosensors for hexavalent chromate anions (CrO4(2-)/Cr2O7(2-)) and 2,4,6-trinitrophenol (TNP) because it was observed that the emission intensity of aqueous suspensions of CPs selectively quenches by chromate anions or TNP among large pools of different anions or nitro compounds, respectively. Competitive experiments in the presence of interfering anions/other nitro compounds also revealed no major effect in the quenching efficiency, suggesting the selective detection of hexavalent chromate anions as well as TNP by the LCPs. The limits of detection by CP1 for CrO4(2-)/Cr2O7(2-) and TNP are 4 ppm/4 ppm and 28 ppb, respectively, whereas the limits of detection by CP2 for the same analytes are 1 ppm/1 ppm and 14 ppb, respectively. A probable mechanism for the quenching phenomena is also discussed.

  17. The importance of correcting for variable probe-sample interactions in AFM-IR spectroscopy: AFM-IR of dried bacteria on a polyurethane film.

    PubMed

    Barlow, Daniel E; Biffinger, Justin C; Cockrell-Zugell, Allison L; Lo, Michael; Kjoller, Kevin; Cook, Debra; Lee, Woo Kyung; Pehrsson, Pehr E; Crookes-Goodson, Wendy J; Hung, Chia-Suei; Nadeau, Lloyd J; Russell, John N

    2016-08-02

    AFM-IR is a combined atomic force microscopy-infrared spectroscopy method that shows promise for nanoscale chemical characterization of biological-materials interactions. In an effort to apply this method to quantitatively probe mechanisms of microbiologically induced polyurethane degradation, we have investigated monolayer clusters of ∼200 nm thick Pseudomonas protegens Pf-5 bacteria (Pf) on a 300 nm thick polyether-polyurethane (PU) film. Here, the impact of the different biological and polymer mechanical properties on the thermomechanical AFM-IR detection mechanism was first assessed without the additional complication of polymer degradation. AFM-IR spectra of Pf and PU were compared with FTIR and showed good agreement. Local AFM-IR spectra of Pf on PU (Pf-PU) exhibited bands from both constituents, showing that AFM-IR is sensitive to chemical composition both at and below the surface. One distinct difference in local AFM-IR spectra on Pf-PU was an anomalous ∼4× increase in IR peak intensities for the probe in contact with Pf versus PU. This was attributed to differences in probe-sample interactions. In particular, significantly higher cantilever damping was observed for probe contact with PU, with a ∼10× smaller Q factor. AFM-IR chemical mapping at single wavelengths was also affected. We demonstrate ratioing of mapping data for chemical analysis as a simple method to cancel the extreme effects of the variable probe-sample interactions.

  18. Silk and PEG as means to stiffen a parylene probe for insertion in the brain: toward a double time-scale tool for local drug delivery

    NASA Astrophysics Data System (ADS)

    Lecomte, A.; Castagnola, V.; Descamps, E.; Dahan, L.; Blatché, M. C.; Dinis, T. M.; Leclerc, E.; Egles, C.; Bergaud, C.

    2015-12-01

    The use of soft materials as substrate for neural probes aims at achieving better compliance with the surrounding neurons while maintaining minimal rejection. Many strategies have emerged to enable such probes to penetrate the cortex, among which the use of resorbable polymers. We performed several tests involving two resorbable polymers considered most promising: polyethylene glycol (PEG) and silk fibroin (SF) from Bombyx Mori silkworms. Our coating method provides a repeatable, uniform structure optimized for a stress-reduced insertion of a parylene-C neural probe. Standard compression tests as well as in vitro and in vivo insertion assessments show that both SF and PEG-coated probes are stiff enough to avoid the buckling effect during insertion in the cortex. However, with a buckling force of 300 mN and a mechanical holding in vitro of tens of minutes, we assess silk fibroin to be more reliable for practical handling. In vivo first try-outs in mouse brain showed neither buckling issues of the probe nor undesired alteration of the signal recording. Moreover, we evidenced two distinct time scales in the bioresorption of our polymer coatings: silk fibroin degrades itself in a matter of weeks and PEG dissolves itself within seconds in the presence of water. We then present a hybrid PEG and SF coating that could be used as a drug delivery system with different time scales to reduce both the acute and the chronic body reaction.

  19. Polystyrene as a model system to probe the impact of ambient gas chemistry on polymer surface modifications using remote atmospheric pressure plasma under well-controlled conditions.

    PubMed

    Bartis, Elliot A J; Luan, Pingshan; Knoll, Andrew J; Hart, Connor; Seog, Joonil; Oehrlein, Gottlieb S

    2015-06-30

    , but nitridation only occurs under specific conditions with the overall nitrogen content never exceeding 3%. Possible mechanisms for these processes are discussed. This work demonstrates the need to control plasma-ambient interactions and indicates a potential to take advantage of plasma-ambient interactions to fine-tune the reactive species output of APP sources, which is required for specialized applications, including polymer surface modifications and plasma medicine.

  20. Degradation of degradable starch-polyethylene plastics in a compost environment

    SciTech Connect

    Johnson, K.E.; Pometto, A.L. III; Nikolov, Z.L. )

    1993-04-01

    Degradable plastics have differing degradation rates. Three types of degradation of polyethylene in the starch-polyethylene polymers can occur: chemical degradation, photodegradation, and biological degradation. This study examines all three types of degradation in 11 commercially produced degradable starch-polyethylene bags. Different rates for chemical and photo-degradation were found within a 20 day or an 8-week period. Results indicated that both the 70[degree]C oven and HT-HH film treatments were appropriate methods to evaluate oxidative degradation. In a compost environment, oxygen tension on the surface of the film appears to be the rate-limiting component for both chemical and biological degradation. Levels of starch in all bags was similar, so the prooxidant additive was critical in promoting the oxidative degradation of polyethylene. The Fe-Mn additive displayed the best catalytic activity. This study overall confirms degradation of starch-polyethylene plastics in a natural environment. 17 refs., 6 figs., 2 tabs.

  1. Degradation of endogenous bacterial cell wall polymers by the muralytic enzyme mutanolysin prevents hepatobiliary injury in genetically susceptible rats with experimental intestinal bacterial overgrowth.

    PubMed Central

    Lichtman, S N; Okoruwa, E E; Keku, J; Schwab, J H; Sartor, R B

    1992-01-01

    Jejunal self-filling blind loops with subsequent small bowel bacterial overgrowth (SBBO) induce hepatobiliary injury in genetically susceptible Lewis rats. Lesions consist of portal tract inflammation, bile duct proliferation, and destruction. To determine the pathogenesis of SBBO-induced hepatobiliary injury, we treated Lewis rats with SBBO by using several agents with different mechanisms of activity. Buffer treatment, ursodeoxycholic acid, prednisone, methotrexate, and cyclosporin A failed to prevent SBBO-induced injury as demonstrated by increased plasma aspartate aminotransferase (AST) and elevated histology scores. However, hepatic injury was prevented by mutanolysin, a muralytic enzyme whose only known activity is to split the beta 1-4 N-acetylmuramyl-N-acetylglucosamine linkage of peptidoglycan-polysaccharide (PG-PS), a bacterial cell wall polymer with potent inflammatory and immunoregulatory properties. Mutanolysin therapy started on the day blind loops were surgically created and continued for 8 wk significantly diminished AST (101 +/- 37 U/liter) and liver histology scores (2.2 +/- 2.7) compared to buffer-treated rats (228 +/- 146 U/liter, P < 0.05, 8.2 +/- 1.9, P < 0.001 respectively). Mutanolysin treatment started during the early phase of hepatic injury, 16-21 d after surgery, decreased AST in 7 of 11 rats from 142 +/- 80 to 103 +/- 24 U/liter contrasted to increased AST in 9 of 11 buffer-treated rats from 108 +/- 52 to 247 +/- 142 U/liter, P < 0.05. Mutanolysin did not change total bacterial numbers within the loop, eliminate Bacteroides sp., have in vitro antibiotic effects, or diminish mucosal PG-PS transport. However, mutanolysin treatment prevented elevation of plasma anti-PG antibodies and tumor necrosis factor-alpha (TNF alpha) levels which occurred in buffer treated rats with SBBO and decreased TNF alpha production in isolated Kupffer cells stimulated in vitro with PG-PS. Based on the preventive and therapeutic activity of this highly specific

  2. Atomic step-and-terrace surface of polyimide sheet for advanced polymer substrate engineering

    NASA Astrophysics Data System (ADS)

    Tan, G.; Shimada, K.; Nozawa, Y.; Kaneko, S.; Urakami, T.; Koyama, K.; Komura, M.; Matsuda, A.; Yoshimoto, M.

    2016-07-01

    Typical thermostable and flexible polyimide polymers exhibit many excellent properties such as strong mechanical and chemical resistance. However, in contrast to single-crystal substrates like silicon or sapphire, polymers mostly display disordered and rough surfaces, which may result in instability and degradation of the interfaces between thin films and polymer substrates. As a step toward the development of next-generation polymer substrates, we here report single-atom-layer imprinting onto the polyimide sheets, resulting in an ultrasmooth 0.3 nm high atomic step-and-terrace surface on the polyimides. The ultrasmooth polymer substrates are expected to be applied to the fabrication of nanostructures such as superlattices, nanowires, or quantum dots in nanoscale-controlled electronic devices. We fabricate smooth and atomically stepped indium tin oxide transparent conducting oxide thin films on the imprinted polyimide sheets for future use in organic-based optoelectronic devices processed with nanoscale precision. Furthermore, toward 2D polymer substrate nanoengineering, we demonstrate nanoscale letter writing on the atomic step-and-terrace polyimide surface via atomic force microscopy probe scratching.

  3. Atomizing apparatus for making polymer and metal powders and whiskers

    DOEpatents

    Otaigbe, Joshua U.; McAvoy, Jon M.; Anderson, Iver E.; Ting, Jason; Mi, Jia; Terpstra, Robert

    2003-03-18

    Method for making polymer particulates, such as spherical powder and whiskers, by melting a polymer material under conditions to avoid thermal degradation of the polymer material, atomizing the melt using gas jet means in a manner to form atomized droplets, and cooling the droplets to form polymer particulates, which are collected for further processing. Atomization parameters can be controlled to produce polymer particulates with controlled particle shape, particle size, and particle size distribution. For example, atomization parameters can be controlled to produce spherical polymer powders, polymer whiskers, and combinations of spherical powders and whiskers. Atomizing apparatus also is provided for atoomizing polymer and metallic materials.

  4. Microgravity Polymers

    NASA Technical Reports Server (NTRS)

    1986-01-01

    A one-day, interactive workshop considering the effects of gravity on polymer materials science was held in Cleveland, Ohio, on May 9, 1985. Selected programmatic and technical issues were reviewed to introduce the field to workshop participants. Parallel discussions were conducted in three disciplinary working groups: polymer chemistry, polymer physics, and polymer engineering. This proceedings presents summaries of the workshop discussions and conclusions.

  5. Degradable polyethylene: fantasy or reality.

    PubMed

    Roy, Prasun K; Hakkarainen, Minna; Varma, Indra K; Albertsson, Ann-Christine

    2011-05-15

    Plastic waste disposal is one of the serious environmental issues being tackled by our society today. Polyethylene, particularly in packaging films, has received criticism as it tends to accumulate over a period of time, leaving behind an undesirable visual footprint. Degradable polyethylene, which would enter the eco-cycle harmlessly through biodegradation would be a desirable solution to this problem. However, the "degradable polyethylene" which is presently being promoted as an environmentally friendly alternative to the nondegradable counterpart, does not seem to meet this criterion. This article reviews the state of the art on the aspect of degradability of polyethylene containing pro-oxidants, and more importantly the effect these polymers could have on the environment in the long run. On exposure to heat, light, and oxygen, these polymers disintegrate into small fragments, thereby reducing or increasing the visual presence. However, these fragments can remain in the environment for prolonged time periods. This article also outlines important questions, particularly in terms of time scale of complete degradation, environmental fate of the polymer residues, and possible accumulation of toxins, the answers to which need to be established prior to accepting these polymers as environmentally benign alternatives to their nondegradable equivalents. It appears from the existing literature that our search for biodegradable polyethylene has not yet been realized.

  6. Synthetic Polymers from Readily Available Monosaccharides

    NASA Astrophysics Data System (ADS)

    Galbis, J. A.; García-Martín, M. G.

    The low degradability of petroleum-based polymers and the massive use of these materials constitute a serious problem because of the environmental pollution that they can cause. Thus, sustained efforts have been extensively devoted to produce new polymers based on natural renewing resources and with higher degradability. Of the different natural sources, carbohydrates stand out as highly convenient raw materials because they are inexpensive, readily available, and provide great stereochemical diversity. New polymers, analogous to the more accredited technical polymers, but based on chiral monomers, have been synthesized from natural and available sugars. This chapter describes the potential of sugar-based monomers as precursors to a wide variety of macromolecular materials.

  7. Fracto-Emission from Polymers.

    DTIC Science & Technology

    1983-06-01

    ways serves as a probe of the electronic and chemical activity of the fracture surfaces . The work described in this report represents the results of...evidence from fracture experiments, we present results from studies of electron bombardment of a polymer surface . t -9- I. INTRODUCTION Fracto-emission (FE...RE has been detected previously by Derjaguin , et al. (8) during the separation of polymer films from dielectric surfaces at pressures considerably

  8. Optical probe

    DOEpatents

    Hencken, Kenneth; Flower, William L.

    1999-01-01

    A compact optical probe is disclosed particularly useful for analysis of emissions in industrial environments. The instant invention provides a geometry for optically-based measurements that allows all optical components (source, detector, rely optics, etc.) to be located in proximity to one another. The geometry of the probe disclosed herein provides a means for making optical measurements in environments where it is difficult and/or expensive to gain access to the vicinity of a flow stream to be measured. Significantly, the lens geometry of the optical probe allows the analysis location within a flow stream being monitored to be moved while maintaining optical alignment of all components even when the optical probe is focused on a plurality of different analysis points within the flow stream.

  9. Thermal degradation of polyketones. Vibrational spectroscopy studies

    NASA Astrophysics Data System (ADS)

    Conti, G.; Sommazzi, A.

    1993-03-01

    Thermal degradation studies of regular alternating polymers of carbon monoxide and olefin have been followed by FT-IR spectroscopy. The I.R spectra of solid samples, performed in inert atmosphere and in high vacuum, were recorded as a function of time at different temperatures. From the I.R. data it is possible to conclude that the reaction process, near the melting point of the polymers, could consist of intra or intermolecular hydrogen transfer yielding an enol and a small quantity of insaturations. The thermal degradation process, at temperatures higher than melting point, involves the scission of the polymer chain and produces fragments with a large number of insaturations.

  10. Information storage and retrieval for probe storage using optical diffraction patterns

    NASA Astrophysics Data System (ADS)

    van Honschoten, Joost W.; de Jong, Henri W.; Koelmans, Wabe W.; Parnell, Thomas P.; Zaboronski, Oleg

    2011-11-01

    A method for fast information retrieval from a probe storage device is considered. It is shown that information can be stored and retrieved using the optical diffraction patterns obtained by the illumination of a large array of cantilevers by a monochromatic light source. In thermo-mechanical probe storage, the information is stored as a sequence of indentations on the polymer medium. To retrieve the information, the array of probes is actuated by applying a bending force to the cantilevers. Probes positioned over indentations experience deflection by the depth of the indentation, probes over the flat media remain un-deflected. Thus the array of actuated probes can be viewed as an irregular optical grating, which creates a data-dependent diffraction pattern when illuminated by laser light. We develop a low complexity modulation scheme, which allows the extraction of information stored in the pattern of indentations on the media from Fourier coefficients of the intensity of the diffraction pattern. We then derive a low-complexity maximum-likelihood sequence detection algorithm for retrieving the user information from the Fourier coefficients. The derivation of both the modulation and the detection schemes is based on the Fraunhofer formula for data-dependent diffraction patterns. The applicability of Fraunhofer diffraction theory to the optical set-up relevant for probe storage is established both theoretically and experimentally. We confirm the potential of the optical readout technique by demonstrating that the impairment characteristics of probe storage channels (channel noise, global positioning errors, small indentation depth) do not lead to an unacceptable increase in data recovery error rates. We also show that for as long as the Fresnel number F ≤ 0.1, the optimal channel detector derived from Fraunhofer diffraction theory does not suffer any significant performance degradation.

  11. Mechanosensitive membrane probes.

    PubMed

    Dal Molin, Marta; Verolet, Quentin; Soleimanpour, Saeideh; Matile, Stefan

    2015-04-13

    This article assembles pertinent insights behind the concept of planarizable push-pull probes. As a response to the planarization of their polarized ground state, a red shift of their excitation maximum is expected to report on either the disorder, the tension, or the potential of biomembranes. The combination of chromophore planarization and polarization contributes to various, usually more complex processes in nature. Examples include the color change of crabs or lobsters during cooking or the chemistry of vision, particularly color vision. The summary of lessons from nature is followed by an overview of mechanosensitive organic materials. Although often twisted and sometimes also polarized, their change of color under pressure usually originates from changes in their crystal packing. Intriguing exceptions include the planarization of several elegantly twisted phenylethynyl oligomers and polymers. Also mechanosensitive probes in plastics usually respond to stretching by disassembly. True ground-state planarization in response to molecular recognition is best exemplified with the binding of thoughtfully twisted cationic polythiophenes to single- and double-stranded oligonucleotides. Molecular rotors, en vogue as viscosity sensors in cells, operate by deplanarization of the first excited state. Pertinent recent examples are described, focusing on λ-ratiometry and intracellular targeting. Complementary to planarization of the ground state with twisted push-pull probes, molecular rotors report on environmental changes with quenching or shifts in emission rather than absorption. The labeling of mechanosensitive channels is discussed as a bioengineering approach to bypass the challenge to create molecular mechanosensitivity and use biological systems instead to sense membrane tension. With planarizable push-pull probes, this challenge is met not with twistome screening, but with "fluorescent flippers," a new concept to insert large and bright monomers into oligomeric

  12. Probing Polymer-Segment Motions By ESR

    NASA Technical Reports Server (NTRS)

    Tsay, Fun-Dow; Gupta, Amitava

    1988-01-01

    Molecular origins of mechanical properties and aging processes studied. Rotational motions of segments of poly(methyl methacrylate) molecules studied theoretically and experimentally. Activation energies of these motions as determined from temperature dependencies of ESR spectra agree closely with predictions of theory.

  13. Durability Improvements Through Degradation Mechanism Studies

    SciTech Connect

    Borup, Rodney L.; Mukundan, Rangachary; Spernjak, Dusan; Baker, Andrew M.; Lujan, Roger W.; Langlois, David Alan; Ahluwalia, Rajesh; Papadia, D. D.; Weber, Adam Z.; Kusoglu, Ahmet; Shi, Shouwnen; More, K. L.; Grot, Steve

    2015-08-03

    The durability of polymer electrolyte membrane (PEM) fuel cells is a major barrier to the commercialization of these systems for stationary and transportation power applications. By investigating cell component degradation modes and defining the fundamental degradation mechanisms of components and component interactions, new materials can be designed to improve durability. To achieve a deeper understanding of PEM fuel cell durability and component degradation mechanisms, we utilize a multi-institutional and multi-disciplinary team with significant experience investigating these phenomena.

  14. Triggerable Degradation of Polyurethanes for Tissue Engineering Applications.

    PubMed

    Xu, Cancan; Huang, Yihui; Wu, Jinglei; Tang, Liping; Hong, Yi

    2015-09-16

    Tissue engineered and bioactive scaffolds with different degradation rates are required for the regeneration of diverse tissues/organs. To optimize tissue regeneration in different tissues, it is desirable that the degradation rate of scaffolds can be manipulated to comply with various stages of tissue regeneration. Unfortunately, the degradation of most degradable polymers relies solely on passive controlled degradation mechanisms. To overcome this challenge, we report a new family of reduction-sensitive biodegradable elastomeric polyurethanes containing various amounts of disulfide bonds (PU-SS), in which degradation can be initiated and accelerated with the supplement of a biological product: antioxidant-glutathione (GSH). The polyurethanes can be processed into films and electrospun fibrous scaffolds. Synthesized materials exhibited robust mechanical properties and high elasticity. Accelerated degradation of the materials was observed in the presence of GSH, and the rate of such degradation depends on the amount of disulfide present in the polymer backbone. The polymers and their degradation products exhibited no apparent cell toxicity while the electrospun scaffolds supported fibroblast growth in vitro. The in vivo subcutaneous implantation model showed that the polymers prompt minimal inflammatory responses, and as anticipated, the polymer with the higher disulfide bond amount had faster degradation in vivo. This new family of polyurethanes offers tremendous potential for directed scaffold degradation to promote maximal tissue regeneration.

  15. Nanostructured conducting polymers and their biomedical applications.

    PubMed

    Wang, G W; Lu, Y N; Wang, L P; Wang, H J; Wang, J Y

    2014-01-01

    Much attention has been paid to nanostructured conducting polymers due to their unique properties, which arise from their nanoscale size, such as their large surface area, high electrical conductivity, electrochemical stability and quantum effects. This article reviews three methods to synthesize nanostructured conducting polymers and their applications in the biomedical field, focusing specifically on neural probes, biosensors, artificial muscles or actuators and controlled drug release. Challenges and future directions of these nanostructured conducting polymer are also discussed.

  16. Probing Aggrecan Interactions with Ions by AFM

    NASA Astrophysics Data System (ADS)

    Chandran, Preethi; Dimitriadis, Emilios; Basser, Peter; Horkay, Ferenc

    2010-03-01

    Aggrecan (MW 2 MDa) is a highly charged bottle-brush shape biological polymer found in the extracellular matrix of tissues. It consists of a protein backbone (400nm long), to which about 100 linear chains of negatively-charged glucosaminoglycans are attached approximately 4 nm apart. The high charge density of the aggrecan bottle-brush allows it to imbibe water, thereby maintaining tissue hydration and permeability, while also binding to cell-signaling molecules. In solution, aggrecan molecules respond differently to varying salt conditions, than other charged biological and synthetic polyelectrolytes like DNA and poly(acrylic acid) (Horkay, 2008). To probe the nature of its interactions with charged surfaces, we looked at the absorption patterns of aggrecan assemblies on controlled surfaces (polylysine, mica) under different ionic conditions, using Atomic Force Microscopy. We propose a simple model of the charge interactions, which relates the surface-adsorption patterns to the solution structures. The study may help understanding how aggrecan loss or degradation with age and joint disease affects tissue microstructure and physical properties.

  17. Inorganic polymer engineering materials

    SciTech Connect

    Stone, M.L.

    1993-06-01

    Phosphazene-based, inorganic-polymer composites have been produced and evaluated as potential engineering materials. The thermal, chemical, and mechanical properties of several different composites made from one polymer formulation have been measured. Measured properties are very good, and the composites show excellent promise for structural applications in harsh environments. Chopped fiberglass, mineral, cellulose, and woodflour filled composites were tested. Chopped fiberglass filled composites showed the best overall properties. The phosphazene composites are very hard and rigid. They have low dielectric constants and typical linear thermal expansion coefficients for polymers. In most cases, the phosphazene materials performed as well or better than analogous, commercially available, filled phenolic composites. After 3 to 5 weeks of exposure, both the phosphazene and phenolics were degraded to aqueous bases and acids. The glass filled phosphazene samples were least affected.

  18. Ultraviolet and thermally stable polymer compositions

    NASA Technical Reports Server (NTRS)

    Reinisch, R. F.; Gloria, H. R.; Goldsberry, R. E.; Adamson, M. J. (Inventor)

    1976-01-01

    A new class of polymers is provided, namely, poly (diarylsiloxy) arylazines. These novel polymers have a basic chemical composition which has the property of stabilizing the optical and physical properties of the polymer against the degradative effect of ultraviolet light and high temperatures. This stabilization occurs at wavelengths including those shorter than found on the surface of the earth and in the absence or presence of oxygen, making the polymers useful for high performance coating applications in extraterrestrial space as well as similar applications in terrestrial service. The invention also provides novel aromatic azines which are useful in the preparation of polymers such as those described.

  19. Ultraviolet and thermally stable polymer compositions

    NASA Technical Reports Server (NTRS)

    Reinisch, R. F.; Gloria, H. R.; Goldsberry, R. E.; Adamson, M. J. (Inventor)

    1974-01-01

    A class of polymers is provided, namely, poly(diarylsiloxy) arylazines. These polymers have a basic chemical composition which has the property of stabilizing the optical and physical properties of the polymer against the degradative effect of ultraviolet light and high temperatures. This stabilization occurs at wavelengths including those shorter than found on the surface of the earth and in the absence or presence of oxygen, making the polymers of the present invention useful for high performance coating applications in extraterrestrial space as well as similar applications in terrestrial service. The invention also provides aromatic azines which are useful in the preparation of polymers such as those of the present invention.

  20. Biodegradation of superabsorbent polymers in soil.

    PubMed

    Stahl, J D; Cameron, M D; Haselbach, J; Aust, S D

    2000-01-01

    Biodegradation of two superabsorbent polymers, a crosslinked, insoluble polyacrylate and an insoluble polyacrylate/ polyacrylamide copolymer, in soil by the white-rot fungus, Phanerochaete chrysosporium was investigated. The polymers were both solubilized and mineralized by the fungus but solubilization and mineralization of the copolymer was much more rapid than of the polyacrylate. Soil microbes poorly solublized the polymers and were unable to mineralize either intact polymer. However, soil microbes cooperated with the fungus during polymer degradation in soil, with the fungus solubilizing the polymers and the soil microbes stimulating mineralization. Further, soil microbes were able to significantly mineralize both polymers after solubilization by P. chrysosporium grown under conditions that produced fungal peroxidases or cellobiose dehydrogenase, or after solubilization by photochemically generated Fenton reagent. The results suggest that biodegradation of these polymers in soil is best under conditions that maximize solubilization.

  1. Biodegradable Polymers for the Environment

    NASA Astrophysics Data System (ADS)

    Gross, Richard A.; Kalra, Bhanu

    2002-08-01

    Biodegradable polymers are designed to degrade upon disposal by the action of living organisms. Extraordinary progress has been made in the development of practical processes and products from polymers such as starch, cellulose, and lactic acid. The need to create alternative biodegradable water-soluble polymers for down-the-drain products such as detergents and cosmetics has taken on increasing importance. Consumers have, however, thus far attached little or no added value to the property of biodegradability, forcing industry to compete head-to-head on a cost-performance basis with existing familiar products. In addition, no suitable infrastructure for the disposal of biodegradable materials exists as yet.

  2. Piezoelectric Polymers

    NASA Technical Reports Server (NTRS)

    Harrison, J. S.; Ounaies, Z.; Bushnell, Dennis M. (Technical Monitor)

    2001-01-01

    The purpose of this review is to detail the current theoretical understanding of the origin of piezoelectric and ferroelectric phenomena in polymers; to present the state-of-the-art in piezoelectric polymers and emerging material systems that exhibit promising properties; and to discuss key characterization methods, fundamental modeling approaches, and applications of piezoelectric polymers. Piezoelectric polymers have been known to exist for more than forty years, but in recent years they have gained notoriety as a valuable class of smart materials.

  3. Regulation of Coal Polymer Degradation by Fungi

    SciTech Connect

    1998-09-01

    During this reporting period we have further studied the oxidation of soluble coal macromolecules by lignin peroxidase from Phanerochaete chrysosporium . Previous studies by others have suggested that a soluble fraction (coal macromolecule B-111) from a nitric acid solubilized North Dakota Lignite is depolymerized by this enzyme. Our investigations indicate that fraction B-111 is a substrate for lignin peroxidase as this material is decolorized in the presence of lignin peroxidase H8 and hydrogen peroxide. Of interest, however, is the observation that little, if any, depolymerization of this material occurs. Instead, it appears that lignin peroxidase and coal macromolecule B-111 form a precipitate. These results are similar to those observed in our investigations of lignin peroxidase mediated oxidation of oxalate solubilize coal macromolecule. Previous studies in our laboratory using a spectrophotometric assay suggested that, in addition to oxalate, several other fungal metabolites are able to solubilize leonardite. We have reinvestigated this phenomenon using a more reliable gravimetric procedure for assessing solubilization. Our results confirm our earlier findings that malate, oxaloacetate and citrate are effective solubilizing agents whereas succinate, fumarate and x-ketoglutarate solubilize relatively small amounts of leonardite. Finally, we have studied the composition of the insoluble material remaining following extensive solubilization by sodium oxalate. The ratio of hydrogen to carbon is increased in the insoluble material relative to the parent leonardite. However, the ratio of oxygen to carbon is also increased in the insoluble material. Thus, the insoluble material does not appear to be more highly reduced that the parent leonardite and is not likely to be a better fuel that the parent material.

  4. Regulation of Coal Polymer Degradation by Fungi

    SciTech Connect

    Irvine, Robert L.; Bumpus, John A.

    1996-12-01

    Several investigations have demonstrated that oxalate anion secreted by fungi is able to mediate solubilization of Ieonardite, a highly oxidized lignite. During this reporting period, we have used a biomimetic approach to study oxalate mediated solubilization of several Argonne Premium Coals. Results showed that, relative to Ieonardite, oxalate solubilized minimal amounts of these coals. Other studies showed that pH has a dramatic effect on solubilization of Ieonardite by several Lewis bases. In general, solubilization appeared to be a function of ionization of the Lewis base. Coal solubilization is estimated by an increase in the visible spectrum of aqueous solutions containing coal and a solubilizing agent. Because Ieonardite solubilization was studied over a broad pH range, it was necessary to determine if pH has a substantial effect on the absorbance of soluble coal macromolecule. Results showed that absorbance at 600 nm increased by {approx}56% between pH 4.5 and pH 12.0. Clearly, this increase must be considered when interpreting coal solubilization data. The decolonization of soluble coal macromolecule in nutrient nitrogen limited cultures of Phanerochaete chrysosporium was also studied. In stationary and agitated cultures, respectively, 83.8% {+-} 2.3% and 89.6% {+-} 1.0% of the coal macromolecule was decolorized during 8 days of incubation.

  5. Degradation of Polymer-Coated Materials

    DTIC Science & Technology

    2013-10-01

    However, the filaments were thinner than was observed when a Boegel conversion coating was used. Comparisons were also made on corrosion site growth at...Movie 1.4.3. With the CCC, corrosion filaments were thinner than with Boegel. Furthermore, the corrosion front was more irregular than with Boegel...should be noted that the corrosion propagation for these coating systems was similar to the samples without topcoat. However, the corrosion filaments

  6. Understanding API-polymer proximities in amorphous stabilized composite drug products using fluorine-carbon 2D HETCOR solid-state NMR.

    PubMed

    Abraham, Anuji; Crull, George

    2014-10-06

    A simple and robust method for obtaining fluorine-carbon proximities was established using a (19)F-(13)C heteronuclear correlation (HETCOR) two-dimensional (2D) solid-state nuclear magnetic resonance (ssNMR) experiment under magic-angle spinning (MAS). The method was applied to study a crystalline active pharmaceutical ingredient (API), avagacestat, containing two types of fluorine atoms and its API-polymer composite drug product. These results provide insight into the molecular structure, aid with assigning the carbon resonances, and probe API-polymer proximities in amorphous spray dried dispersions (SDD). This method has an advantage over the commonly used (1)H-(13)C HETCOR because of the large chemical shift dispersion in the fluorine dimension. In the present study, fluorine-carbon distances up to 8 Å were probed, giving insight into the API structure, crystal packing, and assignments. Most importantly, the study demonstrates a method for probing an intimate molecular level contact between an amorphous API and a polymer in an SDD, giving insights into molecular association and understanding of the role of the polymer in API stability (such as recrystallization, degradation, etc.) in such novel composite drug products.

  7. Oil recovery process using a treated polymer solution

    SciTech Connect

    Luetzelschwab, W.E.

    1989-09-19

    This patent describes a process for recovering oil from a subterranean oil-bearing formation. It comprises the sequential steps of: contacting an aqueous acrylamide polymer-free liquid with an oxygenating agent, wherein the aqueous acrylamide polymer-free liquid initially contains hydrogen sulfide in a sufficient concentration to substantially degrade an acrylamide polymer; reducing the initial hydrogen sulfide concentration of the aqueous acrylamide polymer-free liquid; mixing the aqueous liquid with the acrylamide polymer to form an aqueous acrylamide polymer solution; injecting the aqueous acrylamide polymer solution into the subterranean oil-bearing formation; and recovering oil from the formation.

  8. Pollution Probe.

    ERIC Educational Resources Information Center

    Chant, Donald A.

    This book is written as a statement of concern about pollution by members of Pollution Probe, a citizens' anti-pollution group in Canada. Its purpose is to create public awareness and pressure for the eventual solution to pollution problems. The need for effective government policies to control the population explosion, conserve natural resources,…

  9. Improved performance in polymer - inorganic composite photovoltaics

    NASA Astrophysics Data System (ADS)

    Breeze, Alison J.

    It has become increasingly clear over the past few decades that some form of alternative energy is needed to replace the traditional fossil fuels. I briefly discuss a few of the possible alternative sources, why solar energy is one of the more promising ones, give a short history of the development of the solar cell, and explain the motivations for research into polymer - inorganic composite solar cells. An introduction to conducting and semiconducting polymers, as well as the basics of polymer solar cell operation, is given. I present experimental results on the variation of several parameters such as polymer thickness, TiO2 and polymer morphology, and choice of electrodes for devices of the type ITO/TiO2/photoactive polymer/Au in order to probe the effects of charge transport, carrier mobility, light absorption and direction of the internal field on device efficiency. The results demonstrate that short exciton diffusion lengths, low carrier mobilities, and low absorption are the main factors limiting performance in plain polymer photovoltaics. Nanoparticle - polymer and polymer - polymer blend devices are explored as possible solutions for the first two deficiencies, with the polymer - polymer blend devices achieving the best results with an overall 0.6% power conversion efficiency. Many of the experimental results of polymer photovoltaics can be simulated using a simple model which includes terms for Schottky-like injection, ohmic current leakage, and collected photogenerated current. I discuss both the successes and failures of this model, as well as areas for future improvements.

  10. Synthetic biodegradable polymers for orthopaedic applications.

    PubMed

    Behravesh, E; Yasko, A W; Engel, P S; Mikos, A G

    1999-10-01

    Synthetic biodegradable polymers offer an alternative to the use of autografts, allografts, and nondegradable materials for bone replacement. They can be synthesized with tailored mechanical and degradative properties. They also can be processed to porous scaffolds with desired pore morphologic features conducive to tissue ingrowth. Moreover, functionalized polymers can modulate cellular function and induce tissue ingrowth. This review focuses on four classes of polymers that hold promise for orthopaedic applications: poly alpha-hydroxy esters, polyphosphazenes, polyanhydrides, and polypropylene fumarate crosslinked networks.

  11. Semi-degradable poly(β-amino ester) networks with temporally controlled enhancement of mechanical properties.

    PubMed

    Safranski, David L; Weiss, Daiana; Clark, J Brian; Taylor, W Robert; Gall, Ken

    2014-08-01

    Biodegradable polymers are clinically used in numerous biomedical applications, and classically show a loss of mechanical properties within weeks of implantation. This work demonstrates a new class of semi-degradable polymers that show an increase in mechanical properties through degradation via a controlled shift in a thermal transition. Semi-degradable polymer networks, poly(β-amino ester)-co-methyl methacrylate, were formed from a low glass transition temperature crosslinker, poly(β-amino ester), and high glass transition temperature monomer, methyl methacrylate, which degraded in a manner dependent upon the crosslinker chemical structure. In vitro and in vivo degradation revealed changes in mechanical behavior due to the degradation of the crosslinker from the polymer network. This novel polymer system demonstrates a strategy to temporally control the mechanical behavior of polymers and to enhance the initial performance of smart biomedical devices.

  12. Use of Chiral Alcohols for Elucidating the Mode and Kinetics of Degradation of Fluorotelomer Compounds

    EPA Science Inventory

    Fluorotelomer polymers are the dominant product line of the fluorotelomer industry. Fluorotelomer polymers have been shown to degrade under environmental conditions to form numerous fluorotelomer and perfluorinated monomers that are of environmental and toxicological concern; how...

  13. Binning of shallowly sampled metagenomic sequence fragments reveals that low abundance bacteria play important roles in sulfur cycling and degradation of complex organic polymers in an acid mine drainage community

    NASA Astrophysics Data System (ADS)

    Dick, G. J.; Andersson, A.; Banfield, J. F.

    2007-12-01

    not expected to reflect the tetranucleotide frequency signature of the host genome. Four unknown tetranucleotide frequency clusters with significant sequence (6 Mb total) were noted and analyzed further. Based on phylogenetic markers and BLAST results, these clusters represent low abundance bacteria including Acintobacteria, Firmicutes, and Proteobacteria. Functional analysis of these clusters revealved that the low- abundance bacteria harbor genes that could potentially encode important ecosystem functions such as sulfur utilization (e.g. polysulfide reductase) and polymer degradation (e.g. chitinase and glycoside hydrolase). We conclude that ESOM clustering of tetranucleotide frequency patterns is an effective method for rapidly binning shotgun community genomic sequences and a valuable tool for analyzing minor community members, which despite their low abundance may play crucial ecological roles.

  14. Optimizing Glassy Polymer Network Morphology for Nano-particle Dispersion, Stabilization and Performance

    DTIC Science & Technology

    2016-10-03

    dispersity and polymerization pathway, Moskowitz, Jeremy and Wiggins, Jeffrey, Polymer Degradation and Stability 2016, 125, 76 iv. High Molecular... polymerization pathway, Moskowitz, Jeremy and Wiggins, Jeffrey, Polymer Degradation and Stability 2016, 125, 76 iv. High Molecular Weight and Low Dispersity... Applications Jessica Piness, Katrina Knauer, Jeffrey Wiggins, SAMPE Tech 2015, Baltimore, MD, May 2015 xxvi. Cure behavior and polymer chain dynamics of

  15. Green polymer chemistry: Some recent developments and examples

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Green polymer chemistry continues to be a popular field, with many books and publications in print. Research is being conducted in several areas within this field, including: 1) green catalysis, 2) diverse feedstock base, 3) degradable polymers and waste minimization, 4) recycling of polymer produc...

  16. Fire-retardant epoxy polymers

    NASA Technical Reports Server (NTRS)

    Akawie, R. I.; Bilow, N.; Giants, T. W.

    1978-01-01

    Phosphorus atoms in molecular structure of epoxies make them fire-retardant without degrading their adhesive strength. Moreover, polymers are transparent, unlike compounds that contain arsenic or other inorganics. They have been used to bond polyvinylfluoride and polyether sulfone films onto polyimide glass laminates.

  17. Engineered polymers for advanced drug delivery.

    PubMed

    Kim, Sungwon; Kim, Jong-Ho; Jeon, Oju; Kwon, Ick Chan; Park, Kinam

    2009-03-01

    Engineered polymers have been utilized for developing advanced drug delivery systems. The development of such polymers has caused advances in polymer chemistry, which, in turn, has resulted in smart polymers that can respond to changes in environmental condition such as temperature, pH, and biomolecules. The responses vary widely from swelling/deswelling to degradation. Drug-polymer conjugates and drug-containing nano/micro-particles have been used for drug targeting. Engineered polymers and polymeric systems have also been used in new areas, such as molecular imaging as well as in nanotechnology. This review examines the engineered polymers that have been used as traditional drug delivery systems and as more recent applications in nanotechnology.

  18. Engineered Polymers for Advanced Drug Delivery

    PubMed Central

    Kim, Sungwon; Kim, Jong-Ho; Jeon, Oju; Kwon, Ick Chan; Park, Kinam

    2009-01-01

    Engineered polymers have been utilized for developing advanced drug delivery systems. The development of such polymers has caused advances in polymer chemistry, which, in turn, has resulted in smart polymers that can respond to changes in environmental condition, such as temperature, pH, and biomolecules. The responses vary widely from swelling/deswelling to degradation. Drug-polymer conjugates and drug-containing nano/micro-particles have been used for drug targeting. Engineered polymers and polymeric systems have also been used in new areas, such as molecular imaging as well as in nanotechnology. This review examines the engineered polymers that have been used as traditional drug delivery and as more recent applications in nanotechnology. PMID:18977434

  19. Polymerization of secretory IgM in B lymphocytes is prevented by a prior targeting to a degradation pathway.

    PubMed

    Shachar, I; Amitay, R; Rabinovich, E; Haimovich, J; Bar-Nun, S

    1992-12-05

    B lymphocytes express on their surface a membrane form of IgM (mIgM), and synthesize but fail to secrete a secretory form of IgM (sIgM). Plasma cells shift to the exclusive synthesis and efficient secretion of sIgM. The sIgM in B cells differs from that in plasma cells in its pattern of assembly: in plasma cells, monomers of sIgM are assembled into polymers and only polymers are secreted; in B lymphocytes, monomeric sIgM is neither polymerized nor secreted and is degraded intracellularly. In this article we blocked the export of proteins from the endoplasmic reticulum at low temperatures or with energy poisons or brefeldin A, and localized the different assembly steps of mIgM and sIgM in the 38C B lymphocytes and of sIgM in the 38C-derived sIgM-secreting D2 hybridoma. In both cell lines, sIgM assembly into monomers was not affected, whereas polymerization of sIgM in D2 cells and monomer formation of mIgM in 38C cells were strongly inhibited. Moreover, probing with specific lectins revealed galactosylated monomers and polymers in D2 cells and galactosylated hemimer and monomers only of mIgM in 38C cells. In addition, when Golgi functions were hampered with Tris base, monomerization of mIgM and polymerization of sIgM were attenuated. These results indicate that polymerization of sIgM in D2 cells and monomerization of mIgM in 38C cells are post-endoplasmic reticulum events, occurring in or beyond the trans-Golgi galactosylation compartment. Since only polymers are secreted from D2 cells and only monomeric mIgM is displayed on the surface of 38C cells, partially assembled molecules may traverse the secretory pathway yet are restricted from the cell surface. Furthermore, monomeric sIgM in 38C cells is never galactosylated, thus it is degraded prior to the galactosylation compartment. We conclude that targeting of sIgM to degradation in 38C cells precedes its assembly site into polymers in D2 cells. This implies that degradation of sIgM does not result from the

  20. Degradation and acute toxicity studies of degradable implant materials

    NASA Astrophysics Data System (ADS)

    Taylor, Michelle Suzette

    The present study investigated the acute toxicities of the degradation product components of six degradable polymers, the acute toxicities of nine metallic ions and accelerated degradation of one degradable polymer. Prior to these studies, the effect of the anticipated test conditions on the Microtox acute toxicity assay was determined. It was shown that the Microtox is unaffected by pH of water within the range of 5 to 10 and that the test is unaffected by tris buffer at physiologic pH and concentration. The toxicity and rates of degradation of poly(glycolic acid), PGA; two samples of poly(L-lactic acid), PLLA; samples of different molecular weights, poly(caprolactone), PCL; poly(ortho ester), POE; and poly(hydroxybutyrate-cohydroxyvalerate), PHBV, were compared, along with the toxicity of their degradation product components. The toxic concentrations ranged from 100 muM (lactic acid) to 125,000 muM (pentaerythritol). The degradation product components in order of most toxic to least toxic are lactic acid, caproic acid, glycolic acid, cyclohexanedimethanol, propionic acid, hydroxybutyric acid, 1,6-hexanediol, pentaerythritol dipropionate, pentaerythritol and hydroxyvaleric acid. Acute toxicity was determined for metallic ions in water and buffer. The toxic concentrations ranged from 33 muM (Tisp{4+} in water) to 3,580 muM (Wsp{6+} in buffer). The four most toxic ions in water (Tisp{4+}, Mosp{5+}, Fesp{3+}, Crsp{3+}) caused solution pH to decrease markedly. The six other ions (Vasp{3+}, Cosp{3+}, Alsp{3+,} Tisp{4+} adjusted to pH 6.1, Nisp{2+} and Wsp{6+}) markedly. The six other ions (Vasp{3+}, Cosp{3+}, Alsp{3+}, Tisp{4+} adjusted to pH 6.1, Nisp{2+} and Wsp{6+}) did not appreciably affect pH. In buffer, Alsp{3+}, Nisp{2+}, Wsp{6+} and Vsp{3+} became much less toxic, suggesting formation of complexes. In general the least toxic ions do not create an acid environment and/or do form protective complexes. PHBV has good mechanical properties and, compared with the

  1. Synthesis of Clickable Coating Polymers by Postpolymerization Modification: Applications in Microarray Technology.

    PubMed

    Sola, Laura; Damin, Francesco; Gagni, Paola; Consonni, Roberto; Chiari, Marcella

    2016-10-11

    In this paper, we report on the postpolymerization modification (PPM) of a polymer to introduce new functionalities that enable click chemistry reactions for microarray applications. The parent polymer, named copoly(DMA-NAS-MAPS), is composed of N,N-dimethylacrylamide (DMA), a monomer that self-adsorbs onto different materials through weak interactions such as hydrogen bonding or van der Waals forces, 3-(trimethoxysilyl)propyl methacrylate (MAPS) that strengthens the stability of the coating through the formation of covalent bonds with siloxane groups on the surface to be coated, and N-acryloyloxysuccinimide (NAS), an active ester group, highly reactive toward nucleophiles, which enables bioprobe immobilization. This copolymer has been widely exploited to coat surfaces for microarray applications but exhibits some limitations because of the potential hydrolysis of the active ester (NHS ester). The degradation of the NHS ester hampers the use of this coating in some situations, for example, when probe immobilization cannot be accomplished through a microspotting situation, but in large volumes, for example, in microchannel derivatization or micro-/nanoparticle functionalization. To overcome the limitations of NHS esters, we have developed a family of polymers that originate from the common copolymer precursor, by reacting the active ester contained in the polymer chain with a bifunctional amine. In particular, the functional groups introduced in the polymer using PPM enable click chemistry reactions such as azide/alkyne or thiol/maleimide "click" reactions, with suitably modified biomolecules. The advantages of such reactions are quantitative yields, orthogonality of functional groups, and insensitivity of the reaction to pH. The new click functionalities, inserted with quantitative yields, improve the stability of the coating, enabling the attachment of biomolecules directly from a solution and avoiding the spotting of reduced volumes (pL) of probes. Finally, we

  2. Investigating buried polymer interfaces using sum frequency generation vibrational spectroscopy

    PubMed Central

    Chen, Zhan

    2010-01-01

    This paper reviews recent progress in the studies of buried polymer interfaces using sum frequency generation (SFG) vibrational spectroscopy. Both buried solid/liquid and solid/solid interfaces involving polymeric materials are discussed. SFG studies of polymer/water interfaces show that different polymers exhibit varied surface restructuring behavior in water, indicating the importance of probing polymer/water interfaces in situ. SFG has also been applied to the investigation of interfaces between polymers and other liquids. It has been found that molecular interactions at such polymer/liquid interfaces dictate interfacial polymer structures. The molecular structures of silane molecules, which are widely used as adhesion promoters, have been investigated using SFG at buried polymer/silane and polymer/polymer interfaces, providing molecular-level understanding of polymer adhesion promotion. The molecular structures of polymer/solid interfaces have been examined using SFG with several different experimental geometries. These results have provided molecular-level information about polymer friction, adhesion, interfacial chemical reactions, interfacial electronic properties, and the structure of layer-by-layer deposited polymers. Such research has demonstrated that SFG is a powerful tool to probe buried interfaces involving polymeric materials, which are difficult to study by conventional surface sensitive analytical techniques. PMID:21113334

  3. MALDI-TOF MS Imaging evidences spatial differences in the degradation of solid polycaprolactone diol in water under aerobic and denitrifying conditions.

    PubMed

    Rivas, Daniel; Ginebreda, Antoni; Pérez, Sandra; Quero, Carmen; Barceló, Damià

    2016-10-01

    Degradation of solid polymers in the aquatic environment encompasses a variety of biotic and abiotic processes giving rise to heterogeneous patterns across the surface of the material, which cannot be investigated using conventional Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS) that only renders an "average" picture of the sample. In that context, MALDI-TOF MS Imaging (MALDI MSI) provides a rapid and efficient tool to study 2D spatial changes occurred in the chemical composition of the polymer surface. Commercial polycaprolactone diol (average molecular weight of 1250Da) was selected as test material because it had been previously known to be amenable to biological degradation. The test oligomer probe was incubated under aerobic and denitrifying conditions using synthetic water and denitrifying mixed liquor obtained from a wastewater treatment plant respectively. After ca. seven days of exposure the mass spectra obtained by MALDI MSI showed the occurrence of chemical modifications in the sample surface. Observed heterogeneity across the probe's surface indicated significant degradation and suggested the contribution of biotic processes. The results were investigated using different image processing tools. Major changes on the oligomer surface were observed when exposed to denitrifying conditions.

  4. Transient Thermal Stability of Polymer Nanocomposites

    DTIC Science & Technology

    2012-08-01

    Temperatures exceed melting point and degradation temp of base polymer • Nanoclay and Nanotubes provide degradation resistance • Novel TGA-LPH...difference in heating rate 0 500 1000 1500 2000 0 4 8 12 time (ms) S u rf a c e t e m p e ra tu re ( K ) 120mm cannon Use polypropylene as a model...system to investigate degradation kinetics during transient heating Goal of this project Materials Isotactic Polypropylene + 0-50 wt % nanoclay

  5. Star Polymers.

    PubMed

    Ren, Jing M; McKenzie, Thomas G; Fu, Qiang; Wong, Edgar H H; Xu, Jiangtao; An, Zesheng; Shanmugam, Sivaprakash; Davis, Thomas P; Boyer, Cyrille; Qiao, Greg G

    2016-06-22

    Recent advances in controlled/living polymerization techniques and highly efficient coupling chemistries have enabled the facile synthesis of complex polymer architectures with controlled dimensions and functionality. As an example, star polymers consist of many linear polymers fused at a central point with a large number of chain end functionalities. Owing to this exclusive structure, star polymers exhibit some remarkable characteristics and properties unattainable by simple linear polymers. Hence, they constitute a unique class of technologically important nanomaterials that have been utilized or are currently under audition for many applications in life sciences and nanotechnologies. This article first provides a comprehensive summary of synthetic strategies towards star polymers, then reviews the latest developments in the synthesis and characterization methods of star macromolecules, and lastly outlines emerging applications and current commercial use of star-shaped polymers. The aim of this work is to promote star polymer research, generate new avenues of scientific investigation, and provide contemporary perspectives on chemical innovation that may expedite the commercialization of new star nanomaterials. We envision in the not-too-distant future star polymers will play an increasingly important role in materials science and nanotechnology in both academic and industrial settings.

  6. Polymer Chemistry

    NASA Technical Reports Server (NTRS)

    Williams, Martha; Roberson, Luke; Caraccio, Anne

    2010-01-01

    This viewgraph presentation describes new technologies in polymer and material chemistry that benefits NASA programs and missions. The topics include: 1) What are Polymers?; 2) History of Polymer Chemistry; 3) Composites/Materials Development at KSC; 4) Why Wiring; 5) Next Generation Wiring Materials; 6) Wire System Materials and Integration; 7) Self-Healing Wire Repair; 8) Smart Wiring Summary; 9) Fire and Polymers; 10) Aerogel Technology; 11) Aerogel Composites; 12) Aerogels for Oil Remediation; 13) KSC's Solution; 14) Chemochromic Hydrogen Sensors; 15) STS-130 and 131 Operations; 16) HyperPigment; 17) Antimicrobial Materials; 18) Conductive Inks Formulations for Multiple Applications; and 19) Testing and Processing Equipment.

  7. Biodegradable polymers for microencapsulation of drugs.

    PubMed

    Park, Jae Hyung; Ye, Mingli; Park, Kinam

    2005-01-31

    Drug delivery has become increasingly important mainly due to the awareness of the difficulties associated with a variety of old and new drugs. Of the many polymeric drug delivery systems, biodegradable polymers have been used widely as drug delivery systems because of their biocompatibility and biodegradability. The majority of biodegradable polymers have been used in the form of microparticles, from which the incorporated drug is released to the environment in a controlled manner. The factors responsible for controlling the drug release rate are physicochemical properties of drugs, degradation rate of polymers, and the morphology and size of microparticles. This review discusses the conventional and recent technologies for microencapsulation of the drugs using biodegradable polymers. In addition, this review presents characteristics and degradation behaviors of biodegradable polymers which are currently used in drug delivery.

  8. Solid polymer membrane program

    NASA Technical Reports Server (NTRS)

    1971-01-01

    The results are presented for a solid polymer electrolyte fuel cell development program. Failure mechanism was identified and resolution of the mechanism experienced in small stack testing was demonstrated. The effect included laboratory analysis and evaluation of a matrix of configurations and operational variables for effects on the degree of hydrogen fluoride released from the cell and on the degree of blistering/delamination occurring in the reactant inlet areas of the cell and to correlate these conditions with cell life capabilities. The laboratory evaluation tests were run at conditions intended to accelerate the degradation of the solid polymer electrolyte in order to obtain relative evaluations as quick as possible. Evaluation of the resolutions for the identified failure mechanism in space shuttle configuration cell assemblies was achieved with the fabrication and life testing of two small stack buildups of four cell assemblies and eight cells each.

  9. Polymers & People

    ERIC Educational Resources Information Center

    Lentz, Linda; Robinson, Thomas; Martin, Elizabeth; Miller, Mary; Ashburn, Norma

    2004-01-01

    Each Tuesday during the fall of 2002, teams of high school students from three South Carolina counties conducted a four-hour polymer institute for their peers. In less than two months, over 300 students visited the Charleston County Public Library in Charleston, South Carolina, to explore DNA, nylon, rubber, gluep, and other polymers. Teams of…

  10. More Than Just a Polymer

    NASA Technical Reports Server (NTRS)

    2001-01-01

    Triton atomic Oxygen Resistant polymers TOR(TM), were developed by Chelmsford, Massachusetts-based Triton Systems, Inc., through a Small Business Innovation Research (SBIR) contract from NASA's Langley Research Center. The new family of polymers comes from a Langley-developed polymer technology, which marks a new class of aerospace materials that resist the extreme effects of low Earth orbit (LEO). When applied to spacecraft surfaces, TOR polymers protect against erosion caused by the atomic oxygen and radiation present in space. Other polymers, such as Teflon(R) and Kapton(R), are subject to degradation from atomic oxygen and ultraviolet radiation, but TOR polymers use atomic oxygen to their advantage. A long-lasting protective barrier means major savings in the cost of spacecraft maintenance and the time spent performing repairs. While the obvious application of this material lies with the aerospace industry, an underlying benefit is found in the field of electronics. TOR polymers can be made electrically conductive, and then utilized in the creation of sensors that react to the presence of chemical and biological agents by exhibiting a detectable change in electrical conductivity. These sensors have applications in the defense, medical, and industrial sectors.

  11. Polymer concepts in tissue engineering.

    PubMed

    Peter, S J; Miller, M J; Yasko, A W; Yaszemski, M J; Mikos, A G

    1998-01-01

    Traumatic injuries, cancer treatment, and congenital abnormalities are often associated with abnormal bone shape or segmental bone loss. Restoration of normal structure and function in these cases requires replacement of the missing bone that may be accomplished by surgical transfer of natural tissue from an uninjured location elsewhere in the body. However, this procedure is limited by availability, adequate blood supply, and secondary deformities at the donor site. One strategy to overcome these problems is to develop living tissue substitutes based on synthetic biodegradable polymers. Three methods of bone regeneration using biodegradable polymers are being studied in our laboratory: tissue induction, cell transplantation, and fabrication of vascularized bone flaps. Injectable polymers are used for filling skeletal defects and guiding bone tissue growth. Their main advantage is minimizing the surgical intervention or the severity of the surgery. Polymer-cell constructs also hold great promise in the field of tissue engineering. They provide a scaffold on which cells grow and organize themselves. As the cells begin to secrete their own extracellular matrix, the polymer degrades and is eventually eliminated from the body, resulting in completely natural tissue replacement. Bone flaps can be fabricated ectopically into precise shapes and sizes. With an attached vascular supply, these flaps can be transferred into areas deficient in vascularity. This article discusses polymer concepts regarding bone tissue engineering and reviews recent advances of our laboratory on guided bone regeneration using biodegradable polymer scaffolds.

  12. Radiation degradation of cellulose

    NASA Astrophysics Data System (ADS)

    Leonhardt, J.; Arnold, G.; Baer, M.; Langguth, H.; Gey, M.; Hübert, S.

    The application of straw and other cellulose polymers as feedstuff for ruminants is limited by its low digestibility. During recent decades it was attempted to increase the digestibility of straw by several chemical and physical methods. In this work some results of the degradation of gamma and electron treated wheat straw are reported. Complex methods of treatment (e.g. radiation influence and influence of lyes) are taken into consideration. In vitro-experiments with radiation treated straw show that the digestibility can be increased from 20 % up to about 80 %. A high pressure liquid chromatography method was used to analyze the hydrolysates. The contents of certain species of carbohydrates in the hydrolysates in dependence on the applied dose are given.

  13. Effect of solvents on the enzyme mediated degradation of copolymers

    NASA Astrophysics Data System (ADS)

    Banerjee, Aditi; Chatterjee, Kaushik; Madras, Giridhar

    2015-09-01

    The biodegradation of polycaprolactone (PCL), polylactic acid (PLA), polyglycolide (PGA) and their copolymers, poly (lactide-co-glycolide) and poly (D, L-lactide-co-caprolactone) (PLCL) was investigated. The influence of different solvents on the degradation of these polymers at 37 °C in the presence of two different lipases namely Novozym 435 and the free lipase of porcine pancreas was investigated. The rate coefficients for the polymer degradation and enzyme deactivation were determined using continuous distribution kinetics. Among the homopolymers, the degradation of PGA was nearly an order of magnitude lower than that for PCL and PLA. The overall rate coefficients of the copolymers were higher than their respective homopolymers. Thus, PLCL degraded faster than either PCL or PLA. The degradation was highly dependent on the viscosity of the solvent used with the highest degradation observed in acetone. The degradation of the polymers in acetone was nearly twice that observed in dimethyl sulfoxide indicating that the degradation decreases with increase in the solvent viscosity. The degradation of the polymers in water-solvent mixtures indicated an optimal water content of 2.5 wt% of water.

  14. THERMAL DEGRADATION OF POLY (ALPHA-METHYLSTYRENE) IN SOLUTION

    EPA Science Inventory

    The thermal degradation of poly(alpha-methylstyrene) in solution was investigated at various temperatures (150-225 C) and polymer concentrations (2.00-20-0 g/l) at 6.8 MPa (1000 psig). The molecular weight distributions (MWDs) of the reacted polymer at these conditions were exami...

  15. Synthetic biodegradable functional polymers for tissue engineering: a brief review.

    PubMed

    BaoLin, Guo; Ma, Peter X

    2014-04-01

    Scaffolds play a crucial role in tissue engineering. Biodegradable polymers with great processing flexibility are the predominant scaffolding materials. Synthetic biodegradable polymers with well-defined structure and without immunological concerns associated with naturally derived polymers are widely used in tissue engineering. The synthetic biodegradable polymers that are widely used in tissue engineering, including polyesters, polyanhydrides, polyphosphazenes, polyurethane, and poly (glycerol sebacate) are summarized in this article. New developments in conducting polymers, photoresponsive polymers, amino-acid-based polymers, enzymatically degradable polymers, and peptide-activated polymers are also discussed. In addition to chemical functionalization, the scaffold designs that mimic the nano and micro features of the extracellular matrix (ECM) are presented as well, and composite and nanocomposite scaffolds are also reviewed.

  16. Production and Characterization of a Polymer from Arthrobacter sp

    PubMed Central

    Bodie, Elizabeth A.; Schwartz, Robert D.; Catena, Anthony

    1985-01-01

    An Arthrobacter sp. isolated from a glucose-sucrose agar plate was found to produce a neutral, extremely viscous, opalescent extracellular polymer. Growth, polymer production, and rheological properties and chemical composition of the isolated polymer were examined. The polymer was found to be substantially different from other arthrobacter polymers. Some unusual properties included irreversible loss of viscosity with high temperature and degradation of the polymer during fermentation and upon storage at 4°C. Other characteristics included dependence on sucrose for polymer production, relative pH stability, increased viscosity with increased salt concentration, and pseudoplasticity. The polymer was found to be composed primarily (if not entirely) of d-fructose. The fructose content and other characteristics suggested that the polymer was a levan. PMID:16346883

  17. Semi-Degradable Poly(β-amino ester) Networks with Temporally-Controlled Enhancement of Mechanical Properties

    PubMed Central

    Safranski, David L.; Weiss, Daiana; Clark, J. Brian; Taylor, W.R.; Gall, Ken

    2014-01-01

    Biodegradable polymers are clinically used in numerous biomedical applications, and classically show a loss in mechanical properties within weeks of implantation. This work demonstrates a new class of semi-degradable polymers that show an increase in mechanical properties through degradation via a controlled shift in a thermal transition. Semi-degradable polymer networks, poly(β-amino ester)-co-methyl methacrylate, were formed from a low glass transition temperature crosslinker, poly(β-amino ester), and high glass transition temperature monomer, methyl methacrylate, which degraded in a manner dependent upon the crosslinker chemical structure. In vitro and in vivo degradation revealed changes in mechanical behavior due to the degradation of the crosslinker from the polymer network. This novel polymer system demonstrates a strategy to temporally control the mechanical behavior of polymers and to enhance the initial performance of smart biomedical devices. PMID:24769113

  18. Predicting radiation sensitivity of polymers

    NASA Technical Reports Server (NTRS)

    Osullivan, D.; Price, P. B.; Kinoshita, K.; Willson, C. G.

    1982-01-01

    Recently two independent applications have emerged for highly radiation-sensitive polymers: as resists for production of microelectronic circuitry and as materials to record the tracks of energetic nuclear particles. The relief images used for masking in resist materials are generated by radiation-induced differential dissolution rates, whereas the techniques used in recording nuclear particle tracks employ differential etching processes, that is, development by a chemical etchant that actually degrades the polymer. It is found that the sensitivity of materials to these very different processes is related to their gamma-ray scission efficiency. This correlation provides a predictive capability.

  19. Thermal oxidative degradation of ethylene tetrafluoroethylene copolymer systems

    NASA Astrophysics Data System (ADS)

    Elders, Jonathan Patrick

    Thermo-oxidative degradation of ethylene tetrafluoroethylene (ETFE) was investigated to determine how modifications for use in an electrical wire system affected its thermal stability. Modifications included electron irradiation and subsequent cross-linking during manufacture and contact with a metal surface. Samples with irradiation histories between 0 and 48 MRads were investigated. Degradation of ETFE was enhanced by contact with a metal "conductor" surface: silver - coated copper. Polymer degradation was analyzed by weight loss kinetics (thermogravimetric analysis (TGA)), changes in polymer morphology (differential scanning calorimetry (DSC)), optical microscopy, attenuated total reflectance (ATR) infrared spectroscopy, and gas chromatography - mass spectroscopy (GC/MS). Conductor aging (copper permeation through silver with subsequent oxidation) was investigated using scanning Auger Electron Spectroscopy (AES). Conductor aging is enhanced in the presence of the polymer surface. Interactions between conductor and polymer were analyzed by optical microscopy, scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS). The rate of polymer degradation from 220°C to 280°C was independent of time and extent of degradation, and rate was proportional to irradiation dose. The activation energy for degradation of unirradiated ETFE was 227 kJ/mol and decreased from 150 to 138 kJ/mol for ETFE irradiated to doses between 6 and 48 MRads. Rates of degradation at 300°C to 320°C were dependent on the extent of degradation. Rates of degradation at temperatures between 230°C and 310°C were an order of magnitude larger in the presence of a conductor than in its absence, and activation energies for degradation in the presence of conductor were reduced to 120 kJ/mol. Degradation was modeled as the combination of bulk polymer degradation and catalytic degradation at the polymer-metal interface. ETFE aged at 250°C in the presence or absence of a conductor

  20. Improved Process for Fabricating Carbon Nanotube Probes

    NASA Technical Reports Server (NTRS)

    Stevens, R.; Nguyen, C.; Cassell, A.; Delzeit, L.; Meyyappan, M.; Han, Jie

    2003-01-01

    An improved process has been developed for the efficient fabrication of carbon nanotube probes for use in atomic-force microscopes (AFMs) and nanomanipulators. Relative to prior nanotube tip production processes, this process offers advantages in alignment of the nanotube on the cantilever and stability of the nanotube's attachment. A procedure has also been developed at Ames that effectively sharpens the multiwalled nanotube, which improves the resolution of the multiwalled nanotube probes and, combined with the greater stability of multiwalled nanotube probes, increases the effective resolution of these probes, making them comparable in resolution to single-walled carbon nanotube probes. The robust attachment derived from this improved fabrication method and the natural strength and resiliency of the nanotube itself produces an AFM probe with an extremely long imaging lifetime. In a longevity test, a nanotube tip imaged a silicon nitride surface for 15 hours without measurable loss of resolution. In contrast, the resolution of conventional silicon probes noticeably begins to degrade within minutes. These carbon nanotube probes have many possible applications in the semiconductor industry, particularly as devices are approaching the nanometer scale and new atomic layer deposition techniques necessitate a higher resolution characterization technique. Previously at Ames, the use of nanotube probes has been demonstrated for imaging photoresist patterns with high aspect ratio. In addition, these tips have been used to analyze Mars simulant dust grains, extremophile protein crystals, and DNA structure.

  1. Fast and reliable method of conductive carbon nanotube-probe fabrication for scanning probe microscopy

    SciTech Connect

    Dremov, Vyacheslav Fedorov, Pavel; Grebenko, Artem; Fedoseev, Vitaly

    2015-05-15

    We demonstrate the procedure of scanning probe microscopy (SPM) conductive probe fabrication with a single multi-walled carbon nanotube (MWNT) on a silicon cantilever pyramid. The nanotube bundle reliably attached to the metal-covered pyramid is formed using dielectrophoresis technique from the MWNT suspension. It is shown that the dimpled aluminum sample can be used both for shortening/modification of the nanotube bundle by applying pulse voltage between the probe and the sample and for controlling the probe shape via atomic force microscopy imaging the sample. Carbon nanotube attached to cantilever covered with noble metal is suitable for SPM imaging in such modulation regimes as capacitance contrast microscopy, Kelvin probe microscopy, and scanning gate microscopy. The majority of such probes are conductive with conductivity not degrading within hours of SPM imaging.

  2. Lifetime of biomolecules in polymer-based hybrid nanodevices

    NASA Astrophysics Data System (ADS)

    Brunner, Christian; Ernst, Karl-Heinz; Hess, Henry; Vogel, Viola

    2004-10-01

    Prolonging the lifetime of biomolecules in their functional states is critical for many applications where biomolecules are integrated into synthetic materials or devices. A simplified molecular shuttle system, which consists of fluorescently labelled microtubules propelled by kinesin motor proteins bound to the surface of a flowcell, served here as a model system to probe the lifetime of a hybrid device. In this system, the functional decay can easily be assayed by utilizing optical microscopy to detect motility and disintegration of microtubules. We found that the lifetimes of these hybrid systems were mainly limited by the stability of microtubules (MTs), rather than of kinesin. To determine the biocompatibility of polymers widely used in microfabrication, we assembled flowcells with glass bottom surfaces and covers fabricated from glass, poly(urethane) (PU), poly(methyl-methacrylate) (PMMA), poly(dimethylsiloxane) (PDMS) and ethylene-vinyl alcohol copolymer (EVOH). Without illumination, only PU had a substantial negative impact on MT stability, while PMMA, PDMS and EVOH showed stabilities comparable to glass. Under the influence of light, however, the MTs degraded rapidly in the presence of PDMS or PMMA, even in the presence of oxygen scavengers. A similar effect was observed on glass if oxygen scavengers were not added to the medium. Strong bleaching of the fluorophores was again only found on the polymer substrates and photobleaching coincided with an accelerated depolymerization of the MTs.

  3. Organometallic Polymers.

    ERIC Educational Resources Information Center

    Carraher, Charles E., Jr.

    1981-01-01

    Reactions utilized to incorporate a metal-containing moiety into a polymer chain (addition, condensation, and coordination) are considered, emphasizing that these reactions also apply to smaller molecules. (JN)

  4. Polymer flooding

    SciTech Connect

    Littmann, W.

    1988-01-01

    This book covers all aspects of polymer flooding, an enhanced oil recovery method using water soluble polymers to increase the viscosity of flood water, for the displacement of crude oil from porous reservoir rocks. Although this method is becoming increasingly important, there is very little literature available for the engineer wishing to embark on such a project. In the past, polymer flooding was mainly the subject of research. The results of this research are spread over a vast number of single publications, making it difficult for someone who has not kept up-to-date with developments during the last 10-15 years to judge the suitability of polymer flooding to a particular field case. This book tries to fill that gap. An indispensable book for reservoir engineers, production engineers and lab. technicians within the petroleum industry.

  5. An SEC/MALS Study of Alternan Degradation During Size-exclusion Chromatographic Analysis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The degradation of high molar mass polymers during size-exclusion chromatography (SEC) analysis has been a topic of interest for several decades. Should a polymer degrade during analysis, the accuracy of the molar mass (M) and architectural information obtained will be compromised. To this effect,...

  6. Polymers All Around You!

    ERIC Educational Resources Information Center

    Gertz, Susan

    Background information on natural polymers, synthetic polymers, and the properties of polymers is presented as an introduction to this curriculum guide. Details are provided on the use of polymer products in consumer goods, polymer recycling, polymer densities, the making of a polymer such as GLUEP, polyvinyl alcohol, dissolving plastics, polymers…

  7. Environmental durability of polymer concrete

    SciTech Connect

    Palmese, G.R.; Chawalwala, A.J.

    1996-12-31

    Over the past two decades, polymer concrete has increasingly been used for a number of applications including piping, machine bases, chemically resistant flooring, and bridge overlays. Currently, the use of polymer concrete as a wear surface for polymeric composite bridge decks is being investigated. Polymer concrete is a particulate composite comprised of mineral aggregate bound by a polymeric matrix. Such materials possess significantly higher mechanical properties than Portland cement concrete. However, the mechanical characteristics and environmental durability of polymer concrete are influenced by a number of factors. Among these are the selection of aggregate and resin, surface treatment, and cure conditions. In this work the influence of matrix selection and cure history on the environmental durability of polymer concrete was investigated. Particular attention was given to the effects of water on composite properties and to the mechanisms by which degradation occurs. The basalt-based polymer concrete systems investigated were susceptible to attack by water. Furthermore, results suggest that property loss associated with water exposure was primarily a result of interfacial weakening.

  8. Polysaccharide Degradation

    NASA Astrophysics Data System (ADS)

    Stone, Bruce A.; Svensson, Birte; Collins, Michelle E.; Rastall, Robert A.

    An overview of current and potential enzymes used to degrade polysaccharides is presented. Such depolymerases are comprised of glycoside hydrolases, glycosyl transferases, phosphorylases and lyases, and their classification, active sites and action patterns are discussed. Additionally, the mechanisms that these enzymes use to cleave glycosidic linkages is reviewed as are inhibitors of depolymerase activity; reagents which react with amino acid residues, glycoside derivatives, transition state inhibitors and proteinaceous inhibitors. The characterization of various enzymes of microbial, animal or plant origin has led to their widespread use in the production of important oligosaccharides which can be incorporated into food stuffs. Sources of polysaccharides of particular interest in this chapter are those from plants and include inulin, dextran, xylan and pectin, as their hydrolysis products are purported to be functional foods in the context of gastrointestinal health. An alternative use of degraded polysaccharides is in the treatment of disease. The possibility exists to treat bacterial exopolysaccharide with lyases from bacteriophage to produce oligosaccharides exhibiting bioactive sequences. Although this area is currently in its infancy the knowledge is available to investigate further.

  9. Photocatalytic activity of PANI loaded coordination polymer composite materials: Photoresponse region extension and quantum yields enhancement via the loading of PANI nanofibers on surface of coordination polymer

    SciTech Connect

    Cui, Zhongping; Qi, Ji; Xu, Xinxin Liu, Lu; Wang, Yi

    2013-09-15

    To enhance photocatalytic property of coordination polymer in visible light region, polyaniline (PANI) loaded coordination polymer photocatalyst was synthesized through in-situ chemical oxidation of aniline on the surface of coordination polymer. The photocatalytic activity of PANI loaded coordination polymer composite material for degradation of Rhodamine B (RhB) was investigated. Compared with pure coordination polymer photocatalyst, which can decompose RhB merely under UV light irradiation, PANI loaded coordination polymer photocatalyst displays more excellent photocatalytic activity in visible light region. Furthermore, PANI loaded coordination polymer photocatalyst exhibits outstanding stability during the degradation of RhB. - Graphical abstract: PANI loaded coordination polymer composite material, which displays excellent photocatalytic activity under visible light was firstly synthesized through in-situ chemical oxidation of aniline on surface of coordination polymer. Display Omitted - Highlights: • This PANI loaded coordination polymer composite material represents the first conductive polymer loaded coordination polymer composite material. • PANI/coordination polymer composite material displays more excellent photocatalytic activity for the degradation of MO in visible light region. • The “combination” of coordination polymer and PANI will enable us to design high-activity, high-stability and visible light driven photocatalyst in the future.

  10. Final report for the designed synthesis of controlled degradative materials LDRD

    SciTech Connect

    LOY,DOUGLAS A.; ULIBARRI,TAMARA A.; CURRO,JOHN G.; SAUNDERS,R.; DERZON,DORA K.; GUESS,TOMMY R.; BAUGHER,B.M.

    2000-02-01

    The main goal of this research was to develop degradable systems either by developing weaklink-containing polymers or identifying commercial polymeric systems which are easily degraded. In both cases, the degradation method involves environmentally friendly chemistries. The weaklinks are easily degradable fragments which are introduced either randomly or regularly in the polymer backbone or as crosslinking sites to make high molecular weight systems via branching. The authors targeted three general application areas: (1) non-lethal deterrents, (2) removable encapsulants, and (3) readily recyclable/environmentally friendly polymers for structural and thin film applications.

  11. Band bending in conjugated polymer layers.

    PubMed

    Lange, Ilja; Blakesley, James C; Frisch, Johannes; Vollmer, Antje; Koch, Norbert; Neher, Dieter

    2011-05-27

    We use the Kelvin probe method to study the energy-level alignment of four conjugated polymers deposited on various electrodes. Band bending is observed in all polymers when the substrate work function exceeds critical values. Through modeling, we show that the band bending is explained by charge transfer from the electrodes into a small density of states that extends several hundred meV into the band gap. The energetic spread of these states is correlated with charge-carrier mobilities, suggesting that the same states also govern charge transport in the bulk of these polymers.

  12. Dendritic polymer imaging systems for the evaluation of conjugate uptake and cleavage.

    PubMed

    Krüger, Harald R; Nagel, Gregor; Wedepohl, Stefanie; Calderón, Marcelo

    2015-03-07

    Fluorescent turn-on probes combined with polymers have a broad range of applications, e.g. for intracellular sensing of ions, small molecules, or DNA. In the field of polymer therapeutics, these probes can be applied to extend the in vitro characterization of novel conjugates beyond cytotoxicity and cellular uptake studies. This is particularly true in cases in which polymer conjugates contain drugs attached by cleavable linkers. Better information on the intracellular linker cleavage and drug release would allow a faster evaluation and optimization of novel polymer therapeutic concepts. We therefore developed a fluorescent turn-on probe that enables direct monitoring of pH-mediated cleavage processes over time. This is achieved by exploiting the fluorescence resonance energy transfer (FRET) between two dyes that have been coupled to a dendritic polymer. We demonstrate the use of this probe to evaluate polymer uptake and intracellular release of cargo in a cell based microplate assay that is suitable for high throughput screening.

  13. Transiently thermoresponsive polymers and their applications in biomedicine.

    PubMed

    Vanparijs, Nane; Nuhn, Lutz; De Geest, Bruno G

    2017-02-20

    The focus of this review is on the class of transiently thermoresponsive polymers. These polymers are thermoresponsive, but gradually lose this property upon chemical transformation - often a hydrolysis reaction - in the polymer side chain or backbone. An overview of the different approaches used for the design of these polymers along with their physicochemical properties is given. Their amphiphilic properties and degradability into fully soluble compounds make this class of responsive polymers attractive for drug delivery and tissue engineering applications. Examples of these are also provided in this review.

  14. Investigations on degradation of the long-term proton exchange membrane water electrolysis stack

    NASA Astrophysics Data System (ADS)

    Sun, Shucheng; Shao, Zhigang; Yu, Hongmei; Li, Guangfu; Yi, Baolian

    2014-12-01

    A 9-cell proton exchange membrane (PEM) water electrolysis stack is developed and tested for 7800 h. The average degradation rate of 35.5 μV h-1 per cell is measured. The 4th MEA of the stack is offline investigated and characterized. The electrochemical impedance spectroscopy (EIS) shows that the charge transfer resistance and ionic resistance of the cell both increase. The linear sweep scan (LSV) shows the hydrogen crossover rate of the membrane has slight increase. The electron probe X-ray microanalyze (EPMA) illustrates further that Ca, Cu and Fe elements distribute in the membrane and catalyst layers of the catalyst-coated membranes (CCMs). The cations occupy the ion exchange sites of the Nafion polymer electrolyte in the catalyst layers and membrane, which results in the increase in the anode and the cathode overpotentials. The metallic impurities originate mainly from the feed water and the components of the electrolysis unit. Fortunately, the degradation was reversible and can be almost recovered to the initial performance by using 0.5 M H2SO4. This indicates the performance degradation of the stack running 7800 h is mainly caused by a recoverable contamination.

  15. Drug Release Kinetics and Transport Mechanisms of Non-degradable and Degradable Polymeric Delivery Systems

    PubMed Central

    Fu, Yao; Kao, Weiyuan John

    2010-01-01

    Importance of the field The advancement in material design and engineering has led to the rapid development of novel materials with increasing complexity and functions. Both non-degradable and degradable polymers have found wide applications in the controlled delivery field. Studies on drug release kinetics provide important information into the function of material systems. To elucidate the detailed transport mechanism and the structure-function relationship of a material system, it is critical to bridge the gap between the macroscopic data and the transport behavior at the molecular level. Areas covered in this review The structure and function information of selected non-degradable and degradable polymers have been collected and summarized from literatures published after 1990s. The release kinetics of selected drug compounds from various material systems will be discussed in case studies. Recent progresses in the mathematical models based on different transport mechanisms will be highlighted. What the reader will gain This article aims to provide an overview of structure-function relationships of selected non-degradable and degradable polymers as drug delivery matrices. Take home message Understanding the structure-function relationship of the material system is key to the successful design of a delivery system for a particular application. Moreover, developing complex polymeric matrices requires more robust mathematical models to elucidate the solute transport mechanisms. PMID:20331353

  16. Local mobility of polymer chain grafted onto polyethylene monitored by fluorescence depolarization

    NASA Astrophysics Data System (ADS)

    Tsuneda, Satoshi; Endo, Toshihiro; Saito, Kyoichi; Sugita, Kazuyuki; Horie, Kazuyuki; Yamashita, Takashi; Sugo, Takanobu

    1997-08-01

    The fluorescence depolarization method was used for investigating the local mobility of polymer chains grafted onto a porous polyethylene membrane. The real value of the rotational diffusion coefficient of a dansyl probe attached to the grafted polymer chain was obtained by using a correction method which eliminated the effect of multiple scattering on fluorescence anisotropy. The rotational mobility of the dansyl probe attached to the grafted polymer chain was sensitive to both degree of grafting and solvent polarity, which indicated that the conformation of the grafted polymer chain and the pore size of the base membrane strongly governed the dynamic parameters of the grafted polymer chain.

  17. Antimocrobial Polymer

    DOEpatents

    McDonald, William F.; Huang, Zhi-Heng; Wright, Stacy C.

    2005-09-06

    A polymeric composition having antimicrobial properties and a process for rendering the surface of a substrate antimicrobial are disclosed. The composition comprises a crosslinked chemical combination of (i) a polymer having amino group-containing side chains along a backbone forming the polymer, (ii) an antimicrobial agent selected from quaternary ammonium compounds, gentian violet compounds, substituted or unsubstituted phenols, biguanide compounds, iodine compounds, and mixtures thereof, and (iii) a crosslinking agent containing functional groups capable of reacting with the amino groups. In one embodiment, the polymer is a polyamide formed from a maleic anhydride or maleic acid ester monomer and alkylamines thereby producing a polyamide having amino substituted alkyl chains on one side of the polyamide backbone; the crosslinking agent is a phosphine having the general formula (A)3P wherein A is hydroxyalkyl; and the antimicrobial agent is chlorhexidine, dimethylchlorophenol, cetyl pyridinium chloride, gentian violet, triclosan, thymol, iodine, and mixtures thereof.

  18. Antimicrobial Polymer

    DOEpatents

    McDonald, William F.; Wright, Stacy C.; Taylor, Andrew C.

    2004-09-28

    A polymeric composition having antimicrobial properties and a process for rendering the surface of a substrate antimicrobial are disclosed. The polymeric composition comprises a crosslinked chemical combination of (i) a polymer having amino group-containing side chains along a backbone forming the polymer, (ii) an antimicrobial agent selected from metals, metal alloys, metal salts, metal complexes and mixtures thereof, and (iii) a crosslinking agent containing functional groups capable of reacting with the amino groups. In one example embodiment, the polymer is a polyamide formed from a maleic anhydride or maleic acid ester monomer and alkylamines thereby producing a polyamide having amino substituted alkyl chains on one side of the polyamide backbone; the crosslinking agent is a phosphine having the general formula (A).sub.3 P wherein A is hydroxyalkyl; and the metallic antimicrobial agent is selected from chelated silver ions, silver metal, chelated copper ions, copper metal, chelated zinc ions, zinc metal and mixtures thereof.

  19. Polymer inflation

    NASA Astrophysics Data System (ADS)

    Hassan, Syed Moeez; Husain, Viqar; Seahra, Sanjeev S.

    2015-03-01

    We consider the semiclassical dynamics of a free massive scalar field in a homogeneous and isotropic cosmological spacetime. The scalar field is quantized using the polymer quantization method assuming that it is described by a Gaussian coherent state. For quadratic potentials, the semiclassical equations of motion yield a universe that has an early "polymer inflation" phase which is generic and almost exactly de Sitter, followed by an epoch of slow-roll inflation. We compute polymer corrections to the slow-roll formalism, and discuss the probability of inflation in this model using a physical Hamiltonian arising from time gauge fixing. We also show how in this model, it is possible to obtain a significant amount of slow-roll inflation from sub-Planckian initial data, hence circumventing some of the criticisms of standard scenarios. These results show the extent to which a quantum gravity motivated quantization method affects early universe dynamics.

  20. Charge collection kinetics on ferroelectric polymer surface using charge gradient microscopy

    DOE PAGES

    Choi, Yoon-Young; Tong, Sheng; Ducharme, Stephen P.; ...

    2016-05-03

    Here, a charge gradient microscopy (CGM) probe was used to collect surface screening charges on poly(vinylidene fluoride-trifluoroethylene) [P(VDF-TrFE)] thin films. These charges are naturally formed on unscreened ferroelectric domains in ambient condition. The CGM data were used to map the local electric current originating from the collected surface charges on the poled ferroelectric domains in the P(VDF-TrFE) thin films. Both the direction and amount of the collected current were controlled by changing the polarity and area of the poled domains. The endurance of charge collection by rubbing the CGM tip on the polymer film was limited to 20 scan cycles,more » after which the current reduced to almost zero. This degradation was attributed to the increase of the chemical bonding strength between the external screening charges and the polarization charges. Once this degradation mechanism is mitigated, the CGM technique can be applied to efficient energy harvesting devices using polymer ferroelectrics.« less

  1. Molecular Probe Fluorescence Monitoring of Polymerization

    NASA Technical Reports Server (NTRS)

    Bunton, Patrick

    2002-01-01

    This project investigated the feasibility of using fluorescence spectroscopy to determine viscosity of polymer/monomer in support of Transient Interfacial Phenomena in Miscible Polymer Systems (TIPMPS). This project will attempt to measure gradient induced flow at a miscible interface during and / or after in-flight polymerization of dodecyl acrylate (lauryl acrylate). Concentration and temperature gradients will be intentionally introduced during polymerization and the resultant fluid flow determined by Particle Imaging Velocimetry (PIV). This report describes an investigation of the feasibility of using fluorescence of a probe molecule to monitor viscosity and/or concentration during and after polymerization. The probe used was pyrene which has been shown to be sensitive to its local environment in methyl methacrylate.

  2. Hydrodynamic ultrasonic probe

    DOEpatents

    Day, Robert A.; Conti, Armond E.

    1980-01-01

    An improved probe for in-service ultrasonic inspection of long lengths of a workpiece, such as small diameter tubing from the interior. The improved probe utilizes a conventional transducer or transducers configured to inspect the tubing for flaws and/or wall thickness variations. The probe utilizes a hydraulic technique, in place of the conventional mechanical guides or bushings, which allows the probe to move rectilinearly or rotationally while preventing cocking thereof in the tube and provides damping vibration of the probe. The probe thus has lower friction and higher inspection speed than presently known probes.

  3. Probe tip heating assembly

    SciTech Connect

    Schmitz, Roger William; Oh, Yunje

    2016-10-25

    A heating assembly configured for use in mechanical testing at a scale of microns or less. The heating assembly includes a probe tip assembly configured for coupling with a transducer of the mechanical testing system. The probe tip assembly includes a probe tip heater system having a heating element, a probe tip coupled with the probe tip heater system, and a heater socket assembly. The heater socket assembly, in one example, includes a yoke and a heater interface that form a socket within the heater socket assembly. The probe tip heater system, coupled with the probe tip, is slidably received and clamped within the socket.

  4. Thermal Spray Formation of Polymer Coatings

    NASA Technical Reports Server (NTRS)

    Coquill, Scott; Galbraith, Stephen L.; Tuss. Darren L.; Ivosevic, Milan

    2008-01-01

    This innovation forms a sprayable polymer film using powdered precursor materials and an in-process heating method. This device directly applies a powdered polymer onto a substrate to form an adherent, mechanically-sound, and thickness-regulated film. The process can be used to lay down both fully dense and porous, e.g., foam, coatings. This system is field-deployable and includes power distribution, heater controls, polymer constituent material bins, flow controls, material transportation functions, and a thermal spray apparatus. The only thing required for operation in the field is a power source. Because this method does not require solvents, it does not release the toxic, volatile organic compounds of previous methods. Also, the sprayed polymer material is not degraded because this method does not use hot combustion gas or hot plasma gas. This keeps the polymer from becoming rough, porous, or poorly bonded.

  5. Polymer Interaction in a Model Bioblend

    Technology Transfer Automated Retrieval System (TEKTRAN)

    EBU/PS blends of varying compositions were investigated using TGA, MDSC, and FTIR-PAS methods. The goal of the investigation was that of probing for the presence or lack of intermolecular interactions between the two polymers. The TGA investigation showed at least one blend composition with better...

  6. Surfactant-Polymer Interaction for Improved Oil Recovery

    SciTech Connect

    Gabitto, Jorge; Mohanty, Kishore K.

    2002-01-07

    The goal of this research was to use the interaction between a surfactant and a polymer for efficient displacement of tertiary oil by improving slug integrity, oil solubility in the displacing fluid and mobility control. Surfactant-polymer flooding has been shown to be highly effective in laboratory-scale linear floods. The focus of this proposal is to design an inexpensive surfactant-polymer mixture that can efficiently recover tertiary oil by avoiding surfactant slug degradation and viscous/heterogeneity fingering.

  7. Antimicrobial polymers.

    PubMed

    Jain, Anjali; Duvvuri, L Sailaja; Farah, Shady; Beyth, Nurit; Domb, Abraham J; Khan, Wahid

    2014-12-01

    Better health is basic requirement of human being, but the rapid growth of harmful pathogens and their serious health effects pose a significant challenge to modern science. Infections by pathogenic microorganisms are of great concern in many fields such as medical devices, drugs, hospital surfaces/furniture, dental restoration, surgery equipment, health care products, and hygienic applications (e.g., water purification systems, textiles, food packaging and storage, major or domestic appliances etc.) Antimicrobial polymers are the materials having the capability to kill/inhibit the growth of microbes on their surface or surrounding environment. Recently, they gained considerable interest for both academic research and industry and were found to be better than their small molecular counterparts in terms of enhanced efficacy, reduced toxicity, minimized environmental problems, resistance, and prolonged lifetime. Hence, efforts have focused on the development of antimicrobial polymers with all desired characters for optimum activity. In this Review, an overview of different antimicrobial polymers, their mechanism of action, factors affecting antimicrobial activity, and application in various fields are given. Recent advances and the current clinical status of these polymers are also discussed.

  8. Polymer solutions

    DOEpatents

    Krawczyk, Gerhard Erich; Miller, Kevin Michael

    2011-07-26

    There is provided a method of making a polymer solution comprising polymerizing one or more monomer in a solvent, wherein said monomer comprises one or more ethylenically unsaturated monomer that is a multi-functional Michael donor, and wherein said solvent comprises 40% or more by weight, based on the weight of said solvent, one or more multi-functional Michael donor.

  9. Biological degradation of plastics: a comprehensive review.

    PubMed

    Shah, Aamer Ali; Hasan, Fariha; Hameed, Abdul; Ahmed, Safia

    2008-01-01

    Lack of degradability and the closing of landfill sites as well as growing water and land pollution problems have led to concern about plastics. With the excessive use of plastics and increasing pressure being placed on capacities available for plastic waste disposal, the need for biodegradable plastics and biodegradation of plastic wastes has assumed increasing importance in the last few years. Awareness of the waste problem and its impact on the environment has awakened new interest in the area of degradable polymers. The interest in environmental issues is growing and there are increasing demands to develop material which do not burden the environment significantly. Biodegradation is necessary for water-soluble or water-immiscible polymers because they eventually enter streams which can neither be recycled nor incinerated. It is important to consider the microbial degradation of natural and synthetic polymers in order to understand what is necessary for biodegradation and the mechanisms involved. This requires understanding of the interactions between materials and microorganisms and the biochemical changes involved. Widespread studies on the biodegradation of plastics have been carried out in order to overcome the environmental problems associated with synthetic plastic waste. This paper reviews the current research on the biodegradation of biodegradable and also the conventional synthetic plastics and also use of various techniques for the analysis of degradation in vitro.

  10. Method of making polymer powders and whiskers as well as particulate products of the method and atomizing apparatus

    DOEpatents

    Otaigbe, Joshua U.; McAvoy, Jon M.; Anderson, Iver E.; Ting, Jason; Mi, Jia; Terpstra, Robert

    2001-01-09

    Method for making polymer particulates, such as spherical powder and whiskers, by melting a polymer material under conditions to avoid thermal degradation of the polymer material, atomizing the melt using gas jet means in a manner to form atomized droplets, and cooling the droplets to form polymer particulates, which are collected for further processing. Atomization parameters can be controlled to produce polymer particulates with controlled particle shape, particle size, and particle size distribution. For example, atomization parameters can be controlled to produce spherical polymer powders, polymer whiskers, and combinations of spherical powders and whiskers. Atomizing apparatus also is provided for atoomizing polymer and metallic materials.

  11. Polymer mechanochemistry: from destructive to productive.

    PubMed

    Li, Jun; Nagamani, Chikkannagari; Moore, Jeffrey S

    2015-08-18

    When one brings "polymeric materials" and "mechanical action" into the same conversation, the topic of this discussion might naturally focus on everyday circumstances such as failure of fibers, fatigue of composites, abrasion of coatings, etc. This intuitive viewpoint reflects the historic consensus in both academia and industry that mechanically induced chemical changes are destructive, leading to polymer degradation that limits materials lifetime on both macroscopic and molecular levels. In the 1930s, Staudinger observed mechanical degradation of polymers, and Melville later discovered that polymer chain scission caused the degradation. Inspired by these historical observations, we sought to redirect the destructive mechanical energy to a productive form that enables mechanoresponsive functions. In this Account, we provide a personal perspective on the origin, barriers, developments, and key advancements of polymer mechanochemistry. We revisit the seminal events that offered molecular-level insights into the mechanochemical behavior of polymers and influenced our thinking. We also highlight the milestones achieved by our group along with the contributions from key comrades at the frontier of this field. We present a workflow for the design, evaluation, and development of new "mechanophores", a term that has come to mean a molecular unit that chemically responds in a selective manner to a mechanical perturbation. We discuss the significance of computation in identifying pairs of points on the mechanophore that promote stretch-induced activation. Attaching polymer chains to the mechanophore at the most sensitive pair and locating the mechanophore near the center of a linear polymer are thought to maximize the efficiency of mechanical-to-chemical energy transduction. We also emphasize the importance of control experiments to validate mechanochemical transformations, both in solution and in the solid state, to differentiate "mechanical" from "thermal" activation

  12. Solubilization and spore recovery from silicone polymers. Ph.D. Thesis

    NASA Technical Reports Server (NTRS)

    Hsiao, Y. C.

    1974-01-01

    A non-sporicidal technique for solvent degradation of cured silicone polymers was developed which involves chemical degradation of cured silicone polymers by amine solvents at room temperature. Substantial improvements were obtained in the recovery of seeded spores from room temperature cured polymers as compared to the standard recovery procedures, which indicates that the curing process is not sufficiently exothermic to reduce spore viability. The dissolution reaction of cured silicone polymers whith amine solvents is proposed to occur by bimolecular nucleophilic displacement. The chemical structure of silicone polymers was determined by spectroscopic methods. The phenyl to methyl ratio, R/Si ratio, molecular weight, and hydroxyl content of the silicone resins were determined.

  13. Evaluation of Degradation Properties of Polyglycolide and Its Potential as Delivery Vehicle for Anticancer Agents

    SciTech Connect

    Noorsal, K.; Ghani, S. M.; Yunos, D. M.; Mohamed, M. S. W.; Yahya, A. F.

    2010-03-11

    Biodegradable polymers offer a unique combination of properties that can be tailored to suit nearly any controlled drug delivery application. The most common biodegradable polymers used for biomedical applications are semicrystalline polyesters and polyethers which possess good mechanical properties and have been used in many controlled release applications. Drug release from these polymers may be controlled by several mechanisms and these include diffusion of drug through a matrix, dissolution of polymer matrix and degradation of the polymer. This study aims to investigate the degradation and drug release properties of polyglycolide (1.03 dL/g), in which, cis platin, an anticancer agent was used as the model drug. The degradation behaviour of the chosen polymer is thought to largely govern the release of the anticancer agent in vitro.

  14. Hydrolytic Degradation of Estane 5703

    SciTech Connect

    Wrobleski, D.A.; Smith, M.E.; Orler, E.B.

    1999-04-27

    Relative to the unaged Estane{reg_sign} 5703, heating decreases the modulus and ultimate stress for both the dry and humid samples. The sample aged in dry air, quickly recovered to its original mechanical properties. The reversibility of the mechanical properties is a result of the reorganization of the hard segments into domains. For the Estane 5703 samples aged in humid air, the mechanical properties only partially recovered with time. Molecular weight data confirm that differences in the extent of the recovery for the samples aged under humid environments are likely due to the hydrolytic scission of the polyester soft segments. Since the tensile moduli are similar for the samples aged in both the dry and humid environments, it is believed that the phase behavior of the hard domains dictate the mechanical properties at low extensions. However, at higher elongations, the mechanical properties are dominated by the soft segments. Both the influences of morphological changes and chemical changes induced by heating must be considered in multiphase polymers when accelerated aging is utilized to predict long term polymer properties. After accelerated aging experiments, the morphology must be allowed to recover to equilibrium conditions in order to assess the extent of degradation and aging. Also, the effect of different humidities on the rate of hydrolytic degradation are presented.

  15. Topics in electrochemical degradation of photovoltaic modules

    NASA Technical Reports Server (NTRS)

    Mon, G. R.

    1984-01-01

    Electrochemical degradation of photovoltaic modules was examined. It is found that the extent of electrochemical damage is dependent on the integrated leakage current. The PV electrochemical degradation mechanisms in the two polarities are different: (1) degradation rates in the two polarities are of the same order of magnitude; (2) center tapped grounded arrays are a preferred system configuration to minimize electrochemical degradation. The use of thicker pottant layers and polymer substrate films to reduce equilibrium leakage current values is suggested. A metallized substrate layer, if used, should be isolated from the pottant and the frame by polyester layers, and EVA modules appear to be consistent with 30 year life allocation levels for electrochemical damage. Temperature acceleration factors are well behaved and moderately well understood; humidity acceleration factors vary radically with module construction and materials and require additional research.

  16. Lignin degradation in wood-feeding insects.

    PubMed

    Geib, Scott M; Filley, Timothy R; Hatcher, Patrick G; Hoover, Kelli; Carlson, John E; Jimenez-Gasco, Maria del Mar; Nakagawa-Izumi, Akiko; Sleighter, Rachel L; Tien, Ming

    2008-09-02

    The aromatic polymer lignin protects plants from most forms of microbial attack. Despite the fact that a significant fraction of all lignocellulose degraded passes through arthropod guts, the fate of lignin in these systems is not known. Using tetramethylammonium hydroxide thermochemolysis, we show lignin degradation by two insect species, the Asian longhorned beetle (Anoplophora glabripennis) and the Pacific dampwood termite (Zootermopsis angusticollis). In both the beetle and termite, significant levels of propyl side-chain oxidation (depolymerization) and demethylation of ring methoxyl groups is detected; for the termite, ring hydroxylation is also observed. In addition, culture-independent fungal gut community analysis of A. glabripennis identified a single species of fungus in the Fusarium solani/Nectria haematococca species complex. This is a soft-rot fungus that may be contributing to wood degradation. These results transform our understanding of lignin degradation by wood-feeding insects.

  17. Clickable Antifouling Polymer Brushes for Polymer Pen Lithography.

    PubMed

    Bog, Uwe; de Los Santos Pereira, Andres; Mueller, Summer L; Havenridge, Shana; Parrillo, Viviana; Bruns, Michael; Holmes, Andrea E; Rodriguez-Emmenegger, Cesar; Fuchs, Harald; Hirtz, Michael

    2017-03-23

    Protein-repellent reactive surfaces that promote localized specific binding are highly desirable for applications in the biomedical field. Nonspecific adhesion will compromise the function of bioactive surfaces, leading to ambiguous results of binding assays and negating the binding specificity of patterned cell-adhesive motives. Localized specific binding is often achieved by attaching a linker to the surface, and the other side of the linker is used to bind specifically to a desired functional agent, as e.g. proteins, antibodies, and fluorophores, depending on the function required by the application. We present a protein-repellent polymer brush enabling highly specific covalent surface immobilization of biorecognition elements by strain-promoted alkyne-azide cycloaddition click chemistry for selective protein adhesion. The protein-repellent polymer brush is functionalized by highly localized molecular binding sites in the low micrometer range using polymer pen lithography (PPL). Because of the massive parallelization of writing pens, the tunable PPL printed patterns can span over square centimeter areas. The selective binding of the protein streptavidin to these surface sites is demonstrated while the remaining polymer brush surface is resisting nonspecific adsorption without any prior blocking by bovine serum albumin (BSA). In contrast to the widely used BSA blocking, the reactive polymer brushes are able to significantly reduce nonspecific protein adsorption, which is the cause of biofouling. This was achieved for solutions of single proteins as well as complex biological fluids. The remarkable fouling resistance of the polymer brushes has the potential to improve the multiplexing capabilities of protein probes and therefore impact biomedical research and applications.

  18. Advanced Polymer

    NASA Technical Reports Server (NTRS)

    1992-01-01

    In the mid-1980's, Langley developed a polyimide sulfone, combining desirable properties of two classes of polymers. Composites and other products made from polyimide sulfone can be used with solvents and corrosive fluids, are light weight, low cost and can be easily fabricated for a wide range of industrial uses. High Technology Systems, Inc. obtained a license for the polymer and was awarded a Small Business Innovation Research (SBIR) contract for development in a powder form. Although its principal use is as a matrix resin for composites, the material can also be used as a high temperature structural adhesive for aircraft structures and as a coating for protection from heat and radiation for electronic components.

  19. Theoretical Polymers.

    DTIC Science & Technology

    1976-10-07

    for the correlation length of 3/4, while 0.72 is observed. Then followed several talks on the expansion coefficient a, the virial coefficients and...calculation of the virial coefficient and c~2. These quantities can be considered merely a testing ground for the use of this method to polymer...the second viria]. coefficient , A2, to be zero and the intrinsic viscosity dependent on~VW for polystyrene mole-cular weights between 33,000 and one

  20. Phthalocyanine polymers

    NASA Technical Reports Server (NTRS)

    Achar, B. N.; Fohlen, G. M.; Parker, J. A. (Inventor)

    1985-01-01

    A method of forming 4,4',4'',4''' -tetraamino phthalocyanines involves reducing 4,4',4'',4''' -tetranitro phthalocyanines, polymerizing the metal tetraamino phthalocyanines with a tetracarboxylic dianhydride (preferably aromatic) or copolymerizing with a tetracarboxylic dianhydride and a diamine (preferably also aromatic) to produce amic acids which are then dehydrocyclized to imides. Thermally and oxidatively stable polymers result which form tough, flexible films, varnishes, adhesives, and fibers.

  1. Periodic Polymers

    NASA Astrophysics Data System (ADS)

    Thomas, Edwin

    2013-03-01

    Periodic polymers can be made by self assembly, directed self assembly and by photolithography. Such materials provide a versatile platform for 1, 2 and 3D periodic nano-micro scale composites with either dielectric or impedance contrast or both, and these can serve for example, as photonic and or phononic crystals for electromagnetic and elastic waves as well as mechanical frames/trusses. Compared to electromagnetic waves, elastic waves are both less complex (longitudinal modes in fluids) and more complex (longitudinal, transverse in-plane and transverse out-of-plane modes in solids). Engineering of the dispersion relation between wave frequency w and wave vector, k enables the opening of band gaps in the density of modes and detailed shaping of w(k). Band gaps can be opened by Bragg scattering, anti-crossing of bands and discrete shape resonances. Current interest is in our group focuses using design - modeling, fabrication and measurement of polymer-based periodic materials for applications as tunable optics and control of phonon flow. Several examples will be described including the design of structures for multispectral band gaps for elastic waves to alter the phonon density of states, the creation of block polymer and bicontinuous metal-carbon nanoframes for structures that are robust against ballistic projectiles and quasi-crystalline solid/fluid structures that can steer shock waves.

  2. Synthesis of dual-functional targeting probes for cancer theranostics based on iron oxide nanoparticles coated by centipede-like polymer connected with pH-responsive anticancer drug.

    PubMed

    Zhao, Haochen; Li, Zhiping; Yang, Bohan; Wang, Jingyuan; Li, Yapeng

    2015-01-01

    A tumor-targeted and pH-responsive drug release system based on superparamagnetic iron oxide nanoparticles (IONPs) coated by poly(ethylene glycol) (PEG) and dodecylamine (DDA)-modified polyitaconic acid (PIA) connecting with bortezomib (BTZ) (PIA-PEG-DDA-BTZ@IOs) has been constructed and characterized. The anticancer drug BTZ was first conjugated using dopamine as the linker via catechol borate ester bond, which is acid cleavable and used as an ideal pH-responsive drug release system. The IONPs were then coated by PIA-PEG-DDA-BTZ to form micelles with good biocompatibility. The conjugates were further designed to target liver cancer cells overexpressing vascular endothelial growth factor (VEGF) by the targeting molecule anti-vascular endothelial growth factor (anti-VEGF). The magnetic resonance imaging showed that the targeting capability of IONPs-anti-VEGF conjugates to Hep G2 cells was more significant than that of non-anti-VEGF IONPs. From the above, this kind of novel dual-functional targeting probe could provide a new idea for the diagnosis and treatment of cancer.

  3. Hot-wire probe

    NASA Technical Reports Server (NTRS)

    Mikulla, V.

    1976-01-01

    High-temperature platinum probe measures turbulence and Reynolds shear stresses in high-temperature compressible flows. Probe does not vibrate at high velocities and does not react like strain gage on warmup.

  4. Thermal Spraying of Bioactive Polymer Coatings for Orthopaedic Applications

    NASA Astrophysics Data System (ADS)

    Chebbi, A.; Stokes, J.

    2012-06-01

    Flame sprayed biocompatible polymer coatings, made of biodegradable and non-biodegradable polymers, were investigated as single coatings on titanium and as top coatings on plasma sprayed Hydroxyapatite. Biocompatible polymers can act as drug carriers for localized drug release following implantation. The polymer matrix consisted of a biodegradable polymer, polyhydroxybutyrate 98%/ polyhydroxyvalerate 2% (PHBV) and a non-biodegradable polymer, polymethylmethacrylate (PMMA). Screening tests were performed to determine the suitable range of spraying parameters, followed by a Design of Experiments study to determine the effects of spraying parameters on coating characteristics (thickness, roughness, adhesion, wettability), and to optimize the coating properties accordingly. Coatings characterization showed that optimized flame sprayed biocompatible polymers underwent little chemical degradation, did not produce acidic by-products in vitro, and that cells proliferated well on their surface.

  5. Towards Self-regenerating Antimicrobial Polymer Surfaces.

    PubMed

    Dorner, Franziska; Boschert, David; Schneider, Alexandra; Hartleb, Wibke; Al-Ahmad, Ali; Lienkamp, Karen

    2015-12-15

    Regeneration of functional polymer surfaces after damage or contamination is an unresolved scientific challenge, and also of practical importance. In this proof-of-concept study, we present a method to regenerate a functional surface property using a polymer multi-layer architecture. This is exemplified using antimicrobially active surfaces. The idea is to shed the top layer of the polymer layer stack, like a reptile shedding its skin. The proof-of-concept stack consists of two antimicrobial layers and a degradable interlayer. Shedding of the top layer is enabled by degrading that interlayer. The shedding process was analyzed by quantitative fluorescence microscopy, ellipsometry, and FTIR spectroscopy. Antimicrobial assays revealed that the functionality of the emerging antimicrobial layer was fully retained after shedding.

  6. Breakdown of plastics and polymers by microorganisms.

    PubMed

    Kawai, F

    1995-01-01

    The interest in environmental issues is still growing and there are increasing demands to develop materials which do not burden the environment significantly. Awareness of the waste problem and its impact on the environment has awakened new interest in the area of degradable polymers. Biodegradation is necessary for water-soluble or water-miscible polymers because they eventually enter streams which can neither be recycled nor incinerated. It is important to consider the microbial degradation of natural and synthetic polymers in order to understand what is necessary for biodegradation and the mechanisms involved. This requires both biochemical insight and understanding of the interactions between materials and microorganisms. It is now widely requested that polymeric materials come from renewable resources instead of petrochemical sources. The microbial production of polymeric and oligomeric materials is also described.

  7. Polymer research at NASA Langley Research Center

    NASA Technical Reports Server (NTRS)

    St.clair, T. L.; Johnston, N. J.

    1982-01-01

    Polymer synthesis programs involve the development of Novel thermoplastics, pseudothermoplastics, and thermosets. These systems are prepared to elucidate structure-property relationships involving thermal capabilities, toughness, processability and environmental stability. Easily processable polyimides, solvent-resistant polysulfones and polyphenylquinoxalines, and tougher high and intermediate temperature polymers were developed. Characterization efforts included high pressure liquid chromatography methodology, the development of toughness tests for fiber reinforced composites, a study of electrical properties of metal ion filled polyimides, and a study of the mutagenicity of aromatic diamines. Also the mechanism of cure/degradation of experimental polymers was studied by rheology, mechanical behavior, separation techniques and spectroscopy. The degradative crosslinking of alkyl-containing polyimides, the separation and identification of crosslinked phenylquinoxalines, the rheological behavior of hot-melt polyimides, and the elucidation of the cure of norbornene endcapped imides were also studied.

  8. Study on the degradation of chitosan slurries

    NASA Astrophysics Data System (ADS)

    Martini, Benjamin; Dimida, Simona; De Benedetto, Egidio; Madaghiele, Marta; Demitri, Christian

    In the present work, we measured the degradation rate of different chitosan slurries. Several parameters were monitored such as temperature (25 °C, 37 °C, 50 °C); chitosan concentration (1% and 2% (w/V)); and polymer molecular weight. The samples were tested in dynamic sweep test mode. This test is able to provide a reliable estimation of viscosity variations of the slurries; in turn, these variations could be related to degradation rate of the system in the considered conditions. The resulting information is particularly important especially in applications in which there is a close relationship between physical properties and molecular structure.

  9. Enhanced oil recovery with polymer flooding

    NASA Astrophysics Data System (ADS)

    Parsa, Shima; Weitz, David

    2016-11-01

    Polymer flooding is a method for enhanced oil recovery, however the mechanism responsible for the effectiveness of polymer flooding is not well understood. We use confocal microscopy and bulk transport measurements to probe the effectiveness of different molecular weight and concentrations of Polyacrylamide solution in imbibition of crude oil in 3D micromodel. We show that large molecular weight and moderate to high concentration of polymer is required for enhanced recovery. By directly measuring the pore level velocities in the medium, we show that polymer retention in the medium results in diversion of flow in some pores. The inhomogeneous changes in the flow velocities result in redistribution of viscous forces and enhanced recovery of oil.

  10. Galileo Probe Battery System

    NASA Technical Reports Server (NTRS)

    Dagarin, B. P.; Taenaka, R. K.; Stofel, E. J.

    1997-01-01

    The conclusions of the Galileo probe battery system are: the battery performance met mission requirements with margin; extensive ground-based and flight tests of batteries prior to probe separation from orbiter provided good prediction of actual entry performance at Jupiter; and the Li-SO2 battery was an important choice for the probe's main power.

  11. A Magnetoresistance Measuring Probe.

    DTIC Science & Technology

    The in line four point probe, commonly used for measuring the sheet resistance in a conductor, cannot measure the anisotropic ferromagnetic magnetoresistance. However, the addition of two contact points that are not collinear with the current contacts give the probe the ability to non-destructively measure the anistropic magnetoresistance. Keywords: Magnetoresistance; Anisotropic; Thin-Film; Permalloy; Four Point Probe; Anisotropic Resistance.

  12. Compression of Space for Low Visibility Probes.

    PubMed

    Born, Sabine; Krüger, Hannah M; Zimmermann, Eckart; Cavanagh, Patrick

    2016-01-01

    Stimuli briefly flashed just before a saccade are perceived closer to the saccade target, a phenomenon known as perisaccadic compression of space (Ross et al., 1997). More recently, we have demonstrated that brief probes are attracted towards a visual reference when followed by a mask, even in the absence of saccades (Zimmermann et al., 2014a). Here, we ask whether spatial compression depends on the transient disruptions of the visual input stream caused by either a mask or a saccade. Both of these degrade the probe visibility but we show that low probe visibility alone causes compression in the absence of any disruption. In a first experiment, we varied the regions of the screen covered by a transient mask, including areas where no stimulus was presented and a condition without masking. In all conditions, we adjusted probe contrast to make the probe equally hard to detect. Compression effects were found in all conditions. To obtain compression without a mask, the probe had to be presented at much lower contrasts than with masking. Comparing mislocalizations at different probe detection rates across masking, saccades and low contrast conditions without mask or saccade, Experiment 2 confirmed this observation and showed a strong influence of probe contrast on compression. Finally, in Experiment 3, we found that compression decreased as probe duration increased both for masks and saccades although here we did find some evidence that factors other than simply visibility as we measured it contribute to compression. Our experiments suggest that compression reflects how the visual system localizes weak targets in the context of highly visible stimuli.

  13. Compression of Space for Low Visibility