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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. PMID:25681971

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. Probing platinum degradation in polymer electrolyte membrane fuel cells by synchrotron X-ray microscopy.

    PubMed

    Berejnov, Viatcheslav; Martin, Zulima; West, Marcia; Kundu, Sumit; Bessarabov, Dmitri; Stumper, Jürgen; Susac, Darija; Hitchcock, Adam P

    2012-04-14

    Synchrotron-based scanning transmission X-ray spectromicroscopy (STXM) was used to characterize the local chemical environment at and around the platinum particles in the membrane (PTIM) which form in operationally tested (end-of-life, EOL) catalyst coated membranes (CCMs) of polymer electrolyte membrane fuel cells (PEM-FC). The band of metallic Pt particles in operationally tested CCM membranes was imaged using transmission electron microscopy (TEM). The cathode catalyst layer in the beginning-of-life (BOL) CCMs was fabricated using commercially available catalysts created from Pt precursors with and without nitrogen containing ligands. The surface composition of these catalyst powders was measured by X-ray Photoelectron Spectroscopy (XPS). The local chemical environment of the PTIM in EOL CCMs was found to be directly related to the Pt precursor used in CCM fabrication. STXM chemical mapping at the N 1s edge revealed a characteristic spectrum at and around the dendritic Pt particles in CCMs fabricated with nitrogen containing Pt-precursors. This N 1s spectrum was identical to that of the cathode and different from the membrane. For CCM samples fabricated without nitrogen containing Pt-precursors the N 1s spectrum at the Pt particles was indistinguishable from that of the adjacent membrane. We interpret these observations to indicate that nitrogenous ligands in the nitrogen containing precursors, or decomposition product(s) from that source, are transported together with the dissolved Pt from the cathode into the membrane as a result of the catalyst degradation process. This places constraints on possible mechanisms for the PTIM band formation process.

  8. How do polymers degrade?

    NASA Astrophysics Data System (ADS)

    Lyu, Suping

    2011-03-01

    Materials derived from agricultural products such as cellulose, starch, polylactide, etc. are more sustainable and environmentally benign than those derived from petroleum. However, applications of these polymers are limited by their processing properties, chemical and thermal stabilities. For example, polyethylene terephthalate fabrics last for many years under normal use conditions, but polylactide fabrics cannot due to chemical degradation. There are two primary mechanisms through which these polymers degrade: via hydrolysis and via oxidation. Both of these two mechanisms are related to combined factors such as monomer chemistry, chain configuration, chain mobility, crystallinity, and permeation to water and oxygen, and product geometry. In this talk, we will discuss how these materials degrade and how the degradation depends on these factors under application conditions. Both experimental studies and mathematical modeling will be presented.

  9. 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...

  10. 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, ...

  11. Initiation of polymer degradation via transfer of infectious species.

    SciTech Connect

    Clough, Roger Lee; Jones, Gary Dunn; Celina, Mathias Christopher

    2005-06-01

    A novel dual stage chemiluminescence detection system incorporating individually controlled hot stages has been developed and applied to probe for material interaction effects during polymer degradation. Utilization of this system has resulted in experimental confirmation for the first time that in an oxidizing environment a degrading polymer A (in this case polypropylene, PP) is capable of infecting a different polymer B (in this case polybutadiene, HTPB) over a relatively large distance. In the presence of the infectious degrading polymer A, the thermal degradation of polymer B is observed over a significantly shorter time period. Consistent with infectious volatiles from material A initiating the degradation process in material B it was demonstrated that traces (micrograms) of a thermally sensitive peroxide in the vicinity of PP could induce degradation remotely. This observation documents cross-infectious phenomena between different polymers and has major consequences for polymer interactions, understanding fundamental degradation processes and long-term aging effects under combined material exposures.

  12. Initiation of polymer degradation via transfer of infectious species.

    SciTech Connect

    Clough, Roger Lee; Jones, Gary D.; Celina, Mathias Christopher

    2005-02-01

    A novel dual stage chemiluminescence detection system incorporating individually controlled hot stages has been developed and applied to probe for material interaction effects during polymer degradation. Utilization of this system has resulted in experimental confirmation for the first time that in an oxidizing environment a degrading polymer A (in this case polypropylene, PP) is capable of infecting a different polymer B (in this case polybutadiene, HTPB) over a relatively large distance. In the presence of the infectious degrading polymer A, the thermal degradation of polymer B is observed over a significantly shorter time period. Consistent with infectious volatiles from material A initiating the degradation process in material B it was demonstrated that traces (micrograms) of a thermally sensitive peroxide in the vicinity of PP could induce degradation remotely. This observation documents cross-infectious phenomena between different polymers and has major consequences for polymer interactions, understanding fundamental degradation processes and long-term aging effects under combined material exposures.

  13. 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.

  14. 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.

  15. Degradable vinyl polymers for biomedical applications

    NASA Astrophysics Data System (ADS)

    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.

  16. 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.

  17. Probing properties of cold radiofrequency plasma with polymer probe

    NASA Astrophysics Data System (ADS)

    Bormashenko, E.; Chaniel, G.; Multanen, V.

    2015-01-01

    The probe intended for the characterization of cold plasma is introduced. The probe allows the estimation of Debye length of cold plasma. The probe is based on the pronounced modification of surface properties (wettability) of polymer films by cold plasmas. The probe was tested with the cold radiofrequency inductive air plasma discharge. The Debye length and the concentration of charge carriers were estimated for various gas pressures. The reported results coincide reasonably with the corresponding values established by other methods. The probe makes possible measurement of characteristics of cold plasmas in closed chambers.

  18. A constitutive law for degrading bioresorbable polymers.

    PubMed

    Samami, Hassan; Pan, Jingzhe

    2016-06-01

    This paper presents a constitutive law that predicts the changes in elastic moduli, Poisson's ratio and ultimate tensile strength of bioresorbable polymers due to biodegradation. During biodegradation, long polymer chains are cleaved by hydrolysis reaction. For semi-crystalline polymers, the chain scissions also lead to crystallisation. Treating each scission as a cavity and each new crystal as a solid inclusion, a degrading semi-crystalline polymer can be modelled as a continuum solid containing randomly distributed cavities and crystal inclusions. The effective elastic properties of a degrading polymer are calculated using existing theories for such solid and the tensile strength of the degrading polymer is predicted using scaling relations that were developed for porous materials. The theoretical model for elastic properties and the scaling law for strength form a complete constitutive relation for the degrading polymers. It is shown that the constitutive law can capture the trend of the experimental data in the literature for a range of biodegradable polymers fairly well. PMID:26971070

  19. 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.

  20. Polymer scaffold degradation control via chemical control

    DOEpatents

    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.

  1. 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.

  2. 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.

  3. 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.

  4. 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

  5. Preparation and degradation mechanisms of biodegradable polymer: a review

    NASA Astrophysics Data System (ADS)

    Zeng, S. H.; Duan, P. P.; Shen, M. X.; Xue, Y. J.; Wang, Z. Y.

    2016-07-01

    Polymers are difficult to degrade completely in Nature, and their catabolites may pollute the environment. In recent years, biodegradable polymers have become the hot topic in people's daily life with increasing interest, and a controllable polymer biodegradation is one of the most important directions for future polymer science. This article presents the main preparation methods for biodegradable polymers and discusses their degradation mechanisms, the biodegradable factors, recent researches and their applications. The future researches of biodegradable polymers are also put forward.

  6. 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.

  7. 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.

  8. 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.

  9. 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

  10. 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.

  11. Stable isotope probing identifies anthracene degraders under methanogenic conditions.

    PubMed

    Zhang, Shuying; Wang, Qingfeng; Xie, Shuguang

    2012-04-01

    Polycyclic aromatic hydrocarbons (PAHs) are common contaminants in groundwater. The remediation of PAH-contaminated groundwater often involves anaerobic biodegradation. The knowledge about the microorganisms responsible for PAH degradation in anaerobic subsurface environment is still lacking. DNA-based stable isotope probing (SIP) was applied to discover the microorganisms responsible for anaerobic anthracene degradation within microcosms inoculated with aquifer sediment from landfill leachate-contaminated site. Three phylotypes were identified as the degraders, all falling within the phylum Proteobacteria. Two anthracene degraders were classified within the genera Methylibium and Legionella, while another one was an unclassified Rhizobiales species. They all were first linked to PAH degradation. These findings also provide an illustration of the utility of SIP to discover the roles of uncultured microorganisms in PAH-degrading processes.

  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. Reinforcement and degradation mechanisms in polymer/inorganic nanocomposites

    NASA Astrophysics Data System (ADS)

    Bogdanova, Irina Rifkatovna

    This project accomplished the following goals: preparation of polymer/alumina nanocomposites using a single-screw extrusion approach, a systematic investigation of interfacial interactions, the mechanisms for reinforcement, and the thermal degradation and flame retardant mechanisms in polymer nanocomposites. In this work it was found that the stereochemistry of polymer macromolecules and the shapes of nanoparticles are extremely important in determining the interfacial interactions between them. Understanding of the nature of these interactions can result in a comprehensive understanding of reinforcement mechanisms in polymer nanocomposites. It was found that aromatic polymers such as polycarbonate and polystyrene have stronger interfacial interactions with needle or whisker-shaped nanoparticles than with spherical-shaped nanoparticles, while linear aliphatic polymers such as polymethylmethacrylate showed strong interactions with spherical nanoparticles. Other factors affecting the strength of interfacial interactions such as size, surface modification and concentration of nanoparticles were also studied. The thermal stability of polymer nanocomposites was studied to unravel the thermal degradation mechanisms. It was found that the chemical nature of nanoparticles plays a significant role in the thermal decomposition of polymer nanocomposites. For instance, SEM studies of polymer nanocomposites chars revealed that alumina nanoparticles moved to the surface of nanocomposites, while silica nanoparticles stayed in the body of the material, which enhances char formation. The mechanisms for the flammability in polymer/alumina nanocomposites were found to depend on the viscosity of the melt flow of nanocomposites. FT-IR, MS, and surface free energy characterization for modified alumina surfaces were done. The compatibility of polymer molecules and nanoparticles was studied on the basis of surface free energy. It was shown that modification of the alumina surface with

  14. 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.

  15. Navigating conjugated polymer actuated neural probes in a brain phantom

    NASA Astrophysics Data System (ADS)

    Daneshvar, Eugene D.; Kipke, Daryl; Smela, Elisabeth

    2012-04-01

    Neural probe insertion methods have a direct impact on the longevity of the device in the brain. Initial tissue and vascular damage caused by the probe entering the brain triggers a chronic tissue response that is known to attenuate neural recordings and ultimately encapsulate the probes. Smaller devices have been found to evoke reduced inflammatory response. One way to record from undamaged neural networks may be to position the electrode sites away from the probe. To investigate this approach, we are developing probes with controllably movable electrode projections, which would move outside of the zone that is damaged by the insertion of the larger probe. The objective of this study was to test the capability of conjugated polymer bilayer actuators to actuate neural electrode projections from a probe shank into a transparent brain phantom. Parylene neural probe devices, having five electrode projections with actuating segments and with varying widths (50 - 250 μm) and lengths (200 - 1000 μm) were fabricated. The electroactive polymer polypyrrole (PPy) was used to bend or flatten the projections. The devices were inserted into the brain phantom using an electronic microdrive while simultaneously activating the actuators. Deflections were quantified based on video images. The electrode projections were successfully controlled to either remain flat or to actuate out-of-plane and into the brain phantom during insertion. The projection width had a significant effect on their ability to deflect within the phantom, with thinner probes deflecting but not the wider ones. Thus, small integrated conjugated polymer actuators may enable multiple neuro-experiments and applications not possible before.

  16. Study on degradation process of polymer electrolyte by solution analysis

    NASA Astrophysics Data System (ADS)

    Akiyama, Yoko; Sodaye, Hemant; Shibahara, Yuji; Honda, Yoshihide; Tagawa, Seiichi; Nishijima, Shigehiro

    Degradation process of Nafion which is one of the polymer electrolyte generally used for polymer electrolyte membrane fuel cell was investigated by solution analysis and structural analysis of eluted species. Nafion degraded by gamma-ray irradiation and heat treatment was immersed in distilled water and the solutions were analyzed using ion chromatograph, total organic carbon (TOC) analyzer, and inductively coupled plasma atomic emission spectrometer (ICP-AES). The solutions after the Fenton reaction were also analyzed with the same methods. Proton, sulfide ion, fluorine ion and organic carbon were eliminated into the solution, and their ratio was changed depending on the degradation method. To determine the eliminated species to the solution, structural analysis of concentrated dissolved species was performed using FT-IR. As the results, the initial process of degradation was detected sensitively in solution analysis compared with membrane analysis, and difference of the degradation process under different conditions was clearly observed. It was also found that new functional group COOH was formed in the eliminated species. These results showed that solution analysis are very simple yet powerful methods to elucidate the degradation process, which can also be applied to actual fuel cell operation to track minute changes in the polymer electrolyte.

  17. Aliphatic polyesters: great degradable polymers that cannot do everything.

    PubMed

    Vert, Michel

    2005-01-01

    Nowadays the open and the patent literatures propose a large number of polymers whose main chains can be degraded usefully. Among these degradable polymers, aliphatic polyester-based polymeric structures are receiving special attention because they are all more or less sensitive to hydrolytic degradation, a feature of interest when compared with the fact that living systems function in aqueous media. Only some of these aliphatic polyesters are enzymatically degradable. A smaller number is biodegradable, and an even more limited number is biorecyclable. To be of practical interest, a degradable polymer must fulfill many requirements that depend very much on the targeted application, on the considered living system, and on living conditions. It is shown that aliphatic polyester structures made of repeating units that can generate metabolites upon degradation or biodegradation like poly(beta-hydroxy alkanoate)s and poly(alpha-hydroxy alkanoate)s are of special interest. Their main characteristics are confronted to the specifications required by various potential sectors of applications, namely, surgery, pharmacology, and the environment. It is shown that degradation, bioresorption, and biorecycling that are targets when one wants to respect living systems are also drastic limiting factors when one wants to achieve a device of practical interest. Finding a universal polymer that would be the source of all the polymeric biomaterials needed to work in contact with living organisms of the various life kingdoms and respect them remains a dream. On the other hand, finding one polymeric structure than can fulfill the requirements of one niche application remains a big issue.

  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. 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.

  20. 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.

  1. 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.

  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

    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.

  4. Degradability of an Acrylate-Linked, Fluorotelomer Polymer in Soil

    EPA Science Inventory

    Fluorotelomer polymers are used in a broad array of products in modern societies worldwide and, if they degrade at significant rates, potentially are a significant source of perfluorooctanoic acid (PFOA) and related compounds to the environment. To evaluate this possibility, we i...

  5. 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...

  6. 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.

  7. Electrical Conductivity Studies on Individual Conjugated Polymer Nanowires: Two-Probe and Four-Probe Results

    PubMed Central

    2010-01-01

    Two- and four-probe electrical measurements on individual conjugated polymer nanowires with different diameters ranging from 20 to 190 nm have been performed to study their conductivity and nanocontact resistance. The two-probe results reveal that all the measured polymer nanowires with different diameters are semiconducting. However, the four-probe results show that the measured polymer nanowires with diameters of 190, 95–100, 35–40 and 20–25 nm are lying in the insulating, critical, metallic and insulting regimes of metal–insulator transition, respectively. The 35–40 nm nanowire displays a metal–insulator transition at around 35 K. In addition, it was found that the nanocontact resistance is in the magnitude of 104Ω at room temperature, which is comparable to the intrinsic resistance of the nanowires. These results demonstrate that four-probe electrical measurement is necessary to explore the intrinsic electronic transport properties of isolated nanowires, especially in the case of metallic nanowires, because the metallic nature of the measured nanowires may be coved by the nanocontact resistance that cannot be excluded by a two-probe technique. PMID:20652139

  8. Femtosecond Pump-Push-Probe and Pump-Dump-Probe Spectroscopy of Conjugated Polymers: New Insight and Opportunities.

    PubMed

    Kee, Tak W

    2014-09-18

    Conjugated polymers are an important class of soft materials that exhibit a wide range of applications. The excited states of conjugated polymers, often referred to as excitons, can either deactivate to yield the ground state or dissociate in the presence of an electron acceptor to form charge carriers. These interesting properties give rise to their luminescence and the photovoltaic effect. Femtosecond spectroscopy is a crucial tool for studying conjugated polymers. Recently, more elaborate experimental configurations utilizing three optical pulses, namely, pump-push-probe and pump-dump-probe, have been employed to investigate the properties of excitons and charge-transfer states of conjugated polymers. These studies have revealed new insight into femtosecond torsional relaxation and detrapping of bound charge pairs of conjugated polymers. This Perspective highlights (1) the recent achievements by several research groups in using pump-push-probe and pump-dump-probe spectroscopy to study conjugated polymers and (2) future opportunities and potential challenges of these techniques.

  9. 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

  10. 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.

  11. Enhanced regeneration of degraded polymer solar cells by thermal annealing

    SciTech Connect

    Kumar, Pankaj; Bilen, Chhinder; Zhou, Xiaojing; Belcher, Warwick J.; Dastoor, Paul C.; Feron, Krishna

    2014-05-12

    The degradation and thermal regeneration of poly(3-hexylethiophene) (P3HT):[6,6]-phenyl-C{sub 61}-butyric acid methyl ester (PCBM) and P3HT:indene-C{sub 60} bisadduct (ICBA) polymer solar cells, with Ca/Al and Ca/Ag cathodes and indium tin oxide/poly(ethylene-dioxythiophene):polystyrene sulfonate anode have been investigated. Degradation occurs via a combination of three primary pathways: (1) cathodic oxidation, (2) active layer phase segregation, and (3) anodic diffusion. Fully degraded devices were subjected to thermal annealing under inert atmosphere. Degraded solar cells possessing Ca/Ag electrodes were observed to regenerate their performance, whereas solar cells having Ca/Al electrodes exhibited no significant regeneration of device characteristics after thermal annealing. Moreover, the solar cells with a P3HT:ICBA active layer exhibited enhanced regeneration compared to P3HT:PCBM active layer devices as a result of reduced changes to the active layer morphology. Devices combining a Ca/Ag cathode and P3HT:ICBA active layer demonstrated ∼50% performance restoration over several degradation/regeneration cycles.

  12. Degradable polymers in medicine: updating strategies and terminology.

    PubMed

    Vert, Michel

    2011-02-01

    Today, the field of biodegradable materials and devices attracts polymer scientists and healthcare professionals in surgery, dentistry, pharmacology and regenerative medicine. More than one thousand papers are published per year in the literature, while the topic appears in the title of many patents. However, the number of devices or systems that have been successfully developed for clinical and commercial uses is still very small. A critical examination of the literature suggests two main reasons for this. Firstly, biodegradation is generally considered the main goal to reach, so that academic strategies do not take into account the criteria specific to targeted applications. Secondly, the term "biodegradable" is too often used inappropriately and creates confusion. This paper aims specifically to remind readers of the complexity of in vivo polymer degradation and the need for an enriched and universally recognized terminology in order to clearly distinguish between the various possible stages, and to enable clear communication between specialists when discussing related issues. It also emphasizes the need for any novel polymer to be well characterized and to include application-specific requirements in the research strategy from the very beginning, since these determine its potential clinical and commercial uses. Based on more than a decade of efforts, this would appear to be paramount in order to provide a chance for novel polymers to reach the market.

  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. 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

  15. Probing of polymer surfaces in the viscoelastic regime.

    PubMed

    Chyasnavichyus, Marius; Young, Seth L; Tsukruk, Vladimir V

    2014-09-01

    In this Feature Article, we discussed the experimental and modeling methods and analyzed the limitations of the surface probing of nanomechanical properties of polymeric and biological materials in static and dynamic regimes with atomic force microscopy (AFM), which are widely utilized currently. To facilitate such measurements with minimized ambiguities, in this study we present a combined method to evaluate the viscoelastic properties of compliant polymeric materials. We collected force-distance data in the static regime for a benchmark polymer material (poly(n-butyl methacrylate)) with an easily accessible glass-transition temperature (about 25 °C) at different loading rates and different temperatures across the glassy state, glass-transition region, and rubbery state. For this analysis, we exploited a Johnson-modified Sneddon's approach in a combination with the standard linear solid model. Critical experimental steps suggested for robust probing are (i) the use of a tip with a well-characterized parabolic shape, (ii) probing in a liquid environment in order to reduce jump-in phenomenon, and (iii) minute indentations to ensure the absence of plastic deformation. Whereas the standard Sneddon's model generates quantitatively adequate elastic modulus values below and above the glass transition, this traditional approach can significantly underestimate actual modulus values in the vicinity of the glass-transition region (15 °C above or below Tg), with major deviations occurring at the loss tangent peak. The analysis of the experimental data with Sneddon's model for the elastic region (glassy and rubbery states) and Johnson's model for the viscoelastic region allowed for the restoration of the universal master curve and the evaluation of the storage modulus, loss modulus, loss tangent, relaxation times, and activation energies of the polymer surface across the glass-transition region and at relevant loading rates.

  16. Regulation of coal polymer degradation by fungi. Fifth quarterly report, July 1995--September 1995

    SciTech Connect

    Irvine, R.L.

    1995-10-24

    This research program investigates the solubilization and depolymerization of coal polymer degradation by Fungi. We investigate the hypothesis that solubilization and depolymerization are distinctive events.

  17. 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

    2016-01-01

    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

  18. 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

  19. 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.

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

    SciTech Connect

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

    1988-11-01

    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, /sub e/, with a ductless-siphon technique demonstrates that the enhanced resistance seen at high flow rates is not directly proportional to /sub e/. Furthermore, significant permeability trends in resistance factor and mechanical degradation are observed when plotted vs. strain rate. 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.

  1. 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.

  2. Surface functionalization of degradable polymers by covalent grafting.

    PubMed

    Källrot, Martina; Edlund, Ulrica; Albertsson, A-C

    2006-03-01

    With a new non-destructive and solvent-free photografting technique, N-vinylpyrrolidone was covalently grafted onto the surfaces of degradable polymers; poly(l-lactide), poly(epsilon-caprolactone), poly(lactide-co-glycolide), and poly(trimethylene carbonate). The modified surfaces were characterized by XPS, ATR-FTIR, SEM, and cell growth tests. The wettability was markedly improved, as static contact angles changed from about 80 degrees for the pristine substrates to around 30 degrees after 30min of grafting. Well-defined surface topographies, such as micro-patterns, are preserved in the process since the graft layers are thin. The biological response, measured as cytotoxicity, showed that the modified films provide good substrates, comparable with optimized cell culture plastics, for the adhesion and proliferation of normal human keratinocytes and skin fibroblasts. PMID:16257444

  3. 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.

  4. 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

  5. Side Chain Degradable Cationic-Amphiphilic Polymers with Tunable Hydrophobicity Show in Vivo Activity.

    PubMed

    Uppu, Divakara S S M; Samaddar, Sandip; Hoque, Jiaul; Konai, Mohini M; Krishnamoorthy, Paramanandham; Shome, Bibek R; Haldar, Jayanta

    2016-09-12

    Cationic-amphiphilic antibacterial polymers with optimal amphiphilicity generally target the bacterial membranes instead of mammalian membranes. To date, this balance has been achieved by varying the cationic charge or side chain hydrophobicity in a variety of cationic-amphiphilic polymers. Optimal hydrophobicity of cationic-amphiphilic polymers has been considered as the governing factor for potent antibacterial activity yet minimal mammalian cell toxicity. However, the concomitant role of hydrogen bonding and hydrophobicity with constant cationic charge in the interactions of antibacterial polymers with bacterial membranes is not understood. Also, degradable polymers that result in nontoxic degradation byproducts offer promise as safe antibacterial agents. Here we show that amide- and ester (degradable)-bearing cationic-amphiphilic polymers with tunable side chain hydrophobicity can modulate antibacterial activity and cytotoxicity. Our results suggest that an amide polymer can be a potent antibacterial agent with lower hydrophobicity whereas the corresponding ester polymer needs a relatively higher hydrophobicity to be as effective as its amide counterpart. Our studies reveal that at higher hydrophobicities both amide and ester polymers have similar profiles of membrane-active antibacterial activity and mammalian cell toxicity. On the contrary, at lower hydrophobicities, amide and ester polymers are less cytotoxic, but the former have potent antibacterial and membrane activity compared to the latter. Incorporation of amide and ester moieties made these polymers side chain degradable, with amide polymers being more stable than the ester polymers. Further, the polymers are less toxic, and their degradation byproducts are nontoxic to mice. More importantly, the optimized amide polymer reduces the bacterial burden of burn wound infections in mice models. Our design introduces a new strategy of interplay between the hydrophobic and hydrogen bonding interactions

  6. 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

  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. 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. PMID:26216708

  9. 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

    2016-06-01

    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. PMID:27187246

  10. 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.

  11. 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.

  12. 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.

  13. 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

  14. Probe surface chemistry dependence and local polymer network structure in F-actin microrheology.

    PubMed

    Chae, Byeong Seok; Furst, Eric M

    2005-03-29

    We investigate the dependence of F-actin microrheology on probe surface chemistry using diffusing wave spectroscopy. Polystyrene probe particles exhibit subdiffusive mean-squared displacements, where Deltar(2)(t) approximately t(0.77)(+/-)(0.03) consistent with previous experiments and theory. However, polystyrene probes preadsorbed with bovine serum albumin (BSA) interact weakly with the surrounding polymer network and exhibit a scaling exponent similar to pure diffusion Deltar(2)(t) approximately t, which decreases as particle size and actin concentration increases. Using models of particle diffusion in locally heterogeneous viscoelastic microenvironments, we find that the microrheological response of BSA-treated particles is consistent with the formation of a polymer-depleted shell surrounding the probes. The shell thickness scales with particle size but not polymer concentration. These results suggest that the depletion is caused by exclusion or orientation of actin filaments near probes due to their long length and rigidity.

  15. 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.

  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. 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.

  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. PMID:27470943

  19. 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.

  20. 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.

  1. Probing the interfacial region in polymer-graphene oxide nanocomposites

    NASA Astrophysics Data System (ADS)

    Weir, Michael; Boothroyd, Stephen; Johnson, David; Thompson, Richard; Clarke, Nigel; Coleman, Karl

    2015-03-01

    Graphene and related two-dimensional materials are excellent candidates as filler materials in nanocomposites due to their extraordinary physical properties and high aspect ratio. We are studying graphene oxide (GO), a highly functionalized form of graphene, due to its relative ease of dispersion within polymer matrices. Interruptions to the pristine two-dimensional carbon network by oxygen-containing groups, which provide functionality, also make GO rather flexible. In this paper we show that GO is wrinkled and rough over a hierarchy of length scales from a few nanometers to a few microns, when it is incorporated in composites with poly(methyl methacrylate) (PMMA) and polystyrene (PS). Small-angle neutron scattering measurements, highlighting individual polymer chains, show a decrease in polymer radius of gyration with increasing GO concentration in PMMA/GO nanocomposites. The decrease is consistent with models of a solid interface in a polymer melt. The interface influences the polymer matrix within an interfacial volume stretching on the order of one polymer radius of gyration from the surface. This work is a direct measurement of the effect of the nanofiller upon the polymer matrix and progresses our understanding of interfacial interactions within nanocomposites.

  2. A Single UV or Near IR Triggering Event Leads to Polymer Degradation into Small Molecules.

    PubMed

    de Gracia Lux, Caroline; McFearin, Cathryn L; Joshi-Barr, Shivanjali; Sankaranarayanan, Jagadis; Fomina, Nadezda; Almutairi, Adah

    2012-07-17

    We report two polymers with UV- and NIR-removable end caps that respond to a single light activated event by complete cleavage of the polymer backbone via a self-immolative mechanism. Two photocleavable protecting groups were used to cap the polymers; o-nitrobenzyl alcohol (ONB) and bromo-coumarin (Bhc). GPC and (1)H NMR confirmed complete degradation of the ONB-containing polymer in response to UV. The polymers were formulated into nanoparticles; fluorescence measurements of encapsulated Nile red confirmed release upon photolysis of the endcaps. Contrary to previous work using a similar backbone structure that degrades upon hydrolysis, here, the disassembly process and burst release of the payload are only activated on demand, illustrating the powerful capacity of light to trigger release from polymeric nanoparticles. Our design allows the signal to be amplified in a domino effect to fully degrade the polymer into small molecules. Thus, polymers and nanoparticles can reach maximal degradation without having to use intense and/or long periods of irradiation.

  3. 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.

  4. 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.

  5. 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. PMID:22939355

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

    DOEpatents

    Frechet, Jean M. J.; Standley, Stephany M.; Jain, Rachna; Lee, Cameron C.

    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.

  7. Diversity of Five Anaerobic Toluene-Degrading Microbial Communities Investigated Using Stable Isotope Probing

    PubMed Central

    Sun, Weimin

    2012-01-01

    Time-series DNA-stable isotope probing (SIP) was used to identify the microbes assimilating carbon from [13C]toluene under nitrate- or sulfate-amended conditions in a range of inoculum sources, including uncontaminated and contaminated soil and wastewater treatment samples. In all, five different phylotypes were found to be responsible for toluene degradation, and these included previously identified toluene degraders as well as novel toluene-degrading microorganisms. In microcosms constructed from granular sludge and amended with nitrate, the putative toluene degraders were classified in the genus Thauera, whereas in nitrate-amended microcosms constructed from a different source (agricultural soil), microorganisms in the family Comamonadaceae (genus unclassified) were the key putative degraders. In one set of sulfate-amended microcosms (agricultural soil), the putative toluene degraders were identified as belonging to the class Clostridia (genus Desulfosporosinus), while in other sulfate-amended microcosms, the putative degraders were in the class Deltaproteobacteria, within the family Syntrophobacteraceae (digester sludge) or Desulfobulbaceae (contaminated soil) (genus unclassified for both). Partial benzylsuccinate synthase gene (bssA, the functional gene for anaerobic toluene degradation) sequences were obtained for some samples, and quantitative PCR targeting this gene, along with SIP, was further used to confirm anaerobic toluene degradation by the identified species. The study illustrates the diversity of toluene degraders across different environments and highlights the utility of ribosomal and functional gene-based SIP for linking function with identity in microbial communities. PMID:22156434

  8. In vitro degradation of biodegradable polymer-coated magnesium under cell culture condition

    NASA Astrophysics Data System (ADS)

    Xu, Liping; Yamamoto, Akiko

    2012-06-01

    Magnesium (Mg) coated with four kinds of polymers, poly (L-lactic acid) (PLLA)-high molecular weight (HMW), PLLA-low molecular weight (LMW), poly (ɛ-caprolactone) (PCL)-HMW and PCL-LMW, and uncoated Mg were immersed under cell culture condition to study the degradation/corrosion behavior of the polymer-coated Mg. The releases of Mg2+ are measured during the immersion. Surface morphology and chemical composition are observed and identified by SEM and EDX. The tomography is obtained by X-ray CT observation and degradation rate is calculated by image analysis after 10-day immersion. All kinds of polymer-coated Mg showed significantly low release of Mg2+ (p < 0.05) in the whole immersion process comparing to that of uncoated Mg. In SEM and EDX results show, a corrosion layer can be observed on both polymer-coated and uncoated Mg after immersion. There is no obvious difference on the morphology and chemical composition of the corrosion layer between polymer-coated and uncoated Mg, indicating the corrosion/degradation process and corrosion product of Mg substrate are not changed by the polymer films under the present condition compared with uncoated Mg. Concerning the tomography and degradation rate of 10-day immersion, it can be found that the polymer-coated Mg shows a significantly low corrosion rate (p < 0.05) compared with that of uncoated Mg. PLLA coated Mg shows relatively uniform corrosion than PCL coated Mg and uncoated Mg. The largest pitting corrosion depth of PCL-LMW is about 3 times as large as the PLLA-LMW, which might be attributed to the difference of polymer microstructure. It is suggested that PLLA coating might be a suitable option for retarding the loss of mechanical properties of Mg substrate.

  9. 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

  10. Degradation and stability of R2R manufactured polymer solar cells

    NASA Astrophysics Data System (ADS)

    Norrman, Kion; Krebs, Frederik C.

    2009-08-01

    Polymer solar cells have many advantages such as light weight, flexibility, environmental friendliness, low thermal budget, low cost and most notably very fast modes of production by printing techniques. Production experiments have shown that it is highly feasible with existing technology to mass produce polymer solar cells at a very low cost. We have employed state-of-the-art analytical techniques to address the challenging issues of degradation and stability of R2R manufactured devices. We have specifically studied the relative effect of oxygen and water on the operational devices in regard to degradation.

  11. 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.

  12. Probing charge delocalization in a semi-crystalline supramolecular polymer

    NASA Astrophysics Data System (ADS)

    Kang, Keehoon; Watanabe, Shun; Broch, Katrina; Matsumoto, Daisuke; Marumoto, Kazuhiro; Tanaka, Hisaaki; Kuroda, Shin-Ichi; Heeney, Martin; Sirringhaus, Henning

    2015-03-01

    Various doping methods have achieved metallic conductivity in π-conjugated polymer but most of them suffer from dopant-induced-disorder. We developed a simple and effective method of doping a high mobility semi-crystalline polymer, poly(2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene) (pBTTT) by forming a bi-layer with a small-molecule acceptor, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ). The doping realizes an efficient charge-transfer between pBTTT and F4-TCNQ (conductivity over 150 S/cm), while preserving the structural order of a pristine pBTTT. The charges are discovered to be sufficiently delocalized to give rise to a nearly-ideal Hall effect, and therefore, a coherent transport in a wide temperature range, with a high Hall mobility of 1.8 cm2/Vs at room temperature. The combination of a Pauli magnetic susceptibility and magnetoconductance signatures strengthen the evidence of weak localization in the supramolecular system. Comparison with other amorphous conducting polymers elucidates the role of structural order as an indicator of the degree of charge delocalization.

  13. 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

  14. 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

  15. 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.

  16. Degradation behavior and biocompatibility of PEG/PANI-derived polyurethane co-polymers.

    PubMed

    Luo, Yan-Ling; Nan, Yun-Fei; Xu, Feng; Chen, Ya-Shao; Zhao, Pei

    2010-01-01

    A series of polyurethane (PU) co-polymers with designable molecular weight between cross-linking dots was synthesized by a hydrogen transfer polymerization route from polyaniline (PANI), poly(ethylene glycol) (PEG), various curing agents and chain extenders using dibutyltin dilaurate as a catalyst. Their swelling, hydrophilicity, degradation and biocompatibility were inspected and assessed based on different degrees of polymerization of PANI and PEG, and their component proportion. Fourier transformation infrared spectrometry (FT-IR), (1)H-NMR spectroscopy, scanning electron microscopy (SEM), gel-permeation chromatography (GPC) and goniometry were used to characterize the structure and surface morphology of the synthesized PEG/PANI-based PU co-polymers, PU residues after degradation and degraded polymers at different time periods of hydrolysis. The thermal properties, aggregate structure and surface microstructure were examined by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD) and atomic force microscopy (AFM). Hemolysis, static platelet adhesion, dynamic clotting measurements and MTT assays were adopted to evaluate the hemo- or cytocompatibility. The experimental results indicated that these polymers exhibit various degrees of micro-phase separation, depending on the concentration and degree of polymerization of PANI, molecular weight of PEG, type of curing agent and chain extender, which further influence their swelling, hydrophilicity, degradable properties and biological performances in vitro. The incorporation of PANI and PANI* in co-polymers led to decreased thermal stability but slower decomposition rates than typical PEG-based PUs. The stress-strain tests showed that the as-prepared PU co-polymers possessed increased tensile strength and modulus, and decreased toughness in comparison with the blank PEG-based PU. These co-polymers are expected to find specific applications in tissue engineering or controlled drug release. PMID

  17. Synthesis and characterization of acetalated dextran polymer and microparticles with ethanol as a degradation product.

    PubMed

    Kauffman, Kevin J; Do, Clement; Sharma, Sadhana; Gallovic, Matthew D; Bachelder, Eric M; Ainslie, Kristy M

    2012-08-01

    In the field of drug delivery, pH-sensitive polymeric microparticles can be used to release therapeutic payloads slowly in extracellular conditions (pH 7.4) and faster in more acidic areas in vivo, such as sites of inflammation, tumors, or intracellular conditions. Our group currently uses and is further developing the pH-sensitive polymer acetalated dextran (Ac-DEX), which is a biodegradable polymer with highly tunable degradation kinetics. Ac-DEX has displayed enhanced delivery of vaccine and drug components to immune and other cells, making it an extremely desirable polymer for immune applications. Currently, one of the degradation products of Ac-DEX is methanol, which may cause toxicity issues if applied at high concentrations with repeated doses. Therefore, in this manuscript we report the first synthesis and characterization of an Ac-DEX analog which, instead of a methanol degradation product, has a much safer ethanol degradation product. We abbreviate this ethoxy acetal derivatized acetalated dextran polymer as Ace-DEX, with the 'e' to indicate an ethanol degradation product. Like Ac-DEX, Ace-DEX microparticles have tunable degradation rates at pH 5 (intracellular). These rates range from hours to several days and are controlled simply by reaction time. Ace-DEX microparticles also show minimal cytotoxicity compared to commonly used poly(lactic-co-glycolic acid) (PLGA) microparticles when incubated with macrophages. This study aims to enhance the biocompatibility of acetalated dextran-type polymers to allow their use in high volume clinical applications such as multiple dosing and tissue engineering.

  18. Ferroelectric Polymer Matrix for Probing Molecular Organization in Perylene Diimides.

    PubMed

    Chellappan, Kishore V; Kandappa, Sunil Kumar; Rajaram, Sridhar; Narayan, K S

    2015-01-15

    Ferroelectric films of poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFE) provide a controlled environment to study the aggregation tendency of functional molecules such as perylene diimides (PDIs). The local electric field and free volume confinement parameters offered by the matrix are tailored to study the organizational and assembly characteritics of molecular acceptors. The optical properties of planar and nonplanar PDIs in the ferroelectric polymer matrix were studied systematically over a wide range that encompassed the ferroelectric transition temperature. This approach provides valuable insight into the properties of molecular materials used in applications ranging from bulk heterostructure-based photovoltaics to nonlinear optical materials.

  19. 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

  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. 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.

  3. 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. PMID:25450477

  4. Mechanical characterization of conducting polymer actuated neural probes under physiological settings

    NASA Astrophysics Data System (ADS)

    Daneshvar, Eugene D.; Smela, Elisabeth; Kipke, Daryl R.

    2010-04-01

    Most implantable chronic neural probes have fixed electrode sites on the shank of the probe. Neural probe shapes and insertion methods have been shown to have considerable effects on the resulting chronic reactive tissue response that encapsulates probes. We are developing probes with controllable articulated electrode projections, which are expected to provoke less reactive tissue response due to the projections being minimally sized, as well as to permit a degree of independence from the probe shank allowing the recording sites to "float" within the brain. The objective of this study was to predict and analyze the force-generating capability of conducting polymer bilayer actuators under physiological settings. Custom parylene beams 21 μm thick, 1 cm long, and of varying widths (200 - 1000 μm) were coated with Cr/Au. Electroplated weights were fabricated at the ends of the beams to apply known forces. Polypyrrole was potentiostatically polymerized to varying thicknesses onto the Au at 0.5 V in a solution of 0.1 M pyrrole and 0.1 M dodecylbenzenesulfonate (DBS). Using cyclic voltammetry, the bilayer beams were cycled in artificial cerebrospinal fluid (aCSF) at 37 °C, as well as in aqueous NaDBS as a control. Digital images and video were analyzed to quantify the deflections. The images and the cyclic voltammograms showed that divalent cations in the aCSF interfered with polymer reduction. By integrating polypyrrole-based conducting polymer actuators, we present a type novel neural probe. We demonstrate that actuating PPy(DBS) under physiological settings is possible, and that the technique of microfabricating weights onto the actuators is a useful tool for studying actuation forces.

  5. Trimethylene carbonate and epsilon-caprolactone based (co)polymer networks: mechanical properties and enzymatic degradation.

    PubMed

    Bat, Erhan; Plantinga, Josée A; Harmsen, Martin C; van Luyn, Marja J A; Zhang, Zheng; Grijpma, Dirk W; Feijen, Jan

    2008-11-01

    High molecular weight trimethylene carbonate (TMC) and epsilon-caprolactone (CL) (co)polymers were synthesized. Melt pressed (co)polymer films were cross-linked by gamma irradiation (25 kGy or 50 kGy) in vacuum, yielding gel fractions of up to 70%. The effects of copolymer composition and irradiation dose on the cytotoxicity, surface properties, degradation behavior, and mechanical and thermal properties of these (co)polymers and networks were investigated. Upon incubation with cell culture medium containing extracts of (co)polymers and networks, human foreskin fibroblasts remained viable. For all (co)polymers and networks, cell viabilities were determined to be higher than 94%. The formed networks were flexible, with elastic moduli ranging from 2.7 to 5.8 MPa. Moreover, these form-stable networks were creep resistant under dynamic conditions. The permanent deformation after 2 h relaxation was as low as 1% after elongating to 50% strain for 20 times. The in vitro enzymatic erosion behavior of these hydrophobic (co)polymers and networks was investigated using aqueous lipase solutions. The erosion rates in lipase solution could be tuned linearly from 0.8 to 45 mg/(cm (2) x day) by varying the TMC to CL ratio and the irradiation dose. The copolymers and networks degraded essentially by a surface erosion mechanism. PMID:18855440

  6. 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.

  7. Femtosecond pump-probe spectroscopy of conjugated polymers: Coherent and sequential contributions

    NASA Astrophysics Data System (ADS)

    Bosma, W. B.; Mukamel, S.; Greene, B. I.; Schmitt-Rink, S.

    1992-04-01

    We report femtosecond pump-probe difference absorption experiments on polydiacetylene-para-toluene sulfonate. Theoretical analysis using a three-mode Brownian oscillator model for the nuclear dynamics reveals spectral diffusion in this conjugated polymer; this effect cannot be accounted for using the optical Bloch equations. Sequential (pump first) time ordering is dominant for resonant excitation, whereas experiments utilizing an off-resonant pump are dominated by nonsequential time orderings of the pump and the probe; the latter represent coherent (Raman-type) processes.

  8. Degradation mechanism of a low band gap polymer PTB7 by oxidation

    NASA Astrophysics Data System (ADS)

    Park, Soohyung; Jeong, Junkyeong; Lee, Hyunbok; Yi, Yeonjin

    Recently, the PCE of OPVs is at the 10% mark by using donor materials having a low band gap, such as poly(4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl-alt-3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophene-4,6-diyl) (PTB7) and its analogues. In spite of the significant PCE improvement, the lifetime issue still remains open problem. To solve these technical limitations fundamentally, the degradation mechanism should be understood. It can be revealed by investigating the electronic structures of polymers with controlled exposure of oxygen, moisture and light. In this study, ultraviolet, X-ray and inverse photoelectron spectroscopy measurements were performed with step-by-step exposure of controlled oxygen, moisture and light to investigate the degradation mechanism of each polymer film. Theoretical calculations using density functional theory (DFT) were also performed to understand detailed degradation process. From the experimental results, we demonstrate that push-pull polymers are more sensitive to environmental conditions, compared with non-push-pull (conventional) polymers such as poly (3-hexylthiophene-2,5-diyl) (P3HT). In addition, we show high photo-oxidation of PTB7 is originated from the structural reason.

  9. The Production of Solid Dosage Forms from Non-Degradable Polymers.

    PubMed

    Major, Ian; Fuenmayor, Evert; McConville, Christopher

    2016-01-01

    Non-degradable polymers have an important function in medicine. Solid dosage forms for longer term implantation require to be constructed from materials that will not degrade or erode over time and also offer the utmost biocompatibility and biostability. This review details the three most important non-degradable polymers for the production of solid dosage forms - silicone elastomer, ethylene vinyl acetate and thermoplastic polyurethane. The hydrophobic, thermoset silicone elastomer is utilised in the production of a broad range of devices, from urinary catheter tubing for the prevention of biofilm to intravaginal rings used to prevent HIV transmission. Ethylene vinyl acetate, a hydrophobic thermoplastic, is the material of choice of two of the world's leading forms of contraception - Nuvaring® and Implanon®. Thermoplastic polyurethane has such a diverse range of building blocks that this one polymer can be hydrophilic or hydrophobic. Yet, in spite of this versatility, it is only now finding utility in commercialised drug delivery systems. Separately then one polymer has a unique ability that differentiates it from the others and can be applied in a specific drug delivery application; but collectively these polymers provide a rich palette of material and drug delivery options to empower formulation scientists in meeting even the most demanding of unmet clinical needs. Therefore, these polymers have had a long history in controlled release, from the very beginning even, and it is pertinent that this review examines briefly this history while also detailing the state-of-the-art academic studies and inventions exploiting these materials. The paper also outlines the different production methods required to manufacture these solid dosage forms as many of the processes are uncommon to the wider pharmaceutical industry.

  10. 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.

  11. Suite of activity-based probes for cellulose-degrading enzymes.

    PubMed

    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

    2012-12-19

    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 liquid chromatography-mass spectrometry (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. 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.

  13. 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. PMID:26457462

  14. 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.

  15. DNA detection using water-soluble conjugated polymers and peptide nucleic acid probes

    NASA Astrophysics Data System (ADS)

    Gaylord, Brent S.; Heeger, Alan J.; Bazan, Guillermo C.

    2002-08-01

    The light-harvesting properties of cationic conjugated polymers are used to sensitize the emission of a dye on a specific peptide nucleic acid (PNA) sequence for the purpose of homogeneous, "real-time" DNA detection. Signal transduction is controlled by hybridization of the neutral PNA probe and the negative DNA target. Electrostatic interactions bring the hybrid complex and cationic polymer within distances required for Förster energy transfer. Conjugated polymer excitation provides fluorescein emission >25 times higher than that obtained by exciting the dye, allowing detection of target DNA at concentrations of 10 pM with a standard fluorometer. A simple and highly sensitive assay with optical amplification that uses the improved hybridization behavior of PNA/DNA complexes is thus demonstrated.

  16. 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

  17. 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

    2016-01-01

    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

  18. Application of (13)C-stable isotope probing to identify RDX-degrading microorganisms in groundwater.

    PubMed

    Cho, Kun-Ching; Lee, Do Gyun; Roh, Hyungkeun; Fuller, Mark E; Hatzinger, Paul B; Chu, Kung-Hui

    2013-07-01

    We employed stable isotope probing (SIP) with (13)C-labeled hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) to identify active microorganisms responsible for RDX biodegradation in groundwater microcosms. Sixteen different 16S rRNA gene sequences were derived from microcosms receiving (13)C-labeled RDX, suggesting the presence of microorganisms able to incorporate carbon from RDX or its breakdown products. The clones, residing in Bacteroidia, Clostridia, α-, β- and δ-Proteobacteria, and Spirochaetes, were different from previously described RDX degraders. A parallel set of microcosms was amended with cheese whey and RDX to evaluate the influence of this co-substrate on the RDX-degrading microbial community. Cheese whey stimulated RDX biotransformation, altered the types of RDX-degrading bacteria, and decreased microbial community diversity. Results of this study suggest that RDX-degrading microorganisms in groundwater are more phylogenetically diverse than what has been inferred from studies with RDX-degrading isolates. PMID:23603473

  19. 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

  20. 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

  1. Semiconducting Polymer Nanoparticles as Photoacoustic Molecular Imaging Probes in Living Mice

    PubMed Central

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

    2014-01-01

    Photoacoustic (PA) 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, PA molecular imaging probes have to be developed. Herein we introduce near infrared (NIR) light absorbing semiconducting polymer nanoparticles (SPNs) as a new class of contrast agents for PA molecular imaging. SPNs can produce stronger signal than commonly used single-wall carbon nanotubes and gold nanorods on a per mass basis, permitting whole-body lymph node PA mapping in living mice at a low systematic injection mass. Furthermore, SPNs possess high structural flexibility, narrow PA spectral profiles, and strong resistance to photodegradation and oxidation, which enables development of the first NIR ratiometric PA probe for in vivo real-time imaging of reactive oxygen species—vital chemical mediators of many diseases. These results demonstrate SPNs an ideal nanoplatform for developing PA molecular probes. PMID:24463363

  2. 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

  3. 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

  4. Enzyme-Degradable Hybrid Polymer/Silica Microbubbles as Ultrasound Contrast Agents.

    PubMed

    Tsao, Nadia H; Hall, Elizabeth A H

    2016-06-28

    The fabrication of an enzyme-degradable polymer/silica hybrid microbubble is reported that produces an ultrasound contrast image. The polymer, a triethoxysilane end-capped polycaprolactone (SiPCL), is used to incorporate enzyme-degradable components into a silica microbubble synthesis, and to impart increased elasticity for enhanced acoustic responsiveness. Formulations of 75, 85, and 95 wt % SiPCL in the polymer feed produced quite similar ratios of SiPCL and silica in the final bubble but different surface properties. The data suggest that different regions of the microbubbles were SiPCL-rich: the inner layer next to the polystyrene template core and the outer surface layer, thereby creating a sandwiched silica-rich layer of the bubble shell. Overall, the thickness of the microbubble shell was dependent on the starting TEOS concentration and the reaction time. Despite the layered structure, the microbubble could be efficiently degraded by lipase enzyme, but was stable without enzyme. The ultrasound contrast showed a general trend of increase in image intensity with SiPCL feed ratio, although the 95 wt % SiPCL bubbles did not produce a contrast image, probably due to bubble collapse. At higher normalized peak negative acoustic pressure (mechanical index, MI), a nonlinear frequency response also emerges, characterized by the third harmonic at around 3f0, and increases with MI. The threshold MI transition from linear to nonlinear response increased with decrease in SiPCL. PMID:27245495

  5. 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.

  6. 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

  7. Determination of linear viscoelastic properties of an entangled polymer melt by probe rheology simulations

    NASA Astrophysics Data System (ADS)

    Karim, Mir; Indei, Tsutomu; Schieber, Jay D.; Khare, Rajesh

    2016-01-01

    Particle rheology is used to extract the linear viscoelastic properties of an entangled polymer melt from molecular dynamics simulations. The motion of a stiff, approximately spherical particle is tracked in both passive and active modes. We demonstrate that the dynamic modulus of the melt can be extracted under certain limitations using this technique. As shown before for unentangled chains [Karim et al., Phys. Rev. E 86, 051501 (2012), 10.1103/PhysRevE.86.051501], the frequency range of applicability is substantially expanded when both particle and medium inertia are properly accounted for by using our inertial version of the generalized Stokes-Einstein relation (IGSER). The system used here introduces an entanglement length dT, in addition to those length scales already relevant: monomer bead size d , probe size R , polymer radius of gyration Rg, simulation box size L , shear wave penetration length Δ , and wave period Λ . Previously, we demonstrated a number of restrictions necessary to obtain the relevant fluid properties: continuum approximation breaks down when d ≳Λ ; medium inertia is important and IGSER is required when R ≳Λ ; and the probe should not experience hydrodynamic interaction with its periodic images, L ≳Δ . These restrictions are also observed here. A simple scaling argument for entangled polymers shows that the simulation box size must scale with polymer molecular weight as Mw3. Continuum analysis requires the existence of an added mass to the probe particle from the entrained medium but was not observed in the earlier work for unentangled chains. We confirm here that this added mass is necessary only when the thickness LS of the shell around the particle that contains the added mass, LS>d . We also demonstrate that the IGSER can be used to predict particle displacement over a given timescale from knowledge of medium viscoelasticity; such ability will be of interest for designing nanoparticle-based drug delivery.

  8. 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

  9. Novel aerobic benzene degrading microorganisms identified in three soils by stable isotope probing.

    PubMed

    Xie, Shuguang; Sun, Weimin; Luo, Chunling; Cupples, Alison M

    2011-02-01

    The remediation of benzene contaminated groundwater often involves biodegradation and although the mechanisms of aerobic benzene biodegradation in laboratory cultures have been well studied, less is known about the microorganisms responsible for benzene degradation in mixed culture samples or at contaminated sites. To address this knowledge gap, DNA based stable isotope probing (SIP) was utilized to identify active benzene degraders in microcosms constructed with soil from three sources (a contaminated site and two agricultural sites). For this, replicate microcosms were amended with either labeled (¹³C) or unlabeled benzene and the extracted DNA samples were ultracentrifuged, fractioned and subject to terminal restriction fragment length polymorphism (TRFLP). The dominant benzene degraders (responsible for ¹³C uptake) were determined by comparing relative abundance of TRFLP phylotypes in heavy fractions of labeled benzene (¹³C) amended samples to the controls (from unlabeled benzene amended samples). Two phylotypes (a Polaromonas sp. and an Acidobacterium) were the major benzene degraders in the microcosms constructed from the contaminated site soil, whereas one phylotype incorporated the majority of the benzene-derived ¹³C in each of the agricultural soils ("candidate" phylum TM7 and an unclassified Sphingomonadaceae).

  10. 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

  11. 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.

  12. 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.

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

    DOE PAGES

    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 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

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

    PubMed

    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

  15. 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

  16. 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.

  17. Alkaline degradation studies of anion exchange polymers to enable new membrane designs

    NASA Astrophysics Data System (ADS)

    Nunez, Sean Andrew

    Current performance targets for anion-exchange membrane (AEM) fuel cells call for greater than 95% alkaline stability for 5000 hours at temperatures up to 120 °C. Using this target temperature of 120 °C, an incisive 1H NMR-based alkaline degradation method to identify the degradation products of n-alkyl spacer tetraalkylammonium cations in various AEM polymers and small molecule analogs. Herein, the degradation mechanisms and rates of benzyltrimethylammonium-, n-alkyl interstitial spacer- and n-alkyl terminal pendant-cations are studied on several architectures. These findings demonstrate that benzyltrimethylammonium- and n-alkyl terminal pendant cations are more labile than an n-alkyl interstitial spacer cation and conclude that Hofmann elimination is not the predominant mechanism of alkaline degradation. Additionally, the alkaline stability of an n-alkyl interstitial spacer cation is enhanced when combined with an n-alkyl terminal pendant. Interestingly, at 120 °C, an inverse trend was found in the overall alkaline stability of AEM poly(styrene) and AEM poly(phenylene oxide) samples than was previously shown at 80 °C. Successive small molecule studies suggest that at 120 °C, an anion-induced 1,4-elimination degradation mechanism may be activated on styrenic AEM polymers bearing an acidic alpha-hydrogen. In addition, an ATR-FTIR based method was developed to assess the alkaline stability of solid membranes and any added resistance to degradation that may be due to differential solubilities and phase separation. To increase the stability of anion exchange membranes, Oshima magnesate--halogen exchange was demonstrated as a method for the synthesis of new anion exchange membranes that typically fail in the presence of organolithium or Grignard reagents alone. This new chemistry, applied to non-resinous polymers for the first time, proved effective for the n-akyl interstitial spacer functionalization of poly(phenylene oxide) and poly(styrene- co

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

    NASA Astrophysics Data System (ADS)

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

    The structure of the supramolecular coordination polymer (SCP), [(Ph3Sn)4Fe(CN)6], 1, consists of octahedral [Fe(CN)6]4- building blocks which are connected by the TBPY-5 configured Ph3Sn(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, Kobs. = 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 3 h. 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.

  19. 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.

  20. Thermal desorption characterisation of molecularly imprinted polymers. Part I: A novel study using direct-probe GC-MS analysis.

    PubMed

    Cummins, Wayne; Duggan, Patrick; McLoughlin, Peter

    2008-06-01

    A novel thermal desorption technique using a direct-probe device (Chromatoprobe) attached to a gas chromatograph-mass spectrometer is presented for the thermal pretreatment, characterisation and analysis of molecularly imprinted polymers. The technique is demonstrated as effective for the removal of volatile materials, including template and unreacted monomers, from methacrylic acid-ethylene glycol dimethacrylate copolymers imprinted with 2-aminopyridine. Mass spectrometry is a powerful technique for polymer bleed characterisation. Thermal desorption studies on reloaded template and related compounds are reported as a means of assessing polymer morphology, specific binding by imprinted polymers compared with reference non-imprinted polymers and selective binding by an imprinted polymer for its template. Calibration studies on the thermal desorption technique using an internal standard are presented with R(2) > 0.999. The technique provides a novel method for assessment of polymer thermal stability, composition and morphology.

  1. DNA-based stable isotope probing coupled with cultivation methods implicates Methylophaga in hydrocarbon degradation

    PubMed Central

    Mishamandani, Sara; Gutierrez, Tony; Aitken, Michael D.

    2014-01-01

    Marine hydrocarbon-degrading bacteria perform a fundamental role in the oxidation and ultimate removal of crude oil and its petrochemical derivatives in coastal and open ocean environments. Those with an almost exclusive ability to utilize hydrocarbons as a sole carbon and energy source have been found confined to just a few genera. Here we used stable isotope probing (SIP), a valuable tool to link the phylogeny and function of targeted microbial groups, to investigate hydrocarbon-degrading bacteria in coastal North Carolina sea water (Beaufort Inlet, USA) with uniformly labeled [13C]n-hexadecane. The dominant sequences in clone libraries constructed from 13C-enriched bacterial DNA (from n-hexadecane enrichments) were identified to belong to the genus Alcanivorax, with ≤98% sequence identity to the closest type strain—thus representing a putative novel phylogenetic taxon within this genus. Unexpectedly, we also identified 13C-enriched sequences in heavy DNA fractions that were affiliated to the genus Methylophaga. This is a contentious group since, though some of its members have been proposed to degrade hydrocarbons, substantive evidence has not previously confirmed this. We used quantitative PCR primers targeting the 16S rRNA gene of the SIP-identified Alcanivorax and Methylophaga to determine their abundance in incubations amended with unlabeled n-hexadecane. Both showed substantial increases in gene copy number during the experiments. Subsequently, we isolated a strain representing the SIP-identified Methylophaga sequences (99.9% 16S rRNA gene sequence identity) and used it to show, for the first time, direct evidence of hydrocarbon degradation by a cultured Methylophaga sp. This study demonstrates the value of coupling SIP with cultivation methods to identify and expand on the known diversity of hydrocarbon-degrading bacteria in the marine environment. PMID:24578702

  2. Vacuum ellipsometry as a method for probing glass transition in thin polymer films

    NASA Astrophysics Data System (ADS)

    Efremov, Mikhail Yu.; Soofi, Shauheen S.; Kiyanova, Anna V.; Munoz, Claudio J.; Burgardt, Peter; Cerrina, Franco; Nealey, Paul F.

    2008-04-01

    A vacuum ellipsometer has been designed for probing the glass transition in thin supported polymer films. The device is based on the optics of a commercial spectroscopic phase-modulated ellipsometer. A custom-made vacuum chamber evacuated by oil-free pumps, variable temperature optical table, and computer-based data acquisition system was described. The performance of the tool has been demonstrated using 20-200nm thick poly(methyl methacrylate) and polystyrene films coated on silicon substrates at 10-6-10-8torr residual gas pressure. Both polymers show pronounced glass transitions. The difficulties in assigning in the glass transition temperature are discussed with respect to the experimental challenges of the measurements in thin polymer films. It is found that the experimental curves can be significantly affected by a residual gas. This effect manifests itself at lower temperatures as a decreased or even negative apparent thermal coefficient of expansion, and is related to the uptake and desorption of water by the samples during temperature scans. It is also found that an ionization gauge—the standard accessory of any high vacuum system—can cause a number of spurious phenomena including drift in the experimental data, roughening of the polymer surface, and film dewetting.

  3. Interactions between protein coated particles and polymer surfaces studied with the rotating particles probe.

    PubMed

    Kemper, M; Spridon, D; van IJzendoorn, L J; Prins, M W J

    2012-05-29

    Nonspecific interactions between proteins and polymer surfaces have to be minimized in order to control the performance of biosensors based on immunoassays with particle labels. In this paper we investigate these nonspecific interactions by analyzing the response of protein coated magnetic particles to a rotating magnetic field while the particles are in nanometer vicinity to a polymer surface. We use the fraction of nonrotating (bound) particles as a probe for the interaction between the particles and the surface. As a model system, we study the interaction of myoglobin coated particles with oxidized polystyrene surfaces. We measure the interaction as a function of the ionic strength of the solution, varying the oxidation time of the polystyrene and the pH of the solution. To describe the data we propose a model in which particles bind to the polymer by crossing an energy barrier. The height of this barrier depends on the ionic strength of the solution and two interaction parameters. The fraction of nonrotating particles as a function of ionic strength shows a characteristic shape that can be explained with a normal distribution of energy barrier heights. This method to determine interaction parameters paves the way for further studies to quantify the roles of protein coated particles and polymers in their mutual nonspecific interactions in different matrixes.

  4. 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. PMID:25226910

  5. 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

  6. 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.

  7. 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.

  8. 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

  9. 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.

  10. 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.

  11. 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. PMID:10644964

  12. Biosensor arrays based on the degradation of thin polymer films interrogated by scanning photoinduced impedance microscopy.

    PubMed

    Zhou, Yinglin; Jiang, Shihong; Krause, Steffi; Chazalviel, Jean-Noël

    2007-12-01

    Disposable sensors based on the degradation of thin films as a result of an enzymatic reaction have been developed into efficient enzyme detectors. Film degradation has traditionally been monitored using surface plasmon resonance (SPR), quartz crystal microbalance (QCM), or classical ac impedance measurements. The enzyme detection principle has now been integrated with an array technology derived from a recently developed impedance imaging technique, scanning photoinduced impedance microscopy (SPIM). SPIM is based on photocurrent measurements at field-effect structures. The material under investigation is commonly deposited onto a semiconductor-insulator substrate. In this work, field-effect capacitors were replaced by hydrogenated amorphous silicon (a-Si:H) n-i-p photodiode structures, which have recently been shown to be suitable for SPIM measurements with good lateral resolution. To demonstrate the feasibility of SPIM for the characterization of biosensor arrays, polymer dots of the inert polymer cellulose acetate and an alpha-chymotrypsin-sensitive poly(ester amide) were deposited onto a-Si:H n-i-p/SiO2 structures and their enzymatic degradation was monitored using a laser scanning setup.

  13. 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

  14. Degradable and bioresorbable polymers in surgery and in pharmacology: beliefs and facts.

    PubMed

    Vert, Michel

    2009-02-01

    The number of articles dealing with degradable polymers and macromolecules is increasing rapidly and the number of proposed compounds as well. However, not all have a high potential for effective applications. This contribution examines first the criteria to be taken into account when commercialisation of polymeric compounds and devices aimed at helping the body for a limited period of time, i.e. the healing time, is the main goal. What is really known is tentatively analysed by considering some of the candidates present in literature confronted to the targeted potential applications. Tentative comments are made on what should be done to qualify a candidate. Last but not least, trends in the search for polymers to be exploited in presently attracting areas such as bioresorbable stents, hydrogels to deliver bioactive macromolecules like proteins and polynucleotides or polyelectrolytes to temporarily complex charged biomacromolecules like proteins or genes are considered.

  15. {sup 17}O NMR investigation of oxidative degradation in polymers under gamma-irradiation

    SciTech Connect

    ALAM,TODD M.; CELINA,MATHIAS C.; ASSINK,ROGER A.; CLOUGH,ROGER LEE; GILLEN,KENNETH T.

    2000-03-08

    The {gamma}-irradiated-oxidation of pentacontane (C{sub 50}H{sub 102}) and the polymer polyisoprene was investigated as a function of oxidation level using {sup 17}O nuclear magnetic resonance (NMR) spectroscopy. It is demonstrated that by using {sup 17}O labeled O{sub 2} gas during the {gamma}-irradiation process, details about the oxidative degradation mechanisms can be directly obtained from the analysis of the {sup 17}O NMR spectra. Production of carboxylic acids is the primary oxygen-containing functionality during the oxidation of pentacontane, while ethers and alcohols are the dominant oxidation product observed for polyisoprene. The formation of ester species during the oxidation process is very minor for both materials, with water also being produced in significant amounts during the radiolytic oxidation of polyisoprene. The ability to focus on the oxidative component of the degradation process using {sup 17}O NMR spectroscopy demonstrates the selectivity of this technique over more conventional approaches.

  16. 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

  17. Measuring the degradation level of polymer films subjected to partial discharges

    SciTech Connect

    Bozzo, R.; Gemme, C.; Guastavino, F.; Tiemblo, P.

    1996-12-31

    Polymer films have been subjected to partial discharge (PD) aging. It is shown that statistical quantities derived from partial discharges patterns can be related to test conditions, film characteristics and degradation level. PDs have been measured by means of a digital system. Several resulting PD patterns have been elaborated and about 50 derived and statistical quantities have been obtained for each pattern. The effects of the test conditions on the derived quantities has been studied with relevance to the following items: To recognize the kind of film under test; to correlate the value of quantities with the degradation level of the film (i.e., to focus at the quantities which change with time); to find a link between the quantities values and the test ambient conditions (i.e., relative humidity); to determine the influence of the film thickness; and to evidence the effect of the voltage level.

  18. 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.

  19. Identification of triclosan-degrading bacteria using stable isotope probing, fluorescence in situ hybridization and microautoradiography.

    PubMed

    Lolas, Ihab Bishara; Chen, Xijuan; Bester, Kai; Nielsen, Jeppe Lund

    2012-11-01

    Triclosan is considered a ubiquitous pollutant and can be detected in a wide range of environmental samples. Triclosan removal by wastewater treatment plants has been largely attributed to biodegradation processes; however, very little is known about the micro-organisms involved. In this study, DNA-based stable isotope probing (DNA-SIP) combined with microautoradiography-fluorescence in situ hybridization (MAR-FISH) was applied to identify active triclosan degraders in an enrichment culture inoculated with activated sludge. Clone library sequences of 16S rRNA genes derived from the heavy DNA fractions of enrichment culture incubated with (13)C-labelled triclosan showed a predominant enrichment of a single bacterial clade most closely related to the betaproteobacterial genus Methylobacillus. To verify that members of the genus Methylobacillus were actively utilizing triclosan, a specific probe targeting the Methylobacillus group was designed and applied to the enrichment culture incubated with (14)C-labelled triclosan for MAR-FISH. The MAR-FISH results confirmed a positive uptake of carbon from (14)C-labelled triclosan by the Methylobacillus. The high representation of Methylobacillus in the (13)C-labelled DNA clone library and its observed utilization of (14)C-labelled triclosan by MAR-FISH reveal that these micro-organisms are the primary consumers of triclosan in the enrichment culture. The results from this study show that the combination of SIP and MAR-FISH can shed light on the networks of uncultured micro-organisms involved in degradation of organic micro-pollutants.

  20. 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

  1. Experimental Study of The Degradation of Polymers. Application To The Origin of Extended Sources In Cometary Atmospheres.

    NASA Astrophysics Data System (ADS)

    Fray, N.; Cottin, H.; Gazeau, M. C.; Minard, R. D.; Raulin, F.; Benilan, Y.

    Some molecules or radicals observed in cometary atmospheres present so-called Sex- & cedil;tended sourcesT. It means that their distribution in comae cannot be explained by a direct sublimation from the nucleus, but rather by a production in the coma. The origin of those extended sources is still an unsolved question. Some large organic molecules, like HCN polymers or polyoxymethylene [formaldehyde polymers: (-CH2-O-)n], are sometime evoked as possible parents for the extended sources of CN and H2CO re- spectively. These polymers in solid state on cometary grains could release volatiles through thermal and photolytic degradation. We have developed an experimental pro- gram in order to study the chemical reactions of degradration of solid polymers by UV irradiation and heating. The production of resulting small gaseous molecules is studied through MS, GC and IR analyses and provide identification of the degradation products and the determination of the photodegradation quantum yields or the ther- modegradation kinetics. Those fundamental data are then included into a model of the outer coma in order to interpret observations. We will present our latest results on the degradation of HCN polymers and polyoxymethylene. They show that the degradation of organic polymers is a possible source of molecules and radicals which present an extended source.

  2. 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. PMID:26920783

  3. Fabrication of a polymer-metal combined atomic force microscopy probe for coarse food surface imaging.

    PubMed

    Kang, Hyen-Wook; Muramatsu, Hiroshi; Kwon, Young-Soo

    2013-05-01

    We fabricated a polymer-metal combined atomic force microscopy (AFM) probe by two steps; a polymeric resin was used at first step, and a metal-ion was used at second step which needs more fabricating time than the resin. At first step, we fabricated a cylindrical base on to a commercial cantilever. At second step, we fabricated a conical probe on to the fabricated cylindrical base. To make the conical probe composed with silver, a 0.2 M aqueous solution of silver nitrate (AgNO3) was used. A 50 microm length polymeric-metallic hybrid tip has been fabricated to observe large bio and food samples. Generally, the AFM images of bio/food samples show cliff-like sharp patters in vertical. However, the AFM image by fabricated long tip shows clear structure of each brown rice flours. As most of commercial tips have three-angular pyramidal, the scanned results should be influenced by the lateral face of the three-angular pyramid, which results in cliff-like images. Because the sample size is large, the side area of the sample was adversely affected by the pyramidal structure during imaging. This problem may be resolved by designing conical structure tips. As the conical structure has no edge, the AFM image becomes clear. The fabricated tip has conical structure, and a clear AFM image was achieved. PMID:23858900

  4. 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

  5. An investigation on focused electron/ion beam induced degradation mechanisms of conjugated polymers.

    PubMed

    Sezen, Meltem; Plank, Harald; Fisslthaler, Evelin; Chernev, Boril; Zankel, Armin; Tchernychova, Elena; Blümel, Alexander; List, Emil J W; Grogger, Werner; Pölt, Peter

    2011-12-01

    Irradiation damage, caused by the use of beams in the electron microscopes, leads to undesired physical/chemical material property changes or uncontrollable modification of structures that are being processed. Particularly, soft matter such as polymers or biological materials is highly susceptible and very much prone to react on irradiation by electron and ion beams. The effect is even higher when materials are subjected to energetic species such as ions that possess high momentum and relatively low mean path due to their mass. Especially when Ga(+) ions (used as the ion source in Focused Ion Beam (FIB) instruments) are considered, the end-effect might even be the total loss of the material's properties. This paper will discuss the possible types of degradation mechanisms and defect formations that can take place during ion and electron beam irradiation of the conjugated polymers: e.g. polyfluorene (PF) and poly-3-hexylthiophene (P3HT) thin films. For the investigation of the irradiation induced degradation mechanisms in this study, complementary analytical techniques such as Raman Spectroscopy (RS), Infrared Spectroscopy (IR), Electron Energy Loss Spectroscopy (EELS), Atomic Force Microscopy (AFM), and Fluorescence Microscopy including Photoluminescence (PL) and Electroluminescence (EL) Microscopy were applied.

  6. A Comparison of Degradable Synthetic Polymer Fibers for Anterior Cruciate Ligament Reconstruction

    PubMed Central

    Tovar, Nick; Bourke, Sharon; Jaffe, Michael; Murthy, N. Sanjeeva; Kohn, Joachim; Gatt, Charles; Dunn, Michael G.

    2009-01-01

    We compared mechanical properties, degradation rates, and cellular compatibilities of two synthetic polymer fibers potentially useful as ACL reconstruction scaffolds: poly(desaminotyrosyl-tyrosine dodecyl dodecanedioate)(12,10), p(DTD DD) and poly(L-lactic acid), PLLA. The yield stress of ethylene oxide (ETO) sterilized wet fibers was 150 ± 22 MPa and 87 ± 12 MPa for p(DTD DD) and PLLA, respectively, with moduli of 1.7 ± 0.1 MPa and 4.4 ± 0.43 MPa. Strength and molecular weight retention were determined after incubation under physiological conditions at varying times. After 64 weeks strength decreased to 20 and 37% of the initial sterile fiber values and MW decreased to 41% and 36% of the initial values for p(DTD DD) and PLLA, respectively. ETO sterilization had no significant effect on mechanical properties. Differences in mechanical behavior may be due to the semicrystalline nature of PLLA and the small degree of crystallinity induced by mesogenic ordering in p(DTD DD) suggested by DSC analysis. Fibroblast growth was similar on 50-fiber scaffolds of both polymers through 16 days in vitro. These data suggest that p(DTD DD) fibers, with higher strength, lower stiffness, favorable degradation rate and cellular compatibility, may be a superior alternative to PLLA fibers for development of ACL reconstruction scaffolds. PMID:19623532

  7. An investigation on focused electron/ion beam induced degradation mechanisms of conjugated polymers.

    PubMed

    Sezen, Meltem; Plank, Harald; Fisslthaler, Evelin; Chernev, Boril; Zankel, Armin; Tchernychova, Elena; Blümel, Alexander; List, Emil J W; Grogger, Werner; Pölt, Peter

    2011-12-01

    Irradiation damage, caused by the use of beams in the electron microscopes, leads to undesired physical/chemical material property changes or uncontrollable modification of structures that are being processed. Particularly, soft matter such as polymers or biological materials is highly susceptible and very much prone to react on irradiation by electron and ion beams. The effect is even higher when materials are subjected to energetic species such as ions that possess high momentum and relatively low mean path due to their mass. Especially when Ga(+) ions (used as the ion source in Focused Ion Beam (FIB) instruments) are considered, the end-effect might even be the total loss of the material's properties. This paper will discuss the possible types of degradation mechanisms and defect formations that can take place during ion and electron beam irradiation of the conjugated polymers: e.g. polyfluorene (PF) and poly-3-hexylthiophene (P3HT) thin films. For the investigation of the irradiation induced degradation mechanisms in this study, complementary analytical techniques such as Raman Spectroscopy (RS), Infrared Spectroscopy (IR), Electron Energy Loss Spectroscopy (EELS), Atomic Force Microscopy (AFM), and Fluorescence Microscopy including Photoluminescence (PL) and Electroluminescence (EL) Microscopy were applied. PMID:21993473

  8. Effect of various nanofillers on thermal stability and degradation kinetics of polymer nanocomposites.

    PubMed

    Choudhury, Anusuya; Bhowmick, Anil K; Ong, Christopher; Soddemann, Matthias

    2010-08-01

    Structure of nanofillers and their subsequent interaction with a polymer is very important in determining thermal stability of polymer nanocomposite. In this paper, we tried to correlate structure of various 0, 1 and 2 dimensional nanofillers with the thermal stability of hydrogenated nitrile butadiene rubber (HNBR) nanocomposites. Organically modified and unmodified layered silicates such as montmorillonite (Cloisite Na+, Cloisite 30B and Cloisite 15A), rod-like fibrous filler (sepiolite) and spherical nanoparticles (nanosilica) were chosen for this purpose. A significant improvement in thermal stability (obtained by thermogravimeric analysis and differential scanning calorimetry) was observed for silica-filled nanocomposites. However, the activation energy of the nanocomposites calculated by different kinetic methods (both non-isothermal and isothermal methods) was found to be significantly high for sepiolite, 30B and silica-filled nanocomposites. The results were explained with the help of structure of the nanofillers, their interaction with the elastomer and the subsequent dispersion, as measured by X-ray diffraction, transmission electron microscopy and atomic force microscopy. From these analyses it was concluded that organically modified montmorillonite, sepiolite and nanosilica increase the thermal stability of the nanocomposite to a great extent due to the interaction of the reactive groups on the surface of these fillers with the polymer and high thermal stability of these inorganic fillers. Finally, degradation mechanism of HNBR in presence of the nanofillers at severe operating temperatures was investigated with the help of FTIR spectroscopy. PMID:21125850

  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. Characterization of para-Nitrophenol-Degrading Bacterial Communities in River Water by Using Functional Markers and Stable Isotope Probing

    PubMed Central

    Eyice, Özge; Schäfer, Hendrik; Price, Oliver R.; Finnegan, Christopher J.; van Egmond, Roger A.; Shaw, Liz J.; Barrett, Glyn; Bending, Gary D.

    2015-01-01

    Microbial degradation is a major determinant of the fate of pollutants in the environment. para-Nitrophenol (PNP) is an EPA-listed priority pollutant with a wide environmental distribution, but little is known about the microorganisms that degrade it in the environment. We studied the diversity of active PNP-degrading bacterial populations in river water using a novel functional marker approach coupled with [13C6]PNP stable isotope probing (SIP). Culturing together with culture-independent terminal restriction fragment length polymorphism analysis of 16S rRNA gene amplicons identified Pseudomonas syringae to be the major driver of PNP degradation in river water microcosms. This was confirmed by SIP-pyrosequencing of amplified 16S rRNA. Similarly, functional gene analysis showed that degradation followed the Gram-negative bacterial pathway and involved pnpA from Pseudomonas spp. However, analysis of maleylacetate reductase (encoded by mar), an enzyme common to late stages of both Gram-negative and Gram-positive bacterial PNP degradation pathways, identified a diverse assemblage of bacteria associated with PNP degradation, suggesting that mar has limited use as a specific marker of PNP biodegradation. Both the pnpA and mar genes were detected in a PNP-degrading isolate, P. syringae AKHD2, which was isolated from river water. Our results suggest that PNP-degrading cultures of Pseudomonas spp. are representative of environmental PNP-degrading populations. PMID:26209677

  11. Characterization of para-Nitrophenol-Degrading Bacterial Communities in River Water by Using Functional Markers and Stable Isotope Probing.

    PubMed

    Kowalczyk, Agnieszka; Eyice, Özge; Schäfer, Hendrik; Price, Oliver R; Finnegan, Christopher J; van Egmond, Roger A; Shaw, Liz J; Barrett, Glyn; Bending, Gary D

    2015-10-01

    Microbial degradation is a major determinant of the fate of pollutants in the environment. para-Nitrophenol (PNP) is an EPA-listed priority pollutant with a wide environmental distribution, but little is known about the microorganisms that degrade it in the environment. We studied the diversity of active PNP-degrading bacterial populations in river water using a novel functional marker approach coupled with [(13)C6]PNP stable isotope probing (SIP). Culturing together with culture-independent terminal restriction fragment length polymorphism analysis of 16S rRNA gene amplicons identified Pseudomonas syringae to be the major driver of PNP degradation in river water microcosms. This was confirmed by SIP-pyrosequencing of amplified 16S rRNA. Similarly, functional gene analysis showed that degradation followed the Gram-negative bacterial pathway and involved pnpA from Pseudomonas spp. However, analysis of maleylacetate reductase (encoded by mar), an enzyme common to late stages of both Gram-negative and Gram-positive bacterial PNP degradation pathways, identified a diverse assemblage of bacteria associated with PNP degradation, suggesting that mar has limited use as a specific marker of PNP biodegradation. Both the pnpA and mar genes were detected in a PNP-degrading isolate, P. syringae AKHD2, which was isolated from river water. Our results suggest that PNP-degrading cultures of Pseudomonas spp. are representative of environmental PNP-degrading populations.

  12. 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).

  13. 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.

  14. Positronium formation as a probe of polymer surfaces and thin films

    SciTech Connect

    Xie, L.; DeMaggio, G.B.; Frieze, W.E.; DeVries, J.; Gidley, D.W.; Hristov, H.A.; Yee, A.F.

    1995-06-12

    The lifetime, {tau}{sub 3}, and formation fraction, {ital I}{sub 3}, of triplet positronium decaying in the void volume near a polymer surface are measured versus the positron implantation energy, {ital E}. The strong {ital E} dependence of {ital I}{sub 3} supports a spur-electron capture model of Ps formation with deduced spur sizes ranging from 200 to 660 A. Thin film measurements indicate that the mean probe depth can be much smaller, given mainly by the average positron implantation distance, {ital {bar z}}({ital E}). Surface-induced changes in the void size and glass transition temperature of polystyrene are searched for at{ital {bar z}}{approx}40 {ital @};OA.

  15. Electrical four-point probing of spherical metallic thin films coated onto micron sized polymer particles

    NASA Astrophysics Data System (ADS)

    Pettersen, Sigurd R.; Stokkeland, August Emil; Kristiansen, Helge; Njagi, John; Redford, Keith; Goia, Dan V.; Zhang, Zhiliang; He, Jianying

    2016-07-01

    Micron-sized metal-coated polymer spheres are frequently used as filler particles in conductive composites for electronic interconnects. However, the intrinsic electrical resistivity of the spherical thin films has not been attainable due to deficiency in methods that eliminate the effect of contact resistance. In this work, a four-point probing method using vacuum compatible piezo-actuated micro robots was developed to directly investigate the electric properties of individual silver-coated spheres under real-time observation in a scanning electron microscope. Poly(methyl methacrylate) spheres with a diameter of 30 μm and four different film thicknesses (270 nm, 150 nm, 100 nm, and 60 nm) were investigated. By multiplying the experimental results with geometrical correction factors obtained using finite element models, the resistivities of the thin films were estimated for the four thicknesses. These were higher than the resistivity of bulk silver.

  16. Inhomogeneous radiation degradation in polymers studied with a density gradient column

    NASA Astrophysics Data System (ADS)

    Gillen, K. T.; Clough, R. L.

    Radiation dose-rate effects are known to exist in many polymers and are typically caused by oxidation reactions. Since the buildup of oxidation products often leads to an increase in polymer density, a density gradient column was used in a novel way to study the mechanisms responsible for dose-rate effects in a commercial ethylene propylene rubber (EPR) electrical cable insulation material. After various aging conditions, density profiles of samples were obtained by measuring the density of small pieces cut successively from the outside to the inside of the approximately 1-mm thick insulation. By monitoring density profiles as a function of dose rate and total radiation dose, two inhomogeneous mechanisms were found to be responsible for the observed dose-rate effects in this EPR material. At high dose rates, oxygen-diffusion-limited degradation was identified, as evidenced by a density profile which showed increased density near the air-exposed surfaces of the insulation but little change in density in the interior of the sample. As the dose rate was lowered, the oxidation region spread inward until it encompassed the entire sample at dose rates below about 100 krad/hr. The second mechanism, responsible for continuing the dose-rate effects at lower dose rates, appears to involve copper-catalyzed oxidation. This mechanism is often found to be significant in thermal aging studies; evidence that it may also be significant under room-temperature, radiation-aging conditions came from the density profile results, which revealed large increases in density as the inside of the insulation (near the tinned-copper conductor) was approached. For the same total radiation dose, this increase became larger as the dose rate was lowered. Preliminary chemical analysis profiling techniques indicate significantly enhanced copper and tin concentrations as the inside of the insulation is approached, even for insulation stripped from the metallic conductor before aging. This implies that

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

    PubMed

    Wang, Xiaoqing; Sharp, Christine E; Jones, Gareth M; Grasby, Stephen E; Brady, Allyson L; Dunfield, Peter F

    2015-07-01

    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. (13)C-labeled EPS and (13)C-labeled cellulose were purified from bacterial cultures grown on [(13)C]glucose. Two soils were incubated with these substrates, and bacteria actively assimilating them were identified via pyrosequencing of 16S rRNA genes recovered from (13)C-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

  18. 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

  19. A femtosecond pump-probe spectrometer for dynamics in transmissive polymer films

    NASA Astrophysics Data System (ADS)

    Röttger, K.; Wang, S.; Renth, F.; Bahrenburg, J.; Temps, F.

    2015-02-01

    An experimental setup and data collection strategy for femtosecond transient absorption spectroscopy on thin (1 ) solid polymer film samples is described. The experiment allows for parallel detection of the changes in optical density via broadband supercontinuum probing in the VIS/UV range and single-color detection at an independently selected wavelength from the deep UV to the IR with a sensitivity of per laser shot (r.m.s. standard deviation) and a time resolution below 40 fs. A fast and reproducible bi-directional translation of a two-dimensional film sample of in size is used to measure fresh sample spots at each detection interval. Signal readout at a 1 kHz rate enables single-shot analysis and automated signal discrimination, as well as detailed statistics on sample homogeneity, signal evolution with increasing number of pump pulses, and reproducibility. The technique was employed to study the photoisomerization of Disperse Red 1 in films of polymethylmethacrylate after photoexcitation at nm. The results revealed excited-state dynamics characterized by time constants of and , almost identical as in solution, but evidently enhanced vibrational excitation and slower vibrational cooling (time constant ) after return to the electronic ground state due to the constraining polymer environment.

  20. Degradation and reliability modelling of polymer electrolyte membrane (PEM) fuel cells

    NASA Astrophysics Data System (ADS)

    Fowler, Michael William

    To date there has been very little reliability or end of life analysis conducted for polymer electrolyte membrane (PEM) fuel cell systems. Voltage degradation as a fuel cell ages is a widely observed phenomenon, but little systematic information has been reported, nor has this phenomenon been included in electrochemical models. This work documents and classifies the failure modes that can be experienced in PEM fuel cells. A test station was adapted for the long term operation of a single, 50 cm2, internally hydrated, PEM fuel cell. An endurance test was conducted to age the cell under normal operating conditions for 1350 hours, at which time membrane failure was experienced. Changes in the polarization curve predicted by the Generalized Steady State Electrochemical Degradation Model (GSSEDM) are demonstrated from the data for the performance of typical PEM fuel cell hardware. This work develops and applies the generalized steady state electrochemical model for a PEM cell, and introduces two new terms to account for membrane electrode assembly (MEA) ageing, specifically the ageing of the MEA materials. One term is based on the concept that the water carrying capacity of the membrane deteriorates with time-in-service. The second term involves intrinsic rate constants associated with the reactions on the anode and cathode side, and the changes in catalytic activity due to catalyst degradation. The resulting model is largely mechanistic with most terms being derived from theory or including coefficients that have a theoretical basis, but also includes empirical parameters to deal with the changing performance. The value of such a generic model to predict or correlate PEM fuel cell stack voltages over the life of the fuel cell is demonstrated in this work. From the experimental data a membrane conductivity degradation rate, lambdaDR, was determined, and the value for lambdaDR was found to be -0.0007 hr -1. A term was introduced for degradation rate of the fuel cell due

  1. 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

  2. Contribution to the study of particle resuspension kinetics during thermal degradation of polymers.

    PubMed

    Ouf, F-X; Delcour, S; Azema, N; Coppalle, A; Ferry, L; Gensdarmes, F; Lopez-Cuesta, J-M; Niang, A; Pontreau, S; Yon, J

    2013-04-15

    Experimental results are reported on the resuspension of particles deposited on polymer samples representative of glove boxes used in the nuclear industry, under thermal degradation. A parametric study was carried out on the effects of heat flux, air flow rate, fuel type and particle size distribution. Small-scale experiments were conducted on 10 cm × 10 cm PolyMethyl MethAcrylate (PMMA) and PolyCarbonate (PC) samples covered with aluminium oxide particles with physical geometric diameters of 0.7 and 3.6 μm. It was observed for both polymer (fuel) samples that heat flux has no effect on the airborne release fraction (ARF), whereas particle size is a significant parameter. In the case of the PMMA sample, ARF values for 0.7 and 3.6 μm diameter particles range from 12.2% (± 6.2%) to 2.1% (± 0.6%), respectively, whereas the respective values for the PC sample range from 3.2% (± 0.8%) to 6.9% (± 3.9%). As the particle diameter increases, a significant decrease in particle release is observed for the PMMA sample, whereas an increase is observed for the PC sample. Furthermore, a peak airborne release rate is observed during the first instants of PMMA exposure to thermal stress. An empirical relationship has been proposed between the duration of this peak release and the external heat flux. PMID:23474404

  3. Contribution to the study of particle resuspension kinetics during thermal degradation of polymers.

    PubMed

    Ouf, F-X; Delcour, S; Azema, N; Coppalle, A; Ferry, L; Gensdarmes, F; Lopez-Cuesta, J-M; Niang, A; Pontreau, S; Yon, J

    2013-04-15

    Experimental results are reported on the resuspension of particles deposited on polymer samples representative of glove boxes used in the nuclear industry, under thermal degradation. A parametric study was carried out on the effects of heat flux, air flow rate, fuel type and particle size distribution. Small-scale experiments were conducted on 10 cm × 10 cm PolyMethyl MethAcrylate (PMMA) and PolyCarbonate (PC) samples covered with aluminium oxide particles with physical geometric diameters of 0.7 and 3.6 μm. It was observed for both polymer (fuel) samples that heat flux has no effect on the airborne release fraction (ARF), whereas particle size is a significant parameter. In the case of the PMMA sample, ARF values for 0.7 and 3.6 μm diameter particles range from 12.2% (± 6.2%) to 2.1% (± 0.6%), respectively, whereas the respective values for the PC sample range from 3.2% (± 0.8%) to 6.9% (± 3.9%). As the particle diameter increases, a significant decrease in particle release is observed for the PMMA sample, whereas an increase is observed for the PC sample. Furthermore, a peak airborne release rate is observed during the first instants of PMMA exposure to thermal stress. An empirical relationship has been proposed between the duration of this peak release and the external heat flux.

  4. Evaluation of coating degradation for polymer coated steel exposed to seawater

    SciTech Connect

    Mansfeld, F.; Xiao, H.; Han, L.T.; Lee, C.C.; Chen, C.; Jones-Meehan, J.; Little, B.J.

    1996-10-01

    Three sets of polymer coated steel were exposed to Pacific ocean water (NS) and artificial (AS) sea water. Each set had a different primer -- metallic zinc, IVD-Al or phosphate. Within each set one group of samples had an epoxy coating, the other set had an additional layer of polyurethane as a topcoat. Degradation of the protective properties of the polymer coating was followed by recording impedance spectra and electrochemical potential and current noise data as well as by visual observation. Statistical analyses concerning the effects of the nature of the primer, presence of a topcoat and exposure medium (biotic vs. abiotic) were performed based on the breakpoint frequency f{sub b} obtained from impedance data and the noise resistance R{sub n} and the spectral noise resistance R{sup o}{sub sn} obtained from noise data. Samples exposed to three different colonies of microorganisms containing sulfate reducing-bacteria (SRB) and a control solution were evaluated using electrochemical impedance spectroscopy (EIS). All samples were examined by environmental scanning electron microscopy (ESEM) to determine biofilm distribution and spatial relationships between coating damage and microorganisms.

  5. Synthesis and Study of Polymers Designed for Controlled Degradation with Light as a Trigger

    NASA Astrophysics Data System (ADS)

    Olejniczak, Jason Edward

    Light is an ideal stimulus to externally control the properties of materials for many applications. Light is able to initiate chemical reactions largely independent of a material's local environment making it particularly useful as a bio-orthogonal and on-demand trigger in living systems. The benefits of light as a trigger are diminished by various drawbacks of its use. Light of relatively short wavelengths, in the UV range, is most commonly used to initiate chemistries. This is because UV light has high energy, enough to affect bonds in molecules. But this high energy causes problems in off target effects. Many biological molecules are able to absorb and be modified detrimentally by UV light, limiting the use of UV light in biological systems. The problems of UV light for release in biological systems can be potentially overcome in various ways and this dissertation will describe two main strategies. In the first chapter the use of long wavelength responsive polymers will be described. These materials are intended for the encapsulation of a payload in a polymeric nanoparticle which can degrade and release in response to two-photon absorption of near-infrared light. This long wavelength light is absorbed by far fewer biological molecules and so can penetrate deeper through tissue than UV light while also causing less damage. Another method to mitigate the damaging effects of UV light is by using a material that requires less of a stimulus to release. These materials use UV light to trigger release but are designed to need minimal amounts of light. The polymers described with these properties, a poly(?-hydroxyl acid) in chapter 2 and a polyketal in chapter 3, are intriguing novel polymer backbones on their own and could be applied with appropriate triggering groups to respond to different stimuli.

  6. Ultrasonic degradation of polymers: effect of operating parameters and intensification using additives for carboxymethyl cellulose (CMC) and polyvinyl alcohol (PVA).

    PubMed

    Mohod, Ashish V; Gogate, Parag R

    2011-05-01

    Use of ultrasound can yield polymer degradation as reflected by a significant reduction in the intrinsic viscosity or the molecular weight. The ultrasonic degradation of two water soluble polymers viz. carboxymethyl cellulose (CMC) and polyvinyl alcohol (PVA) has been studied in the present work. The effect of different operating parameters such as time of irradiation, immersion depth of horn and solution concentration has been investigated initially using laboratory scale operation followed by intensification studies using different additives such as air, sodium chloride and surfactant. Effect of scale of operation has been investigated with experiments in the available different capacity reactors with an objective of recommending a suitable type of configuration for large scale operation. The experimental results show that the viscosity of polymer solution decreased with an increase in the ultrasonic irradiation time and approached a limiting value. Use of additives such as air, sodium chloride and surfactant helps in increasing the extent of viscosity reduction. At higher frequency operation the viscosity reduction has been found to be negligible possibly attributed to less contribution of the physical effects. The viscosity reduction in the case of ultrasonic horn has been observed to be more as compared to other large capacity reactors. Kinetic analysis of the polymer degradation process has also been performed. The present work has enabled us to understand the role of the different operating parameters in deciding the extent of viscosity reduction in polymer systems and also the controlling effects of low frequency high power ultrasound with experiments on different scales of operation.

  7. 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...

  8. 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.

  9. 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.; 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, 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

  10. Development of a physics-based degradation model for lithium ion polymer batteries considering side reactions

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

    Experimental investigations conducted on a large format lithium ion polymer battery (LiPB) have revealed that side reactions taking place at anode are the major factor for degradation of the battery performance and lead to capacity and power fade. Side reactions consume ions and solvents from the electrolyte and produce deposits that increase the thickness of the solid electrolyte interphase (SEI) layer and form a new layer between composite anode and separator. These phenomena are described using physical principles based on the Tafel and Nernst equations that are integrated into the developed electrochemical-thermal model. The key parameters for the side reactions used in the model are experimentally determined from self-discharging behavior of the battery. The integrated model is then validated against experimental data obtained from different operating conditions. Analysis has revealed that the capacity fade is predominantly caused by loss of ions and active materials. The results also show that the rate of side reactions and degradations are more severe at charging process under high SOC and high C-rate due to low overpotential of the side reactions.

  11. 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.

  12. Specific identification of fibrin polymers, fibrinogen degradation products, and crosslinked fibrin degradation products in plasma and serum with a new sensitive technique.

    PubMed

    Connaghan, D G; Francis, C W; Lane, D A; Marder, V J

    1985-03-01

    A new method is described for identifying low concentrations of circulating derivatives of fibrinogen and fibrin, even when present in heterogeneous mixtures. This technique is applicable to plasma and serum and uses electrophoresis in 2% agarose in the presence of sodium dodecyl sulfate (SDS) followed by immunological identification of separated derivatives, using radiolabeled antifibrinogen antiserum and autoradiography. Unique electrophoretic patterns distinguish plasmic derivatives of crosslinked fibrin from those of fibrinogen and also identify crosslinked fibrin polymers produced by the combined action of thrombin and factor XIII on fibrinogen. The assay is sensitive to a concentration of 0.1 micrograms/mL of fibrinogen in serum or plasma. Fibrin polymers, plasmic degradation products of fibrinogen, and plasmic degradation products of crosslinked fibrin were detected in the plasma or serum of a patient with disseminated intravascular coagulation. Plasmic derivatives of both fibrinogen and crosslinked fibrin appeared in serum in the course of fibrinolytic therapy for pulmonary embolism, whereas during acute myocardial infarction a marked increase in the proportion of fibrin polymers in plasma was found in comparison with normal controls. Thus, the procedure can distinguish between the simultaneous processes of fibrin polymer formation, fibrinogenolysis, and fibrinolysis, and is sufficiently sensitive to detect relevant quantities of derivatives in pathologic conditions.

  13. Redox polymer and probe DNA tethered to gold electrodes for enzyme-amplified amperometric detection of DNA hybridization.

    PubMed

    Kavanagh, Paul; Leech, Dónal

    2006-04-15

    The detection of nucleic acids based upon recognition surfaces formed by co-immobilization of a redox polymer mediator and DNA probe sequences on gold electrodes is described. The recognition surface consists of a redox polymer, [Os(2,2'-bipyridine)2(polyvinylimidazole)(10)Cl](+/2+), and a model single DNA strand cross-linked and tethered to a gold electrode via an anchoring self-assembled monolayer (SAM) of cysteamine. Hybridization between the immobilized probe DNA of the recognition surface and a biotin-conjugated target DNA sequence (designed from the ssrA gene of Listeria monocytogenes), followed by addition of an enzyme (glucose oxidase)-avidin conjugate, results in electrical contact between the enzyme and the mediating redox polymer. In the presence of glucose, the current generated due to the catalytic oxidation of glucose to gluconolactone is measured, and a response is obtained that is binding-dependent. The tethering of the probe DNA and redox polymer to the SAM improves the stability of the surface to assay conditions of rigorous washing and high salt concentration (1 M). These conditions eliminate nonspecific interaction of both the target DNA and the enzyme-avidin conjugate with the recognition surfaces. The sensor response increases linearly with increasing concentration of target DNA in the range of 1 x 10(-9) to 2 x 10(-6) M. The detection limit is approximately 1.4 fmol, (corresponding to 0.2 nM of target DNA). Regeneration of the recognition surface is possible by treatment with 0.25 M NaOH solution. After rehybridization of the regenerated surface with the target DNA sequence, >95% of the current is recovered, indicating that the redox polymer and probe DNA are strongly bound to the surface. These results demonstrate the utility of the proposed approach. PMID:16615783

  14. 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

  15. Agmatine-Containing Bioreducible Polymer for Gene Delivery Systems and Its Dual Degradation Behavior.

    PubMed

    Choi, Ji-Yeong; Ryu, Kitae; Lee, Gyeong Jin; Kim, Kyunghwan; Kim, Tae-Il

    2015-09-14

    Agmatine-containing bioreducible polymer, poly(cystaminebis(acrylamide)-agmatine) (poly(CBA-AG)) was synthesized for gene delivery systems. It could form 200-300 nm sized and positively charged polyplexes with pDNA, which could release pDNA in reducing the environment due to the internal disulfide bonds cleavage. Poly(CBA-AG) also showed a spontaneous degradation behavior in aqueous condition in contrast to the backbone polymer, poly(cystaminebis(acrylamide)-diaminobutane) (poly(CBA-DAB)) lacking guanidine moieties, probably due to the self-catalyzed hydrolysis of internal amide bonds by guanidine moieties. The cytotoxicity of poly(CBA-AG) was cell-dependent but minimal. Poly(CBA-AG) exhibited highly enhanced transfection efficiency in comparison with poly(CBA-DAB) and even higher transfection efficiency than PEI25k. However, cellular uptake efficiency of the polyplexes did not show positive correlation with the transfection efficiency. Confocal microscopy observation revealed that pDNA delivered by poly(CBA-AG) was strongly accumulated in cell nuclei. These results suggested that high transfection efficiency of poly(CBA-AG) may be derived from the efficient pDNA localization in cell nuclei by guanidine moieties and that the polyplexes dissociation via self-catalyzed hydrolysis as well as disulfide bonds cleavage in cytosol also may facilitate the transfection process. Finally, poly(CBA-AG)/pJDK-apoptin polyplex showed a high anticancer activity induced by apoptosis, demonstrating a potential of poly(CBA-AG) as a gene carrier for cancer gene therapy.

  16. Time-resolved emission of dye probes in a shock-compressed polymer

    NASA Astrophysics Data System (ADS)

    Brown, Kathryn E.; Fu, Yuanxi; Shaw, William L.; Dlott, Dana D.

    2012-11-01

    Simultaneous impact velocity and time-resolved emission measurements are made on shocked poly-methylmethacryalate doped with rhodamine 640 (R640) dye. Planar single-stage shocks in the 0-16 GPa range are produced using a laser-driven flyer plate apparatus. This method allows for reproducible measurements of the time-resolved dye emission intensity, redshift, and spectral width monitored with 1 ns time resolution. The redshift is used to probe the shock front, which has a two-part viscoelastic structure. The maximum dye emission redshift under shock loading stops increasing above ˜6 GPa. In static high-pressure measurements, the redshift continues to increase up to at least 10 GPa. The smaller redshift seen in shock experiments is not an effect of the shock temperature increase, and it is attributed to incomplete polymer configurational relaxation frustrated by the short duration (<15 ns) of the shock. The viscous relaxation behind the shock front has a part whose rate increases with increasing shock pressure and a part that does not. It is this latter part that causes the shock-induced emission redshift to stop increasing above 6 GPa, and the differences between the two types of relaxation are explained in the context of the free-energy needed to surmount configurational barriers.

  17. 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.

  18. 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

  19. Effects of anode flooding on the performance degradation of polymer electrolyte membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Kim, Mansu; Jung, Namgee; Eom, KwangSup; Yoo, Sung Jong; Kim, Jin Young; Jang, Jong Hyun; Kim, Hyoung-Juhn; Hong, Bo Ki; Cho, EunAe

    2014-11-01

    Polymer electrolyte membrane fuel cell (PEMFC) stacks in a fuel cell vehicle can be inevitably exposed to harsh environments such as cold weather in winter, causing water flooding by the direct flow of condensed water to the electrodes. In this study, anode flooding was experimentally investigated with condensed water generated by cooling the anode gas line during a long-term operation (∼1600 h). The results showed that the performance of the PEMFC was considerably degraded. After the long-term experiment, the thickness of the anode decreased, and the ratio of Pt to carbon in the anode increased. Moreover, repeated fuel starvation of the half-cell severely oxidized the carbon surface due to the high induced potential (>1.5 VRHE). The cyclic voltammogram of the anode in the half-cell experiments indicated that the characteristic feature of the oxidized carbon surface was similar to that of the anode in the single cell under anode flooding conditions during the long-term experiment. Therefore, repeated fuel starvation by anode flooding caused severe carbon corrosion in the anode because the electrode potential locally increased to >1.0 VRHE. Consequently, the density of the tri-phase boundary decreased due to the corrosion of carbons supporting the Pt nanoparticles in the anode.

  20. Polymer electrolyte membrane fuel cell performance degradation by coolant leakage and recovery

    NASA Astrophysics Data System (ADS)

    Jung, Ju Hae; Kim, Se Hoon; Hur, Seung Hyun; Joo, Sang Hoon; Choi, Won Mook; Kim, Junbom

    2013-03-01

    Coolant leakage leads to decrease in performance during the operation of electric vehicles which make use of polymer electrolyte membrane fuel cells (PEMFC). This study examines the effects of various coolant leak conditions in 3-cell stack and single cell. The experimental results show that an irreversible reduction in performance occurs after coolant injection into the anode side of the stack. Poisoning of carbon monoxide (CO) on the platinum (Pt) catalyst is caused by electro-oxidation reaction of EG. Water cleaning is selected because CO poisoning is desorbed to reaction with water molecules. Performance is quickly reduced when the interval between coolant injections is short. Performance reduction is indicated by the experimental results for the gas diffusion layer (GDL) and the membrane electrode assembly (MEA). It shows that performance of the MEA with the GDL exposed to coolant decreased, but it is recovered after water cleaning. In contrast, results for performance of the MEA exposed to coolant for long time could not be reversed after water cleaning. Therefore, we propose that performance degradation of coolant leak on the Pt catalyst surface and GDL can be recovered by the water cleaning simply without disassembly of stack.

  1. Gel casting of resorbable polymers. 2. In-vitro degradation of bone graft substitutes.

    PubMed

    Coombes, A G; Heckman, J D

    1992-01-01

    Gel cast microporous materials produced from: slow resorbing, poly(L-lactide); fast resorbing, 50:50 poly(DL lactide coglycolide); and blends of these polymers have been characterized by weight loss, compression testing and thermal analysis after immersion in phosphate buffered saline (37 degrees C, pH 7.4) for times up to 6 months. Increasing weight loss and reduction in compressive properties with immersion time were measured. Blending reduces the rate of weight loss and material shrinkage relative to the copolymer. Thermal analysis of degraded samples revealed evidence of reorganization of the crystalline phase in poly(L-lactide) and a crystalline component in the 50:50 copolymer, estimated at 5-7% of the original material content, which is probably responsible for gel formation. Thermograms of the blend are effectively a superposition of thermograms of the individual components. Gel casting shows potential for varying the resorption rate, form stability and compressive properties of micro/macroporous bone graft substitutes. PMID:1600032

  2. Biodegradable polymer for sealing porous PEO layer on pure magnesium: An in vitro degradation study

    NASA Astrophysics Data System (ADS)

    Alabbasi, Alyaa; Mehjabeen, Afrin; Kannan, M. Bobby; Ye, Qingsong; Blawert, Carsten

    2014-05-01

    An attempt was made to seal the porous silicate-based plasma electrolytic oxidation (PEO) layer on pure magnesium (Mg) with a biodegradable polymer, poly(L-lactide) (PLLA), to delay the localized degradation of magnesium-based implants in body fluid for better in-service mechanical integrity. Firstly, a silicate-based PEO coating on pure magnesium was performed using a pulsed constant current method. In order to seal the pores in the PEO layer, PLLA was coated using a two-step spin coating method. The performance of the PEO-PLLA Mg was evaluated using electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization. The EIS results showed that the polarization resistance (Rp) of the PEO-PLLA Mg was close to two orders of magnitude higher than that of the PEO Mg. While the corrosion current density (icorr) of the pure Mg was reduced by 65% with the PEO coating, the PEO-PLLA coating reduced the icorr by almost 100%. As expected, the Rp of the PEO-PLLA Mg decreased with increase in exposure time. However, it was noted that the Rp of the PEO-PLLA Mg even after 100 h was six times higher than that of the PEO Mg after 48 h exposure, and did not show any visible localized attack.

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

    PubMed Central

    2015-01-01

    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 1H 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. PMID:25997518

  4. Kinetic measurements of the hydrolytic degradation of cefixime: effect of Captisol complexation and water-soluble polymers.

    PubMed

    Mallick, Subrata; Mondal, Arijit; Sannigrahi, Santanu

    2008-07-01

    We have taken kinetic measurements of the hydrolytic degradation of cefixime, and have studied the effect of Captisol complexation and water-soluble polymers on that degradation. The phase solubility of cefixime in Captisol was determined. Kinetic measurements were carried out as a function of pH and temperature. High-performance liquid chromatography (HPLC) was performed to assay all the samples of phase-solubility analysis and kinetic measurements. Chromatographic separation of the degradation products was also performed by HPLC. FT-IR spectroscopy was used to investigate the presence of any interaction between cefixime and Captisol and soluble polymer. The phase-solubility study showed A(L)-type behaviour. The pH-rate profile of cefixime exhibited a U-shaped profile whilst the degradation of cefixime alone was markedly accelerated with elevated temperature. A strong stabilizing influence of the cefixime-Captisol complexation and hypromellose was observed against aqueous mediated degradation, as compared with povidone and macrogol. The unfavourable effect of povidone and macrogol may have been due to the steric hindrance, which prevented the guest molecule from entering the cyclodextrin cavity, whereas hypromellose did not produce any steric hindrance.

  5. Insulation degradation behavior of multilayer ceramic capacitors clarified by Kelvin probe force microscopy under ultra-high vacuum

    NASA Astrophysics Data System (ADS)

    Suzuki, Keigo; Okamoto, Takafumi; Kondo, Hiroyuki; Tanaka, Nobuhiko; Ando, Akira

    2013-02-01

    We investigated surface potential images on the cross section of degraded multilayer ceramic capacitors (MLCCs) by Kelvin probe force microscopy measured under a dc bias voltage in ultra-high vacuum. A highly accelerated lifetime test (HALT) was conducted to obtain degraded MLCCs. The high energy resolution of the present measurement allows us to observe the step-like voltage drops on dielectric layers of as-fired MLCCs. The step-like voltage drops disappear on the dielectric layers of degraded MLCCs, indicating that the resistance at grain boundaries declines with the progress of insulation degradation. Furthermore, the electric field concentrations near the electrodes are clearly observed under forward and backward bias. The discussion based on energy band diagrams suggests that the electric field concentrations near electrodes are attributable to energy barrier formed at the interface between electrode and dielectrics. In particular, the electric field concentration at cathode in HALT measured under backward bias is much higher than that at anode in HALT measured under forward bias. This implies that oxygen vacancies accumulated during HALT cause band bending near the cathode in HALT. We propose that the initial decline of resistance at grain boundaries and following electric-field concentrations at anode in HALT is essential to the insulation degradation on dielectric layers of MLCCs under dc bias voltage.

  6. 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.

  7. 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. PMID:26512003

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

    PubMed Central

    Kutikov, Artem B.; Song, Jie

    2013-01-01

    Electrospun polymer/hydroxyapatite (HA) composites combining biodegradability with osteoconductivity are attractive for skeletal tissue engineering applications. However, most biodegradable polymers such as 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 incorporated a hydrophilic polyethylene glycol (PEG) block to 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 25 wt% 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 osteogenesis 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. PMID:23791675

  9. 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.

  10. Isolation of isoprene degrading bacteria from soils, development of isoA gene probes and identification of the active isoprene-degrading soil community using DNA-stable isotope probing.

    PubMed

    El Khawand, Myriam; Crombie, Andrew T; Johnston, Antonia; Vavlline, Dmitrii V; McAuliffe, Joseph C; Latone, Jacob A; Primak, Yuliya A; Lee, Sang-Kyu; Whited, Gregg M; McGenity, Terry J; Murrell, J Colin

    2016-09-01

    Emissions of biogenic volatile organic compounds (bVOCs), are an important element in the global carbon cycle, accounting for a significant proportion of fixed carbon. They contribute directly and indirectly to global warming and climate change and have a major effect on atmospheric chemistry. Plants emit isoprene to the atmosphere in similar quantities to emissions of methane from all sources and each accounts for approximately one third of total VOCs. Although methanotrophs, capable of growth on methane, have been intensively studied, we know little of isoprene biodegradation. Here, we report the isolation of two isoprene-degrading strains from the terrestrial environment and describe the design and testing of polymerase chain reaction (PCR) primers targeting isoA, the gene encoding the active-site component of the conserved isoprene monooxygenase, which are capable of retrieving isoA sequences from isoprene-enriched environmental samples. Stable isotope probing experiments, using biosynthesized (13) C-labelled isoprene, identified the active isoprene-degrading bacteria in soil. This study identifies novel isoprene-degrading strains using both culture-dependent and, for the first time, culture-independent methods and provides the tools and foundations for continued investigation of the biogeography and molecular ecology of isoprene-degrading bacteria.

  11. Probe-Directed Degradation (PDD) for Flexible Removal of Unwanted cDNA Sequences from RNA-Seq Libraries.

    PubMed

    Archer, Stuart K; Shirokikh, Nikolay E; Preiss, Thomas

    2015-04-01

    Most applications for RNA-seq require the depletion of abundant transcripts to gain greater coverage of the underlying transcriptome. The sequences to be targeted for depletion depend on application and species and in many cases may not be supported by commercial depletion kits. This unit describes a method for generating RNA-seq libraries that incorporates probe-directed degradation (PDD), which can deplete any unwanted sequence set, with the low-bias split-adapter method of library generation (although many other library generation methods are in principle compatible). The overall strategy is suitable for applications requiring customized sequence depletion or where faithful representation of fragment ends and lack of sequence bias is paramount. We provide guidelines to rapidly design specific probes against the target sequence, and a detailed protocol for library generation using the split-adapter method including several strategies for streamlining the technique and reducing adapter dimer content.

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

    PubMed Central

    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. PMID:25360131

  13. 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. PMID:25360131

  14. Scleral reinforcement through host tissue integration with biomimetic enzymatically degradable semi-interpenetrating polymer network.

    PubMed

    Su, James; Wall, Samuel T; Healy, Kevin E; Wildsoet, Christine F

    2010-03-01

    Enzymatically degradable semi-interpenetrating polymer networks (edsIPNs) were explored for their biocompatibility and ability to promote new scleral tissue growth, as a means of reinforcing the posterior wall of the eye. The edsIPNs comprised thermoresponsive poly(N-isopropylacrylamide-co-acrylic acid), customizable peptide crosslinkers cleavable by matrix metalloproteinases, and interpenetrating linear poly(acrylic acid)-graft-peptide chains to engage with cell surface receptors. Rheological studies revealed an increase in stiffness at body temperature; the complex shear modulus |G*| was 14.13 +/- 6.13 Pa at 22 degrees C and 63.18 +/- 12.24 Pa at 37 degrees C, compatible with injection at room temperature. Primary chick scleral fibroblasts and chondrocytes cultured on edsIPN increased by 15.1- and 11.1-fold, respectively, over 11 days; both exhibited delayed onset of exponential growth compared with the cells plated on tissue culture polystyrene. The edsIPN was delivered by retrobulbar injection (100 microL) to nine 2-week-old chicks to assess biocompatibility in vivo. Ocular axial dimensions were assessed using A-scan ultrasonography over 28 days, after which eyes were processed for histological analysis. Although edsIPN injections did not affect the rate of ocular elongation, the outer fibrous sclera showed significant thickening. The demonstration that injectable biomimetic edsIPNs stimulate scleral fibrous tissue growth represents proof-of-principle for a novel approach for scleral reinforcement and a potential therapy for high myopia. PMID:19814587

  15. 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.

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

    PubMed Central

    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.

    2013-01-01

    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. PMID:23584789

  17. Analysis of ER-associated glycoprotein degradation using synthetic glycopeptide probes

    SciTech Connect

    Hagihara, Shinya; Goda, Kazuhito; Matsuo, Ichiro; Ito, Yukishige . E-mail: yukito@riken.jp

    2007-08-24

    Quality control of proteins is an essential process for maintaining normal cell activity. It ensures that only correctly folded proteins are produced and terminally misfolded proteins are eliminated by degradation. ER-associated degradation (ERAD) of misfolded proteins is an important aspect of protein quality control system. Recent studies have revealed that glycoprotein glycans play significant roles in this process. It includes polyubiquitination, deglycosylation, and proteasomal degradation. In the present study, a systematic analysis of these steps was carried out using chemically synthesized glycopeptides. We revealed that N-linked glycopeptides are degraded by 20S proteasome, but with drastically reduced rate compared to non-glycosylated peptide. This result strongly suggests that deglycosylating activity of peptide:N-glycanase (PNGase) is important for the facile degradation of glycoproteins. Our study showed, for the first time, that PNGase cleaves truncated glycans as short as chitobiose from peptide. However, this cleavage required the presence of hydrophobic region nearby N-glycosylation site. Furthermore, analysis of interactions with F-box protein Fbs1 was conducted with fluorescent correlation spectroscopy (FCS). It was shown that the presence of Fbs1 perturb the activity of PNGase toward high-mannose-type glycopeptides.

  18. Probing horseradish peroxidase catalyzed degradation of azo dye from tannery wastewater.

    PubMed

    Preethi, Sadhanandam; Anumary, Ayyappan; Ashokkumar, Meiyazhagan; Thanikaivelan, Palanisamy

    2013-01-01

    Biocatalysis based effluent treatment has outclassed the presently favored physico-chemical treatments due to nil sludge production and monetary savings. Azo dyes are commonly employed in the leather industry and pose a great threat to the environment. Here, we show the degradation of C. I. Acid blue 113 using horseradish peroxidase (HRP) assisted with H2O2 as a co-substrate. It was observed that 0.08 U HRP can degrade 3 mL of 30 mg/L dye up to 80% within 45 min with the assistance of 14 μL of H2O2 at pH 6.6 and 30°C. The feasibility of using the immobilized HRP for dye degradation was also examined and the results show up to 76% dye degradation under similar conditions to that of free HRP with the exception of longer contact time of 240 min. Recycling studies reveal that the immobilized HRP can be recycled up to 3 times for dye degradation. Kinetics drawn for the free HRP catalyzed reaction marked a lower K m and higher V max values, which denotes a proper and faster affinity of the enzyme towards the dye, when compared to the immobilized HRP. The applicability of HRP for treating the actual tannery dye-house wastewater was also demonstrated. PMID:23961406

  19. 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

  20. 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

  1. Fluorescence hydrogen peroxide probe based on a microstructured polymer optical fiber modified with a titanium dioxide film.

    PubMed

    Li, Dongdong; Wang, Lili

    2010-05-01

    A highly sensitive microstructured polymer optical fiber (MPOF) probe for hydrogen peroxide was made by forming a rhodamine 6G-doped titanium dioxide film on the side walls of array holes in an MPOF. It was found that hydrogen peroxide only has a response to the MPOF probe in a certain concentration of potassium iodide in sulfuric acid solution. The calibration graph of fluorescence intensity versus hydrogen peroxide concentration is linear in the range of 1.6 x 10(-7) mol/L to 9.6 x 10(-5) mol/L. The method, with high sensitivity and a wide linear range, has been applied to the determination of trace amounts of hydrogen peroxide in a few real samples, such as rain water and contact lens disinfectant, with satisfactory results.

  2. 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.

  3. Study of thermal stability and degradation of fire resistant candidate polymers for aircraft interiors

    NASA Technical Reports Server (NTRS)

    Hsu, M. T. S.

    1976-01-01

    The thermochemistry of bismaleimide resins and phenolphthalein polycarbonate was studied. Both materials are fire-resistant polymers and may be suitable for aircraft interiors. The chemical composition of the polymers has been determined by nuclear magnetic resonance and infrared spectroscopy and by elemental analysis. Thermal properties of these polymers have been characterized by thermogravimetric analyses. Qualitative evaluation of the volatile products formed in pyrolysis under oxidative and non-oxidative conditions has been made using infrared spectrometry. The residues after pyrolysis were analyzed by elemental analysis. The thermal stability of composite panel and thermoplastic materials for aircraft interiors was studied by thermogravimetric analyses.

  4. 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. PMID:27254797

  5. 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.

  6. 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.

  7. 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.

  8. ω-Azido fatty acids as probes to detect fatty acid biosynthesis, degradation, and modification[S

    PubMed Central

    Pérez, Alexander J.; Bode, Helge B.

    2014-01-01

    FAs play a central role in the metabolism of almost all known cellular life forms. Although GC-MS is regarded as a standard method for FA analysis, other methods, such as HPLC/MS, are nowadays widespread but are rarely applied to FA analysis. Here we present azido-FAs as probes that can be used to study FA biosynthesis (elongation, desaturation) or degradation (β-oxidation) upon their uptake, activation, and metabolic conversion. These azido-FAs are readily accessible by chemical synthesis and their metabolic products can be easily detected after click-chemistry based derivatization with high sensitivity by HPLC/MS, contributing a powerful tool to FA analysis, and hence, lipid analysis in general. PMID:25013232

  9. Probing the weak interaction of proteins with neutral and zwitterionic antifouling polymers.

    PubMed

    Wu, Jiang; Zhao, Chao; Hu, Rundong; Lin, Weifeng; Wang, Qiuming; Zhao, Jun; Bilinovich, Stephanie M; Leeper, Thomas C; Li, Lingyan; Cheung, Harry M; Chen, Shengfu; Zheng, Jie

    2014-02-01

    Protein-polymer interactions are of great interest in a wide range of scientific and technological applications. Neutral poly(ethylene glycol) (PEG) and zwitterionic poly(sulfobetaine methacrylate) (pSBMA) are two well-known nonfouling materials that exhibit strong surface resistance to proteins. However, it still remains unclear or unexplored how PEG and pSBMA interact with proteins in solution. In this work, we examine the interactions between two model proteins (bovine serum albumin and lysozyme) and two typical antifouling polymers of PEG and pSBMA in aqueous solution using fluorescence spectroscopy, atomic force microscopy and nuclear magnetic resonance. The effect of protein:polymer mass ratios on the interactions is also examined. Collective data clearly demonstrate the existence of weak hydrophobic interactions between PEG and proteins, while there are no detectable interactions between pSBMA and proteins. The elimination of protein interaction with pSBMA could be due to an enhanced surface hydration of zwitterionic groups in pSBMA. New evidence is given to demonstrate the interactions between PEG and proteins, which are often neglected in the literature because the PEG-protein interactions are weak and reversible, as well as the structural change caused by hydrophobic interaction. This work provides a better fundamental understanding of the intrinsic structure-activity relationship of polymers underlying polymer-protein interactions, which are important for designing new biomaterials for biosensor, medical diagnostics and drug delivery applications. PMID:24120846

  10. Polymer characterization using the time-resolved phosphorescence of singlet oxygen as a spectroscopic probe

    SciTech Connect

    Ogilby, P.R.; Kristiansen, M.; Dillon, M.P. . Dept. of Chemistry); Taylor, V.L.; Clough, R.L. )

    1990-01-01

    The lowest excited electronic state of molecular oxygen, singlet oxygen ({sup 1}{Delta}{sub g}0{sub 2}), can be produced in solid organic polymers by a variety of different methods. Once produced, singlet oxygen will return to the ground triplet state by two pathways, radiative (phosphorescence) and non-radiative decay. Although the quantum efficiency of phosphorescence is small ({minus}10{sup {minus}5}), singlet oxygen can be detected by its emission at 1270 mn in both steady-state and time-resolved experiments. The phosphorescence of singlet oxygen can be used to characterize many properties of a solid organic polymer. 2 refs., 5 figs.

  11. 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

  12. 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.

  13. Cell protective, ABC triblock polymer-based thermoresponsive hydrogels with ROS-triggered degradation and drug release.

    PubMed

    Gupta, Mukesh K; Martin, John R; Werfel, Thomas A; Shen, Tianwei; Page, Jonathan M; Duvall, Craig L

    2014-10-22

    A combination of anionic and RAFT polymerization was used to synthesize an ABC triblock polymer poly[(propylenesulfide)-block-(N,N-dimethylacrylamide)-block-(N-isopropylacrylamide)] (PPS-b-PDMA-b-PNIPAAM) that forms physically cross-linked hydrogels when transitioned from ambient to physiologic temperature and that incorporates mechanisms for reactive oxygen species (ROS) triggered degradation and drug release. At ambient temperature (25 °C), PPS-b-PDMA-b-PNIPAAM assembled into 66 ± 32 nm micelles comprising a hydrophobic PPS core and PNIPAAM on the outer corona. Upon heating to physiologic temperature (37 °C), which exceeds the lower critical solution temperature (LCST) of PNIPAAM, micelle solutions (at ≥2.5 wt %) sharply transitioned into stable, hydrated gels. Temperature-dependent rheology indicated that the equilibrium storage moduli (G') of hydrogels at 2.5, 5.0, and 7.5 wt % were 20, 380, and 850 Pa, respectively. The PPS-b-PDMA-b-PNIPAAM micelles were preloaded with the model drug Nile red, and the resulting hydrogels demonstrated ROS-dependent drug release. Likewise, exposure to the peroxynitrite generator SIN-1 degraded the mechanical properties of the hydrogels. The hydrogels were cytocompatible in vitro and were demonstrated to have utility for cell encapsulation and delivery. These hydrogels also possessed inherent cell-protective properties and reduced ROS-mediated cellular death in vitro. Subcutaneously injected PPS-b-PDMA-b-PNIPAAM polymer solutions formed stable hydrogels that sustained local release of the model drug Nile red for 14 days in vivo. These collective data demonstrate the potential use of PPS-b-PDMA-b-PNIPAAM as an injectable, cyto-protective hydrogel that overcomes conventional PNIPAAM hydrogel limitations such as syneresis, lack of degradability, and lack of inherent drug loading and environmentally responsive release mechanisms.

  14. Fluorescence Probe Based on Hybrid Mesoporous Silica/Quantum Dot/Molecularly Imprinted Polymer for Detection of Tetracycline.

    PubMed

    Zhang, Liang; Chen, Ligang

    2016-06-29

    A newly designed fluorescence probe made from a hybrid quantum dot/mesoporous silica/molecularly imprinted polymer (QD/MS/MIP) was successfully created, and the probe was used for the detection of tetracycline (TC) in serum sample. QD/MS/MIP was characterized by transmission electron microscope, Fourier transform infrared spectroscopy, UV spectroscopy, X-ray powder diffraction, nitrogen adsorption-desorption experiment and fluorescence spectroscopy. Tetracycline, which is a type of broad-spectrum antibiotic, was selected as the template. The monomer and the template were combined by covalent bonds. After the template was removed to form a binding site, a hydrogen bonding interaction formed between the hole and the target molecule. Moreover, when rebinding TC, a new complex was produced between the amino group of QD/MS/MIP and the hydroxyl group of TC. After that, the energy of the QDs could transfer to the complex, which explains the fluorescence quenching phenomenon. The fluorescent intensity of QD/MS/MIP decreased in 10 min, and an excellent linearity from 50 to 1000 ng mL(-1) was correspondingly obtained. This composite material has a high selectivity with an imprinting factor of 6.71. In addition, the confirmed probe strategy was successfully applied to serum sample analyses, and the recoveries were 90.2%-97.2% with relative standard deviations of 2.2%-5.7%. This current work offers a novel and suitable method to synthesize QD/MS/MIP with a highly selective recognition ability. This composite material will be valuable for use in fluorescence probe applications. PMID:27280785

  15. Bio-polymer coatings on neural probe surfaces: Influence of the initial sample composition

    NASA Astrophysics Data System (ADS)

    Chow, Winnie W. Y.; Herwik, Stanislav; Ruther, Patrick; Göthelid, Emmanuelle; Oscarsson, Sven

    2012-08-01

    This paper presents the results of the study of hyaluronic acid (HyA) coating on two structural materials, silicon oxide (dielectric) surface and platinum (Pt) surface used for fabrication of probes developed for neurological investigations in the framework of the EU-project NeuroProbes. The silicon-based neural probes consist of multiple Pt electrodes on the probe shafts for neural recording applications. HyA coatings were proposed to apply on the probe surfaces to enhance the biocompatibility [1]. This study aims at understanding the influence of the initial composition of the probe surface on the structure and morphology of HyA coating. HyA was chemically functionalized by SS-pyridin using (N-Succinimidyl 3-[2-pyridyldithio]-propionate) (SPDP) and was immobilized on the surfaces via a covalent bond. The dielectric and Pt surfaces were derivatized by use of (3-mercaptopropyl) methyldimethoxysilane (MPMDMS). The silanol groups in MPMDMS bind to the dielectric surface, leaving the thiol groups at the uppermost surface and the thiol groups then bind covalently to the functionalized HyA. On the Pt surface, it is the thiol group which binds on the Pt surface. The coated surfaces were characterized by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). A well-defined HyA layer was observed on both dielectric and Pt surfaces. The coating of two molecular weights (340 kDa and 1.3 MDa) of HyA was examined. The influence of the silanized layer on the HyA coating was also investigated.

  16. Amphiphilic degradable polymers for immobilization and sustained delivery of sphingosine 1-phosphate

    PubMed Central

    Zhang, Jing; Song, Jie

    2014-01-01

    Controlled delivery of angiogenic factor sphingosine 1-phosphate (S1P) represents a promising strategy for promoting vascularization during tissue repair and regeneration. In this study, we developed an amphiphilic biodegradable polymer platform for the stable encapsulation and sustained release of S1P. Mimicking the interaction between amphiphilic S1P and its binding proteins, a series of polymers with hydrophilic poly(ethylene glycol) core and lipophilic flanking segments of polylactide and/or poly(alkylated lactide) with different alkyl chain lengths were synthesized. These polymers were electrospun into fibrous meshes, and loaded with S1P in generally high loading efficiencies (>90%). Sustained S1P release from these scaffolds could be tuned by adjusting the alkyl chain length, blockiness and lipophilic block length, achieving 35-55% and 45-80% accumulative releases in the first 8 h and by 7 days, respectively. Furthermore, using endothelial cell tube formation assay and chicken chorioallantoic membrane (CAM) assay, we showed that the different S1P loading doses and release kinetics translated into distinct pro-angiogenic outcomes. These results suggest that these amphiphilic polymers are effective delivery vehicles for S1P and may be explored as tissue engineering scaffolds where the delivery of lipophilic or amphiphilic bioactive factors are desired. PMID:24631657

  17. 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...

  18. Amphiphilic degradable polymers for immobilization and sustained delivery of sphingosine 1-phosphate.

    PubMed

    Zhang, Jing; Song, Jie

    2014-07-01

    Controlled delivery of the angiogenic factor sphingosine 1-phosphate (S1P) represents a promising strategy for promoting vascularization during tissue repair and regeneration. In this study, we developed an amphiphilic biodegradable polymer platform for the stable encapsulation and sustained release of S1P. Mimicking the interaction between amphiphilic S1P and its binding proteins, a series of polymers with hydrophilic poly(ethylene glycol) core and lipophilic flanking segments of polylactide and/or poly(alkylated lactide) with different alkyl chain lengths were synthesized. These polymers were electrospun into fibrous meshes, and loaded with S1P in generally high loading efficiencies (>90%). Sustained S1P release from these scaffolds could be tuned by adjusting the alkyl chain length, blockiness and lipophilic block length, achieving 35-55% and 45-80% accumulative releases in the first 8h and by 7 days, respectively. Furthermore, using endothelial cell tube formation assay and chicken chorioallantoic membrane assay, we showed that the different S1P loading doses and release kinetics translated into distinct pro-angiogenic outcomes. These results suggest that these amphiphilic polymers are effective delivery vehicles for S1P and may be explored as tissue engineering scaffolds where the delivery of lipophilic or amphiphilic bioactive factors is desired.

  19. 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

  20. “Turn-on” fluorescence probe integrated polymer nanoparticles for sensing biological thiol molecules

    PubMed Central

    Ang, Chung Yen; Tan, Si Yu; Lu, Yunpeng; Bai, Linyi; Li, Menghuan; Li, Peizhou; Zhang, Quan; Selvan, Subramanian Tamil; Zhao, Yanli

    2014-01-01

    A “turn-on” thiol-responsive fluorescence probe was synthesized and integrated into polymeric nanoparticles for sensing intracellular thiols. There is a photo-induced electron transfer process in the off state of the probe, and this process is terminated upon the reaction with thiol compounds. Configuration interaction singles (CIS) calculation was performed to confirm the mechanism of this process. A series of sensing studies were carried out, showing that the probe-integrated nanoparticles were highly selective towards biological thiol compounds over non-thiolated amino acids. Kinetic studies were also performed to investigate the relative reaction rate between the probe and the thiolated amino acids. Subsequently, the Gibbs free energy of the reactions was explored by means of the electrochemical method. Finally, the detection system was employed for sensing intracellular thiols in cancer cells, and the sensing selectivity could be further enhanced with the use of a cancer cell-targeting ligand in the nanoparticles. This development paves a path for the sensing and detection of biological thiols, serving as a potential diagnostic tool in the future. PMID:25394758

  1. Application of Tapping-Mode Scanning Probe Electrospray Ionization to Mass Spectrometry Imaging of Additives in Polymer Films

    PubMed Central

    Shimazu, Ryo; Yamoto, Yoshinari; Kosaka, Tomoya; Kawasaki, Hideya; Arakawa, Ryuichi

    2014-01-01

    We report the application of tapping-mode scanning probe electrospray ionization (t-SPESI) to mass spectrometry imaging of industrial materials. The t-SPESI parameters including tapping solvent composition, solvent flow rate, number of tapping at each spot, and step-size were optimized using a quadrupole mass spectrometer to improve mass spectrometry (MS) imaging of thin-layer chromatography (TLC) and additives in polymer films. Spatial resolution of approximately 100 μm was achieved by t-SPESI imaging mass spectrometry using a fused-silica capillary (50 μm i.d., 150 μm o.d.) with the flow rate set at 0.2 μL/min. This allowed us to obtain discriminable MS imaging profiles of three dyes separated by TLC and the additive stripe pattern of a PMMA model film depleted by UV irradiation. PMID:26819894

  2. Scanning probe microscopy for the analysis of composite Ti/hydrocarbon plasma polymer thin films

    NASA Astrophysics Data System (ADS)

    Choukourov, A.; Grinevich, A.; Slavinska, D.; Biederman, H.; Saito, N.; Takai, O.

    2008-03-01

    Composite Ti/hydrocarbon plasma polymer films with different Ti concentration were deposited on silicon by dc magnetron sputtering of titanium in an atmosphere of argon and hexane. As measured by Kelvin force microscopy and visco-elastic atomic force microscopy, respectively, surface potential and hardness increase with increasing Ti content. Adhesion force to silicon and to fibrinogen molecules was stronger for the Ti-rich films as evaluated from the AFM force-distance curves. Fibrinogen forms a very soft layer on these composites with part of the protein molecules embedded in the outermost region of the plasma polymer. An increase of the surface charge due to fibrinogen adsorption has been observed and attributed to positively charged αC domains of fibrinogen molecule.

  3. An extended micromechanics method for probing interphase properties in polymer nanocomposites

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

    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. 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.

  4. 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)

  5. 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

  6. 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.

  7. Mechanistic insights into ozone-initiated oxidative degradation of saturated hydrocarbons and polymers.

    PubMed

    Lee, Richmond; Coote, Michelle L

    2016-09-21

    Accurate quantum chemical calculations were employed to investigate the mechanism of ozone-initiated oxidation of C-H bonds of saturated hydrocarbons and polymers. Step wise hydrogen atom abstraction generates the first resting state the trihydroxide -COOOH, which undergoes decomposition to produce the free radical species alkoxyl -CO˙ and peroxyl ˙OOH thereby setting off a complex chain of radical processes. The H transfer from peroxyl radical to alkoxyl allows formation of inactive alcohol and the singlet excited dioxygen. Other competitive processes include the self fragmentation or β-scission of the alkoxyl -CO˙ to give rise to a carbonyl (ketone or aldehyde) and a C-centred free radical species. Tertiary C-H bonds are most susceptible to O3 oxidation followed by secondary and primary. Among the polymers studied, poly(styrene) is the least resistant to C-H bond ozonation, followed by poly(propylene), poly(methacrylate), poly(methyl methacrylate) and poly(vinyl chloride). Calculations also reveal catalytic effects of water in promoting the C-H bond oxidation process in polymer systems without competing H-bond donor groups.

  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. Mechanistic insights into ozone-initiated oxidative degradation of saturated hydrocarbons and polymers.

    PubMed

    Lee, Richmond; Coote, Michelle L

    2016-09-21

    Accurate quantum chemical calculations were employed to investigate the mechanism of ozone-initiated oxidation of C-H bonds of saturated hydrocarbons and polymers. Step wise hydrogen atom abstraction generates the first resting state the trihydroxide -COOOH, which undergoes decomposition to produce the free radical species alkoxyl -CO˙ and peroxyl ˙OOH thereby setting off a complex chain of radical processes. The H transfer from peroxyl radical to alkoxyl allows formation of inactive alcohol and the singlet excited dioxygen. Other competitive processes include the self fragmentation or β-scission of the alkoxyl -CO˙ to give rise to a carbonyl (ketone or aldehyde) and a C-centred free radical species. Tertiary C-H bonds are most susceptible to O3 oxidation followed by secondary and primary. Among the polymers studied, poly(styrene) is the least resistant to C-H bond ozonation, followed by poly(propylene), poly(methacrylate), poly(methyl methacrylate) and poly(vinyl chloride). Calculations also reveal catalytic effects of water in promoting the C-H bond oxidation process in polymer systems without competing H-bond donor groups. PMID:27545312

  10. 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. PMID:25079380

  11. 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.

  12. 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.

  13. 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; 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 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

  14. 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.

  15. An effective approach for alleviating cation-induced backbone degradation in aromatic ether-based alkaline polymer electrolytes.

    PubMed

    Han, Juanjuan; Liu, Qiong; Li, Xueqi; Pan, Jing; Wei, Ling; Wu, Ying; Peng, Hanqing; Wang, Ying; Li, Guangwei; Chen, Chen; Xiao, Li; Lu, Juntao; Zhuang, Lin

    2015-02-01

    Aromatic ether-based alkaline polymer electrolytes (APEs) are one of the most popular types of APEs being used in fuel cells. However, recent studies have demonstrated that upon being grafted by proximal cations some polar groups in the backbone of such APEs can be attacked by OH(-), leading to backbone degradation in an alkaline environment. To resolve this issue, we performed a systematic study on six APEs. We first replaced the polysulfone (PS) backbone with polyphenylsulfone (PPSU) and polyphenylether (PPO), whose molecular structures contain fewer polar groups. Although improved stability was seen after this change, cation-induced degradation was still obvious. Thus, our second move was to replace the ordinary quaternary ammonia (QA) cation, which had been closely attached to the polymer backbone, with a pendant-type QA (pQA), which was linked to the backbone through a long side chain. After a stability test in a 1 mol/L KOH solution at 80 °C for 30 days, all pQA-type APEs (pQAPS, pQAPPSU, and pQAPPO) exhibited as low as 8 wt % weight loss, which is close to the level of the bare backbone (5 wt %) and remarkably lower than those of the QA-type APEs (QAPS, QAPPSU, and QAPPO), whose weight losses under the same conditions were >30%. The pQA-type APEs also possessed clear microphase segregation morphology, which led to ionic conductivities that were higher, and water uptakes and degrees of membrane swelling that were lower, than those of the QA-type APEs. These observations unambiguously indicate that designing pendant-type cations is an effective approach to increasing the chemical stability of aromatic ether-based APEs.

  16. An effective approach for alleviating cation-induced backbone degradation in aromatic ether-based alkaline polymer electrolytes.

    PubMed

    Han, Juanjuan; Liu, Qiong; Li, Xueqi; Pan, Jing; Wei, Ling; Wu, Ying; Peng, Hanqing; Wang, Ying; Li, Guangwei; Chen, Chen; Xiao, Li; Lu, Juntao; Zhuang, Lin

    2015-02-01

    Aromatic ether-based alkaline polymer electrolytes (APEs) are one of the most popular types of APEs being used in fuel cells. However, recent studies have demonstrated that upon being grafted by proximal cations some polar groups in the backbone of such APEs can be attacked by OH(-), leading to backbone degradation in an alkaline environment. To resolve this issue, we performed a systematic study on six APEs. We first replaced the polysulfone (PS) backbone with polyphenylsulfone (PPSU) and polyphenylether (PPO), whose molecular structures contain fewer polar groups. Although improved stability was seen after this change, cation-induced degradation was still obvious. Thus, our second move was to replace the ordinary quaternary ammonia (QA) cation, which had been closely attached to the polymer backbone, with a pendant-type QA (pQA), which was linked to the backbone through a long side chain. After a stability test in a 1 mol/L KOH solution at 80 °C for 30 days, all pQA-type APEs (pQAPS, pQAPPSU, and pQAPPO) exhibited as low as 8 wt % weight loss, which is close to the level of the bare backbone (5 wt %) and remarkably lower than those of the QA-type APEs (QAPS, QAPPSU, and QAPPO), whose weight losses under the same conditions were >30%. The pQA-type APEs also possessed clear microphase segregation morphology, which led to ionic conductivities that were higher, and water uptakes and degrees of membrane swelling that were lower, than those of the QA-type APEs. These observations unambiguously indicate that designing pendant-type cations is an effective approach to increasing the chemical stability of aromatic ether-based APEs. PMID:25594224

  17. 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

  18. 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.

  19. 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

    2016-04-01

    (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. PMID:26974858

  20. 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

    2016-04-01

    (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.

  1. 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

  2. Supramolecular assembly of crosslinkable monomers for degradable and fluorescent polymer nanoparticles

    PubMed Central

    Yuan, Conghui; Chang, Ying; Mao, Jie; Yu, Shirong; Luo, Weiang; Xu, Yiting

    2015-01-01

    Intermolecular B-N coordination has been recognized as a promising driving force for molecular self-organization. However, direct utilization of this intermolecular interaction as building bridge for the supramolecular self-assembly of chemical functionalities to form nano-sized architectures remains a daunting challenge. Here, we outline a multiple intermolecular B-N coordination based supramolecular system, where small boronate molecules can be brought together in solution to form nanoparticles with controllable sizes and morphologies. We not only demonstrate the intrinsic switchable fluorescence and the stimuli-responsive capabilities of the designed boronate molecule, but also show that the stabilized or surface functionalized nanoparticles are degradable in response to pH and D-glucose and able to retain the fluorescence features of the boronate molecule. Additionally, the degraded nanoparticles can repair themselves through the reformation of B-N coordination. PMID:26413298

  3. 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.

  4. 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.

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

    PubMed

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

    2015-03-12

    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.

  6. In vitro modulation of macrophage phenotype and inhibition of polymer degradation by dexamethasone in a human macrophage/Fe/stress system.

    PubMed

    Casas, J; Zhao, Q; Donovan, M; Schroeder, P; Stokes, K; Untereker, D

    1999-09-15

    A new in vitro accelerated biological model, the macrophage-FeCl2-stress system was used for the evaluation of dexamethasone (DEX)-polymer formulations. This model combines the effects of cells (macrophages), transition metal ions (Fe2+), and polymer stress to promote material biodegradation. The cell and material effects of DEX, either in solution or incorporated into a polyetherurethane matrix (DEX/PEU), were monitored. Cell morphology and hydroperoxide formation in the polymer during cell culturing were characterized. After a subsequent treatment with FeCl2 the development of environmental stress cracking in the polymer was evaluated. We attempted to duplicate the biodegradation of PEU in terms of environmental stress cracking (ESC). Our results support the direct involvement of macrophages in polyetherurethane oxidation, probably by inducing hydroperoxide formation in the polymer structure. Under the influence of stress or strain, polymers with sufficient hydroperoxides degrade in the presence of Fe2+ metal ions in a manner that closely resembles the stress cracking that is observed in vivo. By contrast, polymers treated with either agents that inhibit cell activation and/or the oxidative burst, or with cells with no oxidative burst did not show signs of the biodegradative process. We demonstrated a reduction in hydroperoxide formation and no later ESC development in macrophage-cultured PEU in the presence of DEX in solution or in DEX-loaded PEU. We believe the prevention of initial polymer oxidation by reducing the cell's potential to produce oxidative stress at the tissue-biomaterial interface can directly inhibit the ESC degradation of chronically implanted polymers. The in vitro macrophage-Fe-stress system is a valuable tool for reliable assessment and cost-effective evaluation of biomaterials. PMID:10398008

  7. 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

  8. 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

  9. Intra-colonic administration of a polymer-bound NIRF probe for improved colorectal cancer detection during colonoscopy.

    PubMed

    Kogan-Zviagin, Inga; Shamay, Yosi; Nissan, Aviram; Sella-Tavor, Osnat; Golan, Moran; David, Ayelet

    2014-10-28

    There is increasing interest in the use of nanoparticle imaging probes for cancer diagnosis. However, various biological barriers limit the efficient delivery of nanoparticles to tumors following parenteral administration. We have investigated the applicability of a water-soluble polymeric imaging probe for improving the detection of gastrointestinal (GI) tumors after intra-luminal (colonic) administration. N-(2-hydroxypropyl)methacrylamide (HPMA) copolymers bearing either fluorescein-isothiocyanate (FITC) or near-infrared fluorescence (NIRF) dye (IR-783) were conjugated with EPPT1 peptide, derived from the CDR3 Vh region of a monoclonal antibody (ASM2) raised against human epithelial cancer cells, for targeting under-glycosylated mucin-1 (uMUC-1) expressed in neoplastic tissues. The targeted FITC-labeled copolymer, P-(EPPT1)-FITC, was investigated for its ability to bind human CRC cells and tissue specimens in vitro. The uMUC-1-targeted NIRF-labeled copolymer, P-(EPPT1)-IR783, was assessed for its ability to detect colonic lesions in vivo. P-(EPPT1)-FITC demonstrated superior binding to colorectal cancer (CRC) cells that over-express the uMUC-1 antigen and exhibited selectivity towards human CRC tissue specimens, as compared to adjacent normal tissues from the same patient. When applied intra-colonically, P-(EPPT1)-IR783 significantly accumulated in cancerous tissue, relative to the adjacent normal mucosa of HT29 and LS174T tumor-bearing mice, and demonstrated higher signal intensities in colonic tumors, as compared to the non-targeted P-(GG-OH)-IR783 probe (i.e., without EPPT1). We found that P-(GG-OH)-IR783 can also accumulate specifically at tumor sites. The cancer-specific uptake and retention of P-(GG-OH)-IR783 was not mediated by organic anion transporting peptides (OATPs). Our findings indicate that the polymer-bound NIRF probe can successfully detect solid tumors in the GI tract following intra-colonic administration, and could be used in conjunction with

  10. Intra-colonic administration of a polymer-bound NIRF probe for improved colorectal cancer detection during colonoscopy.

    PubMed

    Kogan-Zviagin, Inga; Shamay, Yosi; Nissan, Aviram; Sella-Tavor, Osnat; Golan, Moran; David, Ayelet

    2014-10-28

    There is increasing interest in the use of nanoparticle imaging probes for cancer diagnosis. However, various biological barriers limit the efficient delivery of nanoparticles to tumors following parenteral administration. We have investigated the applicability of a water-soluble polymeric imaging probe for improving the detection of gastrointestinal (GI) tumors after intra-luminal (colonic) administration. N-(2-hydroxypropyl)methacrylamide (HPMA) copolymers bearing either fluorescein-isothiocyanate (FITC) or near-infrared fluorescence (NIRF) dye (IR-783) were conjugated with EPPT1 peptide, derived from the CDR3 Vh region of a monoclonal antibody (ASM2) raised against human epithelial cancer cells, for targeting under-glycosylated mucin-1 (uMUC-1) expressed in neoplastic tissues. The targeted FITC-labeled copolymer, P-(EPPT1)-FITC, was investigated for its ability to bind human CRC cells and tissue specimens in vitro. The uMUC-1-targeted NIRF-labeled copolymer, P-(EPPT1)-IR783, was assessed for its ability to detect colonic lesions in vivo. P-(EPPT1)-FITC demonstrated superior binding to colorectal cancer (CRC) cells that over-express the uMUC-1 antigen and exhibited selectivity towards human CRC tissue specimens, as compared to adjacent normal tissues from the same patient. When applied intra-colonically, P-(EPPT1)-IR783 significantly accumulated in cancerous tissue, relative to the adjacent normal mucosa of HT29 and LS174T tumor-bearing mice, and demonstrated higher signal intensities in colonic tumors, as compared to the non-targeted P-(GG-OH)-IR783 probe (i.e., without EPPT1). We found that P-(GG-OH)-IR783 can also accumulate specifically at tumor sites. The cancer-specific uptake and retention of P-(GG-OH)-IR783 was not mediated by organic anion transporting peptides (OATPs). Our findings indicate that the polymer-bound NIRF probe can successfully detect solid tumors in the GI tract following intra-colonic administration, and could be used in conjunction with

  11. Determination of polymer electrolyte membrane (PEM) degradation products in fuel cell water using electrospray ionization tandem mass spectrometry.

    PubMed

    Zedda, Marco; Tuerk, Jochen; Peil, Stefan; Schmidt, Torsten C

    2010-12-30

    Within the scope of research of membrane degradation phenomena during fuel cell operation a reliable analytical procedure for the extraction, detection and quantification of possible membrane oxidation products has been developed. These oxidation products originate from the attack of hydroxyl or peroxyl radicals on the membrane polymer. Such radicals are formed in situ (during fuel cell operation) or ex situ (Fenton test as oxidative stress simulation). The analysis of membrane oxidation products was carried out by electrospray ionization tandem mass spectrometry. Five potential membrane oxidation products (4-hydroxybenzoic acid (4-HBA), 4-hydroxybenzaldehyde (4-HBAD), 4,4-biphenol (4,4-BP), 4-hydroxybenzenesulfonate (4-HBS), and 4,4-sulfonylbiphenol (4,4-SBP)) were selected based on the molecular structure of the sulfonated polyarylether membrane used. In conjunction with the development of a multiple reaction monitoring (MRM) method, the ionization and fragmentation of the selected compounds were investigated. For 4,4-BP a molecular ion (M(+•) ) was observed in the positive ionization mode and used for MRM method development. Reproducible extraction of the model compounds was achieved using a mixed-mode sorbent material with both weak anion-exchange and reversed-phase retention properties. By using the developed analytical procedure, the identities of two membrane degradation products (4-HBA and 4-HBAD) were determined in situ and ex situ. In addition to the investigation of membrane degradation phenomena, the combination of extraction on a mixed-mode sorbent material and tandem mass spectrometric detection is attractive for the analysis of aromatic sulfonic acids, phenolic acids and phenols.

  12. 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.

  13. 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.

  14. 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. PMID:26102520

  15. Balancing the rates of new bone formation and polymer degradation enhances healing of weight-bearing allograft/polyurethane composites in rabbit femoral defects.

    PubMed

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

    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

  16. 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

  17. 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

  18. 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

  19. 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

  20. Regulation of coal polymer degradation by fungi. Eighth quarterly report, [April--June 1996

    SciTech Connect

    Irvine, R.L.; Bumpus, J.A.

    1996-07-28

    This project addresses the solubilization of low-rank coal (leonardite) by lignin degrading fungi. During this reporting period efforts were focused on determining the effect of pH on coal solubilization by oxalate ion and other biologically important compounds that might function as metal chelators, on the role of laccase in coal solubilization and metabolism, on decolorization of soluble coal macromolecule by Phanerochaete chrysosporium and T. versicolor in solid agar media, and on solubilization of coal in slurry cultures and solid phase reactors.

  1. Polymer Aging Techniques Applied to Degradation of a Polyurethane Propellant Binder

    SciTech Connect

    Assink, R.A.; Celina, M.; Graham, A.C.; Minier, L.M.

    1999-07-27

    The oxidative thermal aging of a crosslinked hydroxy-terminated polybutadiene (HTPB)/isophorone diisocyanate (IPDI) polyurethane rubber, commonly used as the polymeric binder matrix in solid rocket propellants, was studied at temperatures of RT to 125 C. We investigate changes in tensile elongation, mechanical hardening, polymer network properties, density, O{sub 2} permeation and molecular chain dynamics using a range of techniques including solvent swelling, detailed modulus profiling and NMR relaxation measurements. Using extensive data superposition and highly sensitive oxygen consumption measurements, we critically evaluate the Arrhenius methodology, which normally assumes a linear extrapolation of high temperature aging data. Significant curvature in the Arrhenius diagram of these oxidation rates was observed similar to previous results found for other rubber materials. Preliminary gel/network properties suggest that crosslinking is the dominant process at higher temperatures. We also assess the importance of other constituents such as ammonium perchlorate or aluminum powder in the propellant formulation.

  2. Probing biofouling resistant polymer brush surfaces by atomic force microscopy based force spectroscopy.

    PubMed

    Schön, Peter; Kutnyanszky, Edit; ten Donkelaar, Bas; Santonicola, M Gabriella; Tecim, Tugba; Aldred, Nick; Clare, Anthony S; Vancso, G Julius

    2013-02-01

    The protein repellency and biofouling resistance of zwitterionic poly(sulfobetaine methacrylate)(pSBMA) brushes grafted via surface initiated polymerization (SIP) from silicon and glass substrata was assessed using atomic force microscopy (AFM) adherence experiments. Laboratory settlement assays were conducted with cypris larvae of the barnacle Balanus amphitrite. AFM adherence includes the determination of contact rupture forces when AFM probe tips are withdrawn from the substratum. When the surface of the AFM tip is modified, adherence can be assessed with chemical specifity using a method known as chemical force microscopy (CFM). In this study, AFM tips were chemically functionalized with (a) fibronectin- here used as model for a nonspecifically adhering protein - and (b) arginine-glycine-aspartic acid (RGD) peptide motifs covalently attached to poly(methacrylic acid) (PMAA) brushes as biomimics of cellular adhesion receptors. Fibronectin functionalized tips showed significantly reduced nonspecific adhesion to pSBMA-modified substrata compared to bare gold (2.3±0.75 nN) and octadecanethiol (ODT) self-assembled monolayers (1.3±0.75 nN). PMAA and PMAA-RGD modified probes showed no significant adhesion to pSBMA modified silicon substrata. The results gathered through AFM protein adherence studies were complemented by laboratory fouling studies, which showed no adhesion of cypris larvae of Balanus amphitrite on pSBMA. With regard to its unusually high non-specific adsorption to a wide variety of materials the behavior of fibronectin is analogous to the barnacle cyprid temporary adhesive that also binds well to surfaces differing in polarity, charge and free energy. The antifouling efficacy of pSBMA may, therefore, be directly related to the ability of this surface to resist nonspecific protein adsorption. PMID:23138001

  3. Protein interactions with bottle-brush polymer layers: Effect of side chain and charge density ratio probed by QCM-D and AFM.

    PubMed

    Olanya, Geoffrey; Thormann, Esben; Varga, Imre; Makuska, Ricardas; Claesson, Per M

    2010-09-01

    Silica surfaces were coated with a range of cationic bottle-brush polymers with 45 units long poly(ethylene oxide) side chains, and their efficiency in reducing protein adsorption was probed by QCM-D, reflectometry and AFM. Preadsorbed layers formed by bottle-brush polymers with different side chain to charge ratio was exposed to two proteins with different net charge, lysozyme and BSA. The reduction in protein adsorption was found to depend on both the type of protein and on the nature of the polyelectrolyte layer. The most pronounced reduction in protein adsorption was achieved when the fraction of charged backbone segments was in the range 0.25-0.5 equivalent to a fraction of poly(ethylene oxide) side chains of 0.75-0.5. It was concluded that these polymers have enough electrostatic attachment points to ensure a strong binding to the surface, and at the same time a sufficient amount of poly(ethylene oxide) side chains to counteract protein adsorption. In contrast, a layer formed by a highly charged polyelectrolyte without side chains was unable to resists protein adsorption. On such a layer the adsorption of negatively charged BSA was strongly enhanced, and positively charged lysozyme adsorbed to a similar extent as to bare silica. AFM colloidal probe force measurement between silica surfaces with preadsorbed layers of bottle-brush polymers were conducted before and after exposure to BSA and lysozyme to gain insight into how proteins were incorporated in the bottle-brush polymer layers.

  4. Degradable polymeric nanoparticles by aggregation of thermoresponsive polymers and "click" chemistry.

    PubMed

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

    2015-10-28

    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. PMID:26399397

  5. 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.

  6. 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

    2016-05-01

    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. PMID:26808242

  7. Probing the adhesion of particles to responsive polymer coatings with hydrodynamic shear stresses

    NASA Astrophysics Data System (ADS)

    Toomey, Ryan; Efe, Gulnur

    2015-03-01

    Lower critical solution temperature (LCST) polymers in confined geometries have found success in applications that benefit from reversible modulation of surface properties, including drug delivery, separations, tissue cultures, and chromatography. In this talk, we present the adhesion of polystyrene microspheres to cross-linked poly(N-isopropylacrylamide), or poly(NIPAAm) coatings, as studied with a spinning disk method. This method applies a linear range of hydrodynamic shear forces to physically adsorbed microspheres along the radius of a coated disk. Quantification of detachment is accomplished by optical microscopy to evaluate the minimum shear stress to remove adherent particles. Experiments were performed to assess the relationship between the surface chemistry of the microsphere, the thickness and cross-link density of the poly(NIPAAm) coating, the adsorption (or incubation) time, and the temperature on the detachment profiles of the microspheres. Results show that both the shear modulus and slow dynamic processes in the poly(NIPAAm) films strongly influence the detachment shear stresses. Moreover, whether an adsorbed microsphere can be released (through a modulation in the swelling of the poly(NIPAAm) coating by temperature) depends on both the surface chemistry of the microsphere and the extent of the adsorption time. Finally, the results show that the structure of the poly(NIPAAm) coating can significantly affect performance, which may explain several of the conflicting findings that have been reported in the literature.

  8. 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.; 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 weremore » more abstruse due to competitive organic anion adsorption on Pt surfaces superimposing with the hydrogen underpotential deposition (HUPD) region.« less

  9. 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.

  10. DNA Compaction Induced by a Cationic Polymer or Surfactant Impact Gene Expression and DNA Degradation

    PubMed Central

    Ainalem, Marie-Louise; Bartles, Andrew; Muck, Joscha; Dias, Rita S.; Carnerup, Anna M.; Zink, Daniele; Nylander, Tommy

    2014-01-01

    There is an increasing interest in achieving gene regulation in biotechnological and biomedical applications by using synthetic DNA-binding agents. Most studies have so far focused on synthetic sequence-specific DNA-binding agents. Such approaches are relatively complicated and cost intensive and their level of sophistication is not always required, in particular for biotechnological application. Our study is inspired by in vivo data that suggest that DNA compaction might contribute to gene regulation. This study exploits the potential of using synthetic DNA compacting agents that are not sequence-specific to achieve gene regulation for in vitro systems. The semi-synthetic in vitro system we use include common cationic DNA-compacting agents, poly(amido amine) (PAMAM) dendrimers and the surfactant hexadecyltrimethylammonium bromide (CTAB), which we apply to linearized plasmid DNA encoding for the luciferase reporter gene. We show that complexing the DNA with either of the cationic agents leads to gene expression inhibition in a manner that depends on the extent of compaction. This is demonstrated by using a coupled in vitro transcription-translation system. We show that compaction can also protect DNA against degradation in a dose-dependent manner. Furthermore, our study shows that these effects are reversible and DNA can be released from the complexes. Release of DNA leads to restoration of gene expression and makes the DNA susceptible to degradation by Dnase. A highly charged polyelectrolyte, heparin, is needed to release DNA from dendrimers, while DNA complexed with CTAB dissociates with the non-ionic surfactant C12E5. Our results demonstrate the relation between DNA compaction by non-specific DNA-binding agents and gene expression and gene regulation can be achieved in vitro systems in a reliable dose-dependent and reversible manner. PMID:24671109

  11. Influence of the Piping-material-originated Metal-ion on Cell Degradation of Polymer Electrolyte Fuel Cell

    NASA Astrophysics Data System (ADS)

    Amitani, Chieko; Ishikawa, Masahiko; Mori, Kouya; Tanaka, Kenji; Hori, Michio

    Influences of metal-ion adulterations into Polymer Electrolyte Fuel Cells (PEFC) were examined on PEFC generation characteristics and structural changes. Cupper and aluminun, novel candidate materials for forthcoming PEFC system, were introduced into polymer electrolyte membranes (PEM) by ion-exchange method as contaminants, and ca. 500-hour generation tests of PEFC cells with these PEMs were conducted in this study. Introduced metal ions were to be combined to sulfonic acid groups in PEMs by electrostatic forces. For the cell containing cupric ions (Cu2+) equivalent to 1000 pmm of supfonic acid groups in PEM, a decrease in deteriorating rate of cell voltage was observed to be 83 mV/kh during 500-hour generation, in comparison with the cell without metal-ion comtamination showing 154 mV/kh. On the other hand, an increase in deteriorating rates were observed for the cells containing 10 % Cu2+ or 1000 ppm aluminum ions (Al3+). Al3+ adulteration in PEFC set off increases in activation overpotential and fluoride ion release rate (FRR) with proceeding genaration test. An increase in activation overpotentials was supressed in 1000 ppm Cu2+-adulterated cell and the reverse was observed in 10 % Cu2+-adulterated one, though Cu2+ adulterations suppressed growths of platinum catalyst particles in size and FRR regardless of Cu2+ concentration. Restriction effect of 1000 ppm Cu2+-adulteration into PEM on PEFC voltage deterioration has found to be the unprecedented knoledge with respect to PEFC degradation phenomena. Mechanisms of those influences were also discussed.

  12. Investigation of degradation effects in polymer electrolyte fuel cells under automotive-related operating conditions

    NASA Astrophysics Data System (ADS)

    Enz, S.; Dao, T. A.; Messerschmidt, M.; Scholta, J.

    2015-01-01

    The influence of artificial starvation effects during automotive-related operating conditions is investigated within a polymer electrolyte fuel cell (PEFC) using non-dispersive infrared sensors and a current scan shunt. Driving cycles (DC) and single load change experiments are performed with specific fuel and oxidant starvation conditions. Within the DC experiments, a maximal CO2 amount of 4.67 μmol per cycle is detected in the cathode and 0.97 μmol per cycle in the anode exhaust without reaching fuel starvation conditions during the DC. Massive cell reversal conditions occur within the single load change experiments as a result of anodic fuel starvation. As soon as a fuel starvation appears, the emitted CO2 increases exponentially in the anode and cathode exhaust. A maximal CO2 amount of 143.8 μmol CO2 on the anode side and 5.8 μmol CO2 on the cathode side is detected in the exhaust gases. The critical cell reversal conditions only occur by using hydrogen reformate as anode reactant. The influence of the starvation effects on the PEFC performance is investigated via polarization curves, cyclic and linear sweep voltammetry as well as electrochemical impedance spectroscopy. The PEFC performance is reduced by 47% as a consequence of the dynamic operation.

  13. Hierarchical analysis of the degradation of fibre-reinforced polymers under the presence of void imperfections.

    PubMed

    Liebig, Wilfried V; Schulte, Karl; Fiedler, Bodo

    2016-07-13

    The subject of this work is the investigation of the influence of voids on the mechanical properties of fibre-reinforced polymers (FRPs) under compression loading. To specify the damage accumulation of FRPs in the presence of voids, the complex three-dimensional structure of the composite including voids was analysed and a reduced mechanical model composite was derived. The hierarchical analysis of the model composite on a micro-scale level implies the description of the stress and strain behaviour of the matrix using the photoelasticity technique and digital image correlation technology. These studies are presented along with an analytical examination of the stability of a single fibre. As a result of the experimental and analytical studies, the stiffness of the matrix and fibre as well as their bonding, the initial fibre orientation and the fibre diameter have the highest impact on the failure initiation. All these facts lead to a premature fibre-matrix debonding with ongoing loss of stability of the fibre and followed by kink-band formation. Additional studies on the meso-scale of transparent glass FRPs including a unique void showed that the experiments carried out on the model composites could be transferred to real composites. This article is part of the themed issue 'Multiscale modelling of the structural integrity of composite materials'. PMID:27242296

  14. Magnetic and degradable polymer/bioactive glass composite nanoparticles for biomedical applications.

    PubMed

    Jayalekshmi, A C; Victor, Sunita Prem; Sharma, Chandra P

    2013-01-01

    The present study focuses on the development of a biocompatible and biodegradable iron oxide incorporated chitosan-gelatin bioglass composite nanoparticles [Fe-BG]. The developed composite nanoparticle was analyzed by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, thermo gravimetric analysis (TG) and differential scanning calorimetry analysis (DSC). The size of the negatively charged composite nanoparticle was in the range of 43-51 nm. The in vitro analysis of the composite nanoparticles was carried out by cell aggregation, protein adsorption and haemolytic activity. The magnetic hysteresis value of the composite nanoparticle showed that it is a soft magnetic material. The presence of iron oxide in the chitosan-gelatin bioglass [BG] matrix enhances biodegradability as indicated in the TG studies. Iron-oxide in equal amount to bioglass in the polymer matrix has been obtained as the optimized system. The developed composite nanoparticle is a soft magnetic material and is suitable for the magnetic hyperthermia treatment and drug delivery. More detailed in vivo studies are needed to confirm the biodegradation profile and biological activity of the material.

  15. 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.

  16. 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

    2015-10-01

    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

  17. 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

    2015-10-01

    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

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

    PubMed

    Washington, John W; Jenkins, Thomas M; Weber, Eric J

    2015-11-17

    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 bond between the α-β carbons for the unsaturated PFCAs (2uPFCAs). Obtaining an authentic sample containing 2uPFOA and 2HPFOA, we optimized a mass-spectrometric multiple-reaction-monitoring (MS/MS) technique and then identified uPFCA and HPFCA homologous series in sludge-applied agricultural soils and fodder grasses for cattle grazing. Analysis of samples from a degradation experiment of commercial fluorotelomer-based polymers (FTPs), the dominant product of the fluorotelomer industry, confirmed that commercial FTPs are a potential source of uPFCAs and HPFCAs to the environment. We further confirmed the identity of the uPFCAs by imposing high-energy ionization to decarboxylate the uPFCAs then focused on the fluorinated chains in the first MS quadrupole. We also employed this high-energy ionization to decarboxylate and analyze PFCAs by MS/MS (for the first time, to our knowledge). In exploratory efforts, we report the possible detection of unsaturated perfluorooctanesulfonate in environmental samples, having a conceptual double-bond structure analogous to uPFOA. Using microcosms spiked with fluorotelomer compounds, we found 2uPFOA and 2HPFOA to be generated from unsaturated 8:2 fluorotelomer acid (8:2 FTUCA) and propose β- and α-oxidation mechanisms for generation of these compounds from 8:2 FTUCA. In light of these experimental results, we also reexamined the proposed biodegradation pathways of 8:2 fluorotelomer alcohol.

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

    PubMed

    Washington, John W; Jenkins, Thomas M; Weber, Eric J

    2015-11-17

    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 bond between the α-β carbons for the unsaturated PFCAs (2uPFCAs). Obtaining an authentic sample containing 2uPFOA and 2HPFOA, we optimized a mass-spectrometric multiple-reaction-monitoring (MS/MS) technique and then identified uPFCA and HPFCA homologous series in sludge-applied agricultural soils and fodder grasses for cattle grazing. Analysis of samples from a degradation experiment of commercial fluorotelomer-based polymers (FTPs), the dominant product of the fluorotelomer industry, confirmed that commercial FTPs are a potential source of uPFCAs and HPFCAs to the environment. We further confirmed the identity of the uPFCAs by imposing high-energy ionization to decarboxylate the uPFCAs then focused on the fluorinated chains in the first MS quadrupole. We also employed this high-energy ionization to decarboxylate and analyze PFCAs by MS/MS (for the first time, to our knowledge). In exploratory efforts, we report the possible detection of unsaturated perfluorooctanesulfonate in environmental samples, having a conceptual double-bond structure analogous to uPFOA. Using microcosms spiked with fluorotelomer compounds, we found 2uPFOA and 2HPFOA to be generated from unsaturated 8:2 fluorotelomer acid (8:2 FTUCA) and propose β- and α-oxidation mechanisms for generation of these compounds from 8:2 FTUCA. In light of these experimental results, we also reexamined the proposed biodegradation pathways of 8:2 fluorotelomer alcohol. PMID:26484632

  20. Development of a novel fluorescent imaging probe for tumor hypoxia by use of a fusion protein with oxygen-dependent degradation domain of HIF-1α

    NASA Astrophysics Data System (ADS)

    Tanaka, Shotaro; Kizaka-Kondoh, Shinae; Harada, Hiroshi; Hiraoka, Masahiro

    2007-02-01

    More malignant tumors contain more hypoxic regions. In hypoxic tumor cells, expression of a series of hypoxiaresponsive genes related to malignant phenotype such as angiogenesis and metastasis are induced. Hypoxia-inducible factor-1 (HIF-1) is a master transcriptional activator of such genes, and thus imaging of hypoxic tumor cells where HIF-1 is active, is important in cancer therapy. We have been developing PTD-ODD fusion proteins, which contain protein transduction domain (PTD) and the VHL-mediated protein destruction motif in oxygen-dependent degradation (ODD) domain of HIF-1 alpha subunit (HIF-1α). Thus PTD-ODD fusion proteins can be delivered to any tissue in vivo through PTD function and specifically stabilized in hypoxic cells through ODD function. To investigate if PTD-ODD fusion protein can be applied to construct hypoxia-specific imaging probes, we first constructed a fluorescent probe because optical imaging enable us to evaluate a probe easily, quickly and economically in a small animal. We first construct a model fusion porein PTD-ODD-EGFP-Cy5.5 named POEC, which is PTD-ODD protein fused with EGFP for in vitro imaging and stabilization of fusion protein, and conjugated with a near-infrared dye Cy5.5. This probe is designed to be degraded in normoxic cells through the function of ODD domain and followed by quick clearance of free fluorescent dye. On the other hand, this prove is stabilized in hypoxic tumor cells and thus the dye is stayed in the cells. Between normoxic and hypoxic conditions, the difference in the clearance rate of the dye will reveals suited contrast for tumor-hypoxia imaging. The optical imaging probe has not been optimized yet but the results presented here exhibit a potential of PTD-ODD fusion protein as a hypoxia-specific imaging probe.

  1. 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. PMID:27511953

  2. Thermal desorption characterisation of molecularly imprinted polymers. Part II: Use of direct probe GC-MS analysis to study crosslinking effects.

    PubMed

    Holland, Niamh; Duggan, Patrick; Owens, Eleanor; Cummins, Wayne; Frisby, June; Hughes, Helen; McLoughlin, Peter

    2008-06-01

    A powerful method utilising direct probe thermal desorption GC-MS is presented for the study of molecularly imprinted polymers (MIPs). A series of 2-aminopyridine (2-apy)-imprinted methacrylic acid-ethyleneglycol dimethacrylate (MAA-EGDMA) copolymers were prepared under identical conditions but with varying amounts of EGDMA (crosslinking monomer). The use of appropriate temperature programmes permitted template removal, and the subsequent assessment of polymer affinity and specificity, all of which were found to be dependent on polymer composition and morphology. The system was sufficiently sensitive to identify a specific response of imprinted polymers over nonimprinted counterparts. Correlations were found to exist between thermal desorption analysis and solution phase binding, which was assessed by UV spectroscopy, where specificity was found to diminish with decreasing EGDMA concentration. This was attributed to the increased number of free carboxyl groups in those polymers containing a lower percentage of EGDMA. Thermal desorption profiles obtained for the analyte were found to be unaffected by the physical and chemical properties of the solvent used for analyte reloading.

  3. 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.

  4. Formation of analogs of cometary nitrogen-rich refractory organics from thermal degradation of tholin and HCN polymer

    NASA Astrophysics Data System (ADS)

    Bonnet, Jean-Yves; Quirico, Eric; Buch, Arnaud; Thissen, Roland; Szopa, Cyril; Carrasco, Nathalie; Cernogora, Guy; Fray, Nicolas; Cottin, Hervé; Roy, Lena Le; Montagnac, Gilles; Dartois, Emmanuel; Brunetto, Rosario; Engrand, Cécile; Duprat, Jean

    2015-04-01

    Nitrogen-rich refractory organics are scarce phases recovered as a fraction of stratospheric IDPs and constitute the bulk of the organic matter of some ultracarbonaceous Antarctic micrometeorites. They are likely formed under very specific conditions within a nitrogen-rich environment and may provide valuable clues on the origin of the population of interplanetary dusts accreted by Earth. In this study, we produced relevant analogs of such refractory organics characterized in three ultracarbonaceous Antarctic micrometeorites, starting from the carbonization of an HCN polymer and a tholin. Indeed, carbonization is a process that can increase the polyaromatic character toward a structure similar to that observed in these cosmomaterials. Both these precursors were degraded in an Ar atmosphere at 300, 500, 700 and 1000 °C over ∼1 h and characterized by elemental analysis, micro-FTIR and Raman micro-spectroscopy (at 244 and 514 nm excitation wavelengths). Our results show that the precursors evolve along distinct chemical and structural pathways during carbonization and that the influence of the precursor structure is still very strong at 1000 °C. Interestingly, these different carbonization routes appear in the spectral characteristics of the G and D bands of their Raman spectra. Several of the residues present chemical and structural similarities with three recently studied ultracarbonaceous micrometeorites (Dobrica et al. [2011]. Meteorit. Planet. Sci. 46, 1363; Dartois et al. [2013]. Icarus 224, 243) and with N-rich inclusions in stratospheric IDPs. However, the residues do not simultaneously account for the carbon structure (Raman) and the chemical composition (IR, N/C ratio). This indicates that the precursors and/or heating conditions in our experiments are not fully relevant. Despite this lack of full relevancy, the formation of a polyaromatic structure fairly similar to that of UCAMMs and IDPs suggests that the origin of N-rich refractory organics lies in a

  5. Patterned enzymatic degradation of poly(ε-caprolactone) by high-affinity microcontact printing and polymer pen lithography.

    PubMed

    Ganesh, Manoj; Nachman, Jonathan; Mao, Zhantong; Lyons, Alan; Rafailovich, Miriam; Gross, Richard

    2013-08-12

    This paper reports deposition of Candida antarctica Lipase B (CALB) on relatively thick poly(ε-caprolactone) (PCL) films (300-500 nm) to create well-defined patterns using two different writing techniques: high-affinity microcontact (HA-μCL) and polymer pen (PPL) lithography. For both, an aqueous CALB ink is absorbed onto a polydimethylsiloxane (PDMS) writing implement (PDMS stamp or a PDMS pen tip), which is transferred to a spun-cast PCL film. HA-μCL experiments demonstrated the importance of applied pressure to obtain high-resolution patterns since uniform contact is needed between raised 20 μm parallel line regions of the PDMS stamp and the surface. AFM imaging shows pattern formation evolves gradually over incubation time only in areas stamped with CALB cutting through spherulites without apparent influence by grain boundaries. Strong binding of CALB to PCL is postulated as the mechanism by which lateral diffusion is limited. PPL enables formation of an arbitrary image by appropriate programming of the robot. The PDMS pen tips were coated with an aqueous CALB solution and then brought into contact with the PCL film to transfer CALB onto the surface. By repeating the ink transfer step multiple times where pen tips are brought into contact with the PCL film at a different locations, a pattern of dots is formed. After printing, patterns were developed at 37 °C and 95% RH. Over a 7-day period, CALB progressively etched the PCL down to the silicon wafer on which it was spun (350 nm) giving round holes with diameters about 10 μm. AFM images show the formation of steep PCL walls indicating CALB degraded the PCL film in areas to which it was applied. This work demonstrates that high-resolution patterns can be achieved without immobilizing the enzyme on the surface of polymeric stamps that limits the depth of features obtained as well as the throughput of the process. PMID:23808571

  6. 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...

  7. Degradation of Terfenol-D particle epoxy composites under low frequency cyclic magneto-mechanical loading: comparisons of matrix polymer

    NASA Astrophysics Data System (ADS)

    Armstrong, William D.; Shanmugham, Manikantan

    2005-05-01

    Magnetostrictive Terfenol-D particle actuated epoxy polymer matrix composites were prepared with polyamine and anhydride cured epoxy polymer matrices. The different matrix epoxies exhibited large differences in glass transition and creep behavior. The differences in matrix thermal-mechanical properties resulted in important differences in temperature dependant damage behavior and magneto-elastic strain output in the Terfenol-D particle actuated epoxy polymer matrix composites.

  8. Use of molecularly imprinted polymers from a mixture of tetracycline and its degradation products to produce affinity membranes for the removal of tetracycline from water.

    PubMed

    Suedee, Roongnapa; Srichana, Teerapol; Chuchome, Thitima; Kongmark, Urairut

    2004-11-25

    The possibility of introducing multiple recognition in artificial receptors by imprinting polymers, using a mixture of tetracycline (TC) and its degradation products as templates, has been examined. The recognition ability of the resulting molecularly imprinted polymer (MIP), as evaluated by batch rebinding assay, was found to be group-specific to tetracyclines, while the single tetracycline imprinted polymer (MIP-2) prepared using TC free from degradation products as the print molecule showed considerably high selectivity for doxycycline (DC) and modest selectivity for TC and other TC derivatives, oxytetracycline (OTC) and chlortetracycline (CTC). Based on the recognition property of the multiple tetracycline imprinted polymer (MIP-1), the polymer was applied in affinity membrane extraction as a class-selective adsorption phase to remove tetracyclines residues from water. For this purpose, the ground MIP was incorporated in a plasticized poly(vinyl chloride)-membrane by casting method. Affinity separation of the obtained membrane was evaluated for the extraction of tetracycline and its analogs (CTC, OTC or DC) in aqueous solutions by a dialysis method. The membrane exhibited significantly stronger extraction ability towards tetracycline and structurally related compounds than a "blank" membrane having a non-printed polymer (NIP) as the adsorption phase. The result of these membrane extraction studies also indicates that the drug saturating at the receptor sites of MIP (deposited in membrane) faster will also be released into the receptor chamber faster. These affinity membranes were able to extract tetracyclines from water at all pHs, the highest selectivity being shown at pH 7 of the feed solution, which gives the lowest flux of the drug. Moreover, presence of salt in the feed solution increases the release of tetracycline bound in membrane. The results of the present study show that imprinting simultaneous with TC and TC degradation products formed in situ as a

  9. 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.

  10. ESR spectroscopy as a powerful tool for probing the quality of conjugated polymers designed for photovoltaic applications.

    PubMed

    Susarova, Diana K; Piven, Natalia P; Akkuratov, Alexander V; Frolova, Lyubov A; Polinskaya, Marina S; Ponomarenko, Sergey A; Babenko, Sergey D; Troshin, Pavel A

    2015-02-11

    Here we report the application of the Electron Spin Resonance (ESR) spectroscopy as a highly sensitive analytical technique for assessment of the electronic quality of organic semiconductor materials, particularly conjugated polymers. It has been shown that different batches of the same conjugated polymer might contain substantially different amounts of radical species which were attributed to structural defects and/or impurities behaving as traps for mobile charge carriers. Good correlations between the concentrations of radicals in various batches of conjugated polymers and their performances in organic solar cells have been revealed. PMID:25370184

  11. Evaluation of atmospheric solid analysis probe ionization coupled to ion mobility mass spectrometry for characterization of poly(ether ether ketone) polymers.

    PubMed

    Cossoul, Emilie; Hubert-Roux, Marie; Sebban, Muriel; Churlaud, Florence; Oulyadi, Hassan; Afonso, Carlos

    2015-01-26

    Recently, the interest of the coupling between atmospheric solid analysis probe (ASAP) and ion mobility-mass spectrometry has been revealed in the field of polymers. This method associates a direct ionization technique with a bi-dimensional separation method. Poly(ether ether ketones) (PEEK) belong to the family of the poly(aryl ether ketones) (PAEK) which are high performance aromatic polymers usually used in aerospace, electronics and nuclear industries. PEEK are important commercial thermoplastics with excellent chemical resistance and good mechanical properties. Because of their low solubility, few structural characterization studies of PEEK have been reported. In mass spectrometry, only MALDI-TOF analyses for polymer synthesis monitoring have been described with the use of strong acids such as sulfuric acid. This work demonstrates that ASAP is particularly efficient for analysis of PEEK in a solvent free approach with the production of intact small oligomers (n≤2). Five types of PEEK oligomers with different end-groups were evidenced. With MALDI-TOF, the same end-groups with almost the same relative abundance were obtained which support the hypothesis that the oligomers detected in ASAP are intact small oligomers and not fragments or pyrolysis products. This is particularly interesting as generally the ASAP analysis of polymers yields pyrolysis products with the loss of end-group information. The end-groups assignments have been confirmed by tandem mass spectrometry (MS/MS) experiments on the M(+) molecular ions, which allowed highlighting some specific neutral or radical losses as well as two diagnostic product ions. Thus, ASAP-IM/MS/MS proves to be a fast and efficient alternative way to characterize low solubility polymers such as PEEK. PMID:25542357

  12. Probing the Degradation Mechanism of Li2MnO3 Cathode for Li-Ion Batteries

    SciTech Connect

    Yan, Pengfei; Xiao, Liang; Zheng, Jianming; Zhou, Yungang; He, Yang; Zu, Xiaotao; Mao, Scott X.; Xiao, Jie; Gao, Fei; Zhang, Jiguang; Wang, Chong M.

    2015-02-10

    Capacity and voltage fading of Li2MnO3 is a major challenge for the application of this category of material, which is believed to be associated with the structural and chemical evolution of the materials. This paper reports the detailed structural and chemical evolutions of Li2MnO3 cathode captured by using aberration corrected scanning/transmission electron microscope (S/TEM) after certain numbers of charge-discharge cycling of the batteries. It is found that structural degradation occurs from the very first cycle and is spatially initiated from the surface of the particle and propagates towards the inner bulk as cyclic number increase, featuring the formation of the surface phase transformation layer and gradual thickening of this layer. The structure degradation is found to follow a sequential phase transformation: monoclinic C2/m → tetragonal I41 → cubic spinel, which is consistently supported by the decreasing lattice formation energy based on DFT calculations. For the first time, high spatial resolution quantitative chemical analysis reveals that 20% oxygen in the surface phase transformation layer is removed and such newly developed surface layer is a Li-depleted layer with reduced Mn cations. This work demonstrates a direct correlation between structural degradation and cell’s electrochemical degradation, which enhances our understanding of Li-Mn-rich (LMR) cathode materials.

  13. 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.

  14. Thickness Dependent Effective Viscosity of a Polymer Solution near an Interface Probed by a Quartz Crystal Microbalance with Dissipation Method

    PubMed Central

    Fang, Jiajie; Zhu, Tao; Sheng, Jie; Jiang, Zhongying; Ma, Yuqiang

    2015-01-01

    The solution viscosity near an interface, which affects the solution behavior and the molecular dynamics in the solution, differs from the bulk. This paper measured the effective viscosity of a dilute poly (ethylene glycol) (PEG) solution adjacent to a Au electrode using the quartz crystal microbalance with dissipation (QCM-D) technique. We evidenced that the effect of an adsorbed PEG layer can be ignored, and calculated the zero shear rate effective viscosity to remove attenuation of high shear frequency oscillations. By increasing the overtone n from 3 to 13, the thickness of the sensed polymer solution decreased from ~70 to 30 nm. The zero shear rate effective viscosity of the polymer solution and longest relaxation time of PEG chains within it decrease with increasing solution thickness. The change trends are independent of the relation between the apparent viscosity and shear frequency and the values of the involved parameter, suggesting that the polymer solution and polymer chains closer to a solid substrate have a greater effective viscosity and slower relaxation mode, respectively. This method can study the effect of an interface presence on behavior and phenomena relating to the effective viscosity of polymer solutions, including the dynamics of discrete polymer chains. PMID:25684747

  15. Thickness Dependent Effective Viscosity of a Polymer Solution near an Interface Probed by a Quartz Crystal Microbalance with Dissipation Method

    NASA Astrophysics Data System (ADS)

    Fang, Jiajie; Zhu, Tao; Sheng, Jie; Jiang, Zhongying; Ma, Yuqiang

    2015-02-01

    The solution viscosity near an interface, which affects the solution behavior and the molecular dynamics in the solution, differs from the bulk. This paper measured the effective viscosity of a dilute poly (ethylene glycol) (PEG) solution adjacent to a Au electrode using the quartz crystal microbalance with dissipation (QCM-D) technique. We evidenced that the effect of an adsorbed PEG layer can be ignored, and calculated the zero shear rate effective viscosity to remove attenuation of high shear frequency oscillations. By increasing the overtone n from 3 to 13, the thickness of the sensed polymer solution decreased from ~70 to 30 nm. The zero shear rate effective viscosity of the polymer solution and longest relaxation time of PEG chains within it decrease with increasing solution thickness. The change trends are independent of the relation between the apparent viscosity and shear frequency and the values of the involved parameter, suggesting that the polymer solution and polymer chains closer to a solid substrate have a greater effective viscosity and slower relaxation mode, respectively. This method can study the effect of an interface presence on behavior and phenomena relating to the effective viscosity of polymer solutions, including the dynamics of discrete polymer chains.

  16. 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.

  17. Two-photon excited quantum dots with compact surface coatings of polymer ligands used as an upconversion luminescent probe for dopamine detection in biological fluids.

    PubMed

    Jin, Hui; Gui, Rijun; Wang, Zonghua; Zhang, Feifei; Xia, Jianfei; Yang, Min; Bi, Sai; Xia, Yanzhi

    2015-03-21

    Water-soluble multidentate polymer coated CdTe quantum dots (QDs) were prepared via a stepwise addition of raw materials in a one-pot aqueous solution under ambient conditions. Just by adjusting the compositions of raw materials, different sized CdTe QDs were achieved within a short time. The as-prepared QDs showed compact surface coating (1.6-1.8 nm) of polymer ligands and photoluminescence (PL) emitted at 533-567 nm, as well as high colloidal/photo-stability and quantum yields (58-67%). Moreover, these QDs exhibited significant upconversion luminescence (UCL) upon excitation using an 800 nm femtosecond laser. Experimental results confirm that the UCL was ascribed to the two-photon assisted process via a virtual energy state. Then, the two-photon excited QDs were further developed as a novel UCL probe of dopamine (DA) due to self-assembled binding of DA molecules with QDs via non-covalent bonding. As a receptor, the DA attached onto the QD surface induced an electron transfer from QDs to DA, triggering UCL quenching of QDs. This UCL probe of DA presented a low limit of detection (ca. 5.4 nM), and high selectivity and sensitivity in the presence of potential interferences. In particular, it was favorably applied to the detection of DA in biological fluids, with quantitative recoveries (96.0-102.6%). PMID:25684191

  18. 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.

  19. Small changes in polymer chemistry have a large effect on the bone-implant interface: evaluation of a series of degradable tyrosine-derived polycarbonates in bone defects.

    PubMed

    James, K; Levene, H; Parsons, J R; Kohn, J

    1999-12-01

    In a series of homologous, tyrosine-based polycarbonates, small changes in the chemical structure of the polymer pendent chain were found to affect the bone response in a long-term (1280 d) implantation study. Identically sized pins, prepared from poly(DTE carbonate), poly(DTB carbonate), poly(DTH carbonate), and poly(DTO carbonate) were implanted transcortically in the proximal tibia and the distal femur of skeletally mature New Zealand White Rabbits. The tissue response at the bone-implant interface was characterized in terms of the absence of a fibrous capsule (direct bone apposition, indicative of a bone bonding response) or the presence of a fibrous capsule (referred to as the encapsulation response). The relative frequency of direct bone apposition versus encapsulation was recorded for each polymer throughout the entire period of the study. While all four polymers were tissue compatible, there was a correlation between the chemical structure of the pendent chain and the type of bone response observed, with poly(DTE carbonate) having the highest tendency to elicit direct bone apposition. Based on in vivo degradation data and the ability of model polymers with carboxylate groups at their surface to chelate calcium ions, it is proposed that the ability of poly(DTE carbonate) to bond to bone is caused by the facile hydrolysis of the pendent ethyl ester groups which creates calcium ion chelation sites on the polymer surface. The incorporation of calcium chelation sites into the chemical structure of an implant material appears to be a key requirement if direct bone apposition/bone bonding is desired. This study demonstrates that very subtle changes in the chemical composition of an implant material can have significant effects on the long-term tissue response in a clinically relevant model.

  20. 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.

  1. 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. PMID:25353500

  2. 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.

  3. 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

  4. A strategy for the systematic development of a liquid chromatographic mass spectrometric screening method for polymer electrolyte membrane degradation products using isocratic and gradient phase optimized liquid chromatography.

    PubMed

    Zedda, M; Tuerk, J; Teutenberg, T; Peil, S; Schmidt, T C

    2009-12-18

    Within the scope of research for target and non-target LC-MS/MS analysis of membrane degradation products of polymer electrolyte membrane fuel cells, a systematic method development for the separation of structurally similar compounds was performed by phase optimized liquid chromatography. Five different stationary phases with different selectivities were used. Isocratic separation for 4-hydroxybenzoic acid, isophthalic acid, terephthalic acid, 4-hydroxybenzaldehyde and 4-formylbenzoic acid was achieved on a C18 and a Phenyl phase. Using the PRISMA model the separation efficiency was optimized. This was achieved on a serially connected mixed stationary phase composed of 30 mm C18, 150 mm Phenyl and 60 mm C30. For the LC-MS screening of unknown degradation products from polymer electrolyte membranes in the product water of a fuel cell, a solvent gradient is mandatory for less polar or later eluting compounds. By means of 4-mercaptobenzoic acid it could be shown that a solvent gradient can be applied in order to elute later eluting compounds in a short time. The adaptability of this method for the qualitative analysis by target and non-target LC-MS/MS screening has been shown by means of 4-hydroxybenzoic acid. The combination of solvent gradient and isocratic conditions makes this approach attractive for the purpose of a screening method for known and unknown analytes in a water sample.

  5. Resonant Soft X-Ray Contrast Variation Methods as Composition-Specific Probes of Thin Polymer Film Structure

    SciTech Connect

    Welch, Cynthia; Welch, Cynthia F.; Hjelm, Rex P.; Mang, Joseph T.; Hawley, Marilyn E.; Wrobleski, Debra A.; Orler, E. Bruce; Kortright, Jeffrey B

    2008-04-04

    We have developed complementary soft x-ray scattering and reflectometry techniques that allow for the morphological analysis of thin polymer films without resorting to chemical modification or isotopic 2 labeling. With these techniques, we achieve significant, x-ray energy-dependent contrast between carbon atoms in different chemical environments using soft x-ray resonance at the carbon edge. Because carbon-containing samples absorb strongly in this region, the scattering length density depends on both the real and imaginary parts of the atomic scattering factors. Using a model polymer film of poly(styrene-b-methyl methacrylate), we show that the soft x-ray reflectivity data is much more sensitive to these atomic scattering factors than the soft x-ray scattering data. Nevertheless, fits to both types of data yield useful morphological details on the polymer?slamellar structure that are consistent with each other and with literature values.

  6. 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.

  7. 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

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

    PubMed

    Congdon, Thomas; Dean, Bethany T; Kasperczak-Wright, James; Biggs, Caroline I; Notman, Rebecca; Gibson, Matthew I

    2015-09-14

    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.

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

    PubMed

    Congdon, Thomas; Dean, Bethany T; Kasperczak-Wright, James; Biggs, Caroline I; Notman, Rebecca; Gibson, Matthew I

    2015-09-14

    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

  10. 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.

  11. Thermal degradation of β-carotene studied by ion mobility atmospheric solid analysis probe mass spectrometry: full product pattern and selective ionization enhancement.

    PubMed

    Xiao, Xiaoyin; Miller, Lance L; Bernstein, Robert; Hochrein, James M

    2016-04-01

    Atmospheric solid analysis probe mass spectrometry has the capability of capturing full product patterns simultaneously including both volatile and semi-volatile compounds produced at elevated temperatures. Real-time low-energy collision-induced fragmentation combined with ion mobility separations enables rapid identification of the chemical structures of products. We present here for the first time the recognition of full product patterns resulting from the thermal degradation of β-carotene at temperatures up to 600 °C. Solvent vapor-induced ionization enhancement is observed, which reveals parallel thermal dissociation processes that lead to even- and odd-numbered mass products. The drift-time distributions of high mass products, along with β-carotene, were monitored with temperature, showing multiple conformations that are associated with the presence of two β-rings. Products of masses 346/347, however, show a single conformation distribution, which indicates the separation of two β-rings resulting from the direct bond scission at the polyene hydrocarbon chain. The thermal degradation pathways are evaluated and discussed. PMID:27041662

  12. 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. PMID:25873466

  13. 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.

  14. 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

  15. Development of efficiency improved polymer-modified TiO2 for the photocatalytic degradation of an organic dye from wastewater environment

    NASA Astrophysics Data System (ADS)

    Sangareswari, Murugan; Meenakshi Sundaram, Mariappan

    2015-10-01

    In this study, the photocatalytic activity of polypyrrole-TiO2 nanocomposite was studied experimentally for the degradation of methylene blue (MB) dye under simulating solar light irradiation. To improve the photocatalytic activity of TiO2 under sunlight irradiation, conducting polymers such as polypyrrole (PPy) and its derivatives are generally used as photosensitizers. The PPy-TiO2 nanocomposite was prepared by the chemical oxidative polymerization method. The prepared nanocomposite showed better photocatalytic activity than bare TiO2 under sunlight irradiation for the degradation of MB dye. The prepared nanocomposite was subjected to characterization techniques such as SEM-EDAX, FT-IR, UV-DRS, XRD, TGA and PL spectral analysis. Different influencing operating parameters like initial concentration of dye, irradiation time, pH and amount of PPy-TiO2 nanocomposite used have also been studied. The optical density of the dye degradation was measured by UV-Visible spectrophotometer. The repeatability of photocatalytic activity was also tested. A plausible mechanism was proposed and discussed on the basis of experimental results.

  16. 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.

  17. Functional analysis of an anaerobic m-xylene-degrading enrichment culture using protein-based stable isotope probing.

    PubMed

    Bozinovski, Dragana; Herrmann, Steffi; Richnow, Hans-Hermann; von Bergen, Martin; Seifert, Jana; Vogt, Carsten

    2012-07-01

    A sulfate-reducing consortium maintained for several years in the laboratory with m-xylene as sole source of carbon and energy was characterized by terminal restriction fragment length polymorphism (T-RFLP) fingerprinting of PCR-amplified 16S rRNA genes and stable isotope probing of proteins (Protein-SIP). During growth upon m-xylene or methyl-labeled m-xylene (1,3-dimethyl-(13)C(2)-benzene), a phylotype affiliated to the family Desulfobacteriaceae became most abundant. A second dominant phylotype was affiliated to the phylum Epsilonproteobacteria. In cultures grown with methyl-labeled m-xylene, 331 proteins were identified by LC-MS/MS analysis. These proteins were either not (13)C-labeled (23%) or showed a (13)C-incorporation of 19-22 atom% (13)C (77%), the latter demonstrating that methyl groups of m-xylene were assimilated. (13)C-labeled proteins were involved in anaerobic m-xylene biodegradation, in sulfate reduction, in the Wood-Ljungdahl-pathway, and in general housekeeping functions. Thirty-eight percent of the labeled proteins were affiliated to Deltaproteobacteria. Probably due to a lack of sequence data from Epsilonproteobacteria, only 14 proteins were assigned to this phylum. Our data suggest that m-xylene is assimilated by the Desulfobacteriaceae phylotype, whereas the role of the Epsilonproteobacterium in the consortium remained unclear.

  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. Probing dispersion and re-agglomeration phenomena upon melt-mixing of polymer-functionalized graphite nanoplates.

    PubMed

    Santos, R M; Vilaverde, C; Cunha, E; Paiva, M C; Covas, J A

    2016-01-01

    A one-step melt-mixing method is proposed to study dispersion and re-agglomeration phenomena of the as-received and functionalized graphite nanoplates in polypropylene melts. Graphite nanoplates were chemically modified via 1,3-dipolar cycloaddition of an azomethine ylide and then grafted with polypropylene-graft-maleic anhydride. The effect of surface functionalization on the dispersion kinetics, nanoparticle re-agglomeration and interface bonding with the polymer is investigated. Nanocomposites with 2 or 10 wt% of as-received and functionalized graphite nanoplates were prepared in a small-scale prototype mixer coupled to a capillary rheometer. Samples were collected along the flow axis and characterized by optical microscopy, scanning electron microscopy and electrical conductivity measurements. The as-received graphite nanoplates tend to re-agglomerate upon stress relaxation of the polymer melt. The covalent attachment of a polymer to the nanoparticle surface enhances the stability of dispersion, delaying the re-agglomeration. Surface modification also improves interfacial interactions and the resulting composites presented improved electrical conductivity. PMID:26439171

  20. 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

    NASA Astrophysics Data System (ADS)

    Miller, Laurence G.; Warner, Karen L.; Baesman, Shaun M.; Oremland, Ronald S.; McDonald, Ian R.; Radajewski, Stefan; Murrell, J. Colin

    2004-08-01

    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.

  1. 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.

  2. Use of field-based stable isotope probing to identify adapted populations and track carbon flow through a phenol-degrading soil microbial community.

    PubMed

    DeRito, Christopher M; Pumphrey, Graham M; Madsen, Eugene L

    2005-12-01

    The goal of this field study was to provide insight into three distinct populations of microorganisms involved in in situ metabolism of phenol. Our approach measured 13CO2 respired from [13C]phenol and stable isotope probing (SIP) of soil DNA at an agricultural field site. Traditionally, SIP-based investigations have been subject to the uncertainties posed by carbon cross-feeding. By altering our field-based, substrate-dosing methodologies, experiments were designed to look beyond primary degraders to detect trophically related populations in the food chain. Using gas chromatography-mass spectrometry (GC/MS), it was shown that (13)C-labeled biomass, derived from primary phenol degraders in soil, was a suitable growth substrate for other members of the soil microbial community. Next, three dosing regimes were designed to examine active members of the microbial community involved in phenol metabolism in situ: (i) 1 dose of [13C]phenol, (ii) 11 daily doses of unlabeled phenol followed by 1 dose of [13C]phenol, and (iii) 12 daily doses of [13C]phenol. GC/MS analysis demonstrated that prior exposure to phenol boosted 13CO2 evolution by a factor of 10. Furthermore, imaging of 13C-treated soil using secondary ion mass spectrometry (SIMS) verified that individual bacteria incorporated 13C into their biomass. PCR amplification and 16S rRNA gene sequencing of 13C-labeled soil DNA from the 3 dosing regimes revealed three distinct clone libraries: (i) unenriched, primary phenol degraders were most diverse, consisting of alpha-, beta-, and gamma-proteobacteria and high-G+C-content gram-positive bacteria, (ii) enriched primary phenol degraders were dominated by members of the genera Kocuria and Staphylococcus, and (iii) trophically related (carbon cross-feeders) were dominated by members of the genus Pseudomonas. These data show that SIP has the potential to document population shifts caused by substrate preexposure and to follow the flow of carbon through terrestrial microbial

  3. 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 ...

  4. Identification of hexahydro-1,3,5-trinitro-1,3,5-triazine-degrading microorganisms via 15N-stable isotope probing.

    PubMed

    Roh, Hyungkeun; Yu, Chang-Ping; Fuller, Mark E; Chu, Kung-Hui

    2009-04-01

    This study reported the application of 15N-stable isotope probing (SIP) to identify active hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX)-utilizing microorganisms in groundwater microcosms. Fifteen 16S rRNA gene sequences were derived from the 15N-DNA fraction (contributed from active microorganisms capable of using RDX as a nitrogen source) of microcosms receiving cheese whey. The 16S rRNA gene sequences belonged to Actinobacteria (two clones), alpha-Proteobacteria (seven clones), and gamma-Proteobacteria (six clones). Except for five sequences with high similarity to two known RDX degraders (Enterobacter cloacae and Pseudomonas fluorescens I-C), our results suggested that phylogenetically diverse microorganisms were capable of using RDX as a nitrogen source. Six sequences of the xplA gene (a known RDX-degrading catabolic gene) were detected from the 15N-DNA fraction. The xplA gene sequences were 96-99% similar to the xplA gene of Rhodococcus sp. DN22(a known RDX utilizer), suggesting that other RDX utilizers might contain xplA-like genes. Twenty-five 16S rRNA gene sequences recovered from the unenriched, RDX-contaminated groundwater clustered differently from those obtained from the 15N-DNA fraction of the cheese-whey-amended microcosm. Our results suggested that active RDX utilizers can be stimulated by nutrient source additions even if they are present at low densities, and that use of 15N-SIP can identifythese functional members of the microbial community.

  5. Catalyzed oxidative degradation of methyl orange over Au catalyst prepared by ionic liquid-polymer modified silica

    NASA Astrophysics Data System (ADS)

    Wang, Y.; Guo, J. S.

    2015-07-01

    A new type of hybrid material was prepared by grafting an ionic liquid monomer, 1-(p-vinylbenzyl)-3-methylimidazolium chloride, on the surface of the porous silica which was synthesized via sodium silicate hydrolysis. The as-synthesized products were characterized by scanning electron microscope, nitrogen physisorption experiment, thermogravimetric analysis and Fourier transform infrared spectra. A catalyst with Au was prepared using the hybrid material as carrier. The experimental results show that the catalyst exhibits a better catalytic effect of hydrogen peroxide on the degradation of methyl orange. The reason may be that the metal component of the catalyst facilitated the dissociation of hydrogen peroxide to produce abundant highly active free radicals which can rapidly ruin the structure of methyl orange molecules in water. Finally, a probable catalytic degradation mechanism based on diffusion was discussed.

  6. 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

  7. 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

  8. Quantitative detection of the oil-degrading bacterium Acinetobacter sp. strain MUB1 by hybridization probe based real-time PCR.

    PubMed

    Phrommanich, Seksan; Suanjit, Sudarat; Upatham, Suchart; Grams, Suksiri Vichasri; Kruatrachue, Maleeya; Pokethitiyook, Prayad; Korge, Günter; Hofmann, Annemarie

    2009-01-01

    Quantitative detection of the oil-degrading bacterium Acinetobacter sp. strain MUB1 was performed using the SoilMaster() DNA Extraction Kit (Epicentre, Madison, Wisconsin) and hybridization probe based real-time PCR. The detection target was the alkane hydroxylase gene (alkM). Standard curve construction showed a linear relation between log values of cell concentrations and real-time PCR threshold cycles over five orders of magnitude between 5.4+/-3.0x10(6) and 5.4+/-3.0x10(2)CFUml(-1) cell suspension. The detection limit was about 540CFUml(-1), which was ten times more sensitive than conventional PCR. The quantification of Acinetobacter sp. strain MUB1 cells in soil samples resulted in 46.67%, 82.41%, and 87.59% DNA recovery with a detection limit of 5.4+/-3.0x10(4)CFUg(-1) dry soil. In this study, a method was developed for the specific, sensitive, and rapid quantification of the Acinetobacter sp. strain MUB1 in soil samples.

  9. 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.

  10. A dynamic supramolecular polymer with stimuli-responsive handedness for in situ probing of enzymatic ATP hydrolysis

    NASA Astrophysics Data System (ADS)

    Kumar, Mohit; Brocorens, Patrick; Tonnelé, Claire; Beljonne, David; Surin, Mathieu; George, Subi J.

    2014-12-01

    Design of artificial systems, which can respond to fluctuations in concentration of adenosine phosphates (APs), can be useful in understanding various biological processes. Helical assemblies of chromophores, which dynamically respond to such changes, can provide real-time chiroptical readout of various chemical transformations. Towards this concept, here we present a supramolecular helix of achiral chromophores, which shows chiral APs responsive tunable handedness along with dynamically switchable helicity. This system, composing of naphthalenediimides with phosphate recognition unit, shows opposite handedness on binding with ATP compared with ADP or AMP, which is comprehensively analysed with molecular dynamic simulations. Such differential signalling along with stimuli-dependent fast stereomutations have been capitalized to probe the reaction kinetics of enzymatic ATP hydrolysis. Detailed chiroptical analyses provide mechanistic insights into the enzymatic hydrolysis and various intermediate steps. Thus, a unique dynamic helical assembly to monitor the real-time reaction processes via its stimuli-responsive chiroptical signalling is conceptualized.

  11. A dynamic supramolecular polymer with stimuli-responsive handedness for in situ probing of enzymatic ATP hydrolysis.

    PubMed

    Kumar, Mohit; Brocorens, Patrick; Tonnelé, Claire; Beljonne, David; Surin, Mathieu; George, Subi J

    2014-01-01

    Design of artificial systems, which can respond to fluctuations in concentration of adenosine phosphates (APs), can be useful in understanding various biological processes. Helical assemblies of chromophores, which dynamically respond to such changes, can provide real-time chiroptical readout of various chemical transformations. Towards this concept, here we present a supramolecular helix of achiral chromophores, which shows chiral APs responsive tunable handedness along with dynamically switchable helicity. This system, composing of naphthalenediimides with phosphate recognition unit, shows opposite handedness on binding with ATP compared with ADP or AMP, which is comprehensively analysed with molecular dynamic simulations. Such differential signalling along with stimuli-dependent fast stereomutations have been capitalized to probe the reaction kinetics of enzymatic ATP hydrolysis. Detailed chiroptical analyses provide mechanistic insights into the enzymatic hydrolysis and various intermediate steps. Thus, a unique dynamic helical assembly to monitor the real-time reaction processes via its stimuli-responsive chiroptical signalling is conceptualized. PMID:25511998

  12. Probing subglass relaxation in polymers via a geometric representation of probabilities, observables, and relaxation modes for discrete stochastic systems.

    PubMed

    Boulougouris, Georgios C; Theodorou, Doros N

    2009-01-28

    The dynamics of many physical, chemical, and biological systems can be reduced to a succession of infrequent transitions in a network of discrete states representing low energy regions in configuration space. This enables accessing long-time dynamics and predicting macroscopic properties. Here we develop a new, perfectly general statistical mechanical/geometric formulation that expresses both state probabilities and all observables in the same Euclidean space, spanned by the eigenvectors of the symmetrized time evolution operator. Our formalism leads to simple expressions for nonequilibrium and equilibrium ensemble averages, variances, and time correlation functions of any observable and allows a rigorous decomposition of the dynamics into relaxation modes. Applying it to subglass segmental relaxation in atactic polystyrene up to times on the order of 10 micros, we probe the molecular mechanism of the gamma and delta processes and unequivocally identify the delta process with rotation of a single phenyl group around its stem.

  13. 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.

  14. 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. PMID:24280050

  15. Lithium dynamics in carbon-rich polymer-derived SiCN ceramics probed by nuclear magnetic resonance

    NASA Astrophysics Data System (ADS)

    Baek, Seung-Ho; Reinold, Lukas Mirko; Graczyk-Zajac, Magdalena; Riedel, Ralf; Hammerath, Franziska; Büchner, Bernd; Grafe, Hans-Joachim

    2014-05-01

    We report 7Li, 29Si, and 13C NMR studies of two different carbon-rich SiCN ceramics SiCN-1 and SiCN-3 derived from the preceramic polymers polyphenylvinylsilylcarbodiimide and polyphenylvinylsilazane, respectively. From the spectral analysis of the three nuclei, we find that only the 13C spectrum is strongly influenced by Li insertion/extraction, suggesting that carbon phases are the major electrochemically active sites for Li storage. Temperature (T) and Larmor frequency (ωL) dependences of the 7Li linewidth and spin-lattice relaxation rates T1-1 are described by an activated law with the activation energy EA of 0.31 eV and the correlation time τ0 in the high temperature limit of 1.3 ps. The 3 / 2 power law dependence of T1-1 on ωL which deviates from the standard Bloembergen, Purcell, and Pound (BPP) model implies that the Li motion on the μs timescale is governed by continuum diffusion mechanism rather than jump diffusion. On the other hand, the rotating frame relaxation rate T1ρ-1 results suggest that the slow motion of Li on the ms timescale may be affected by complex diffusion and/or non-diffusion processes.

  16. Mono/bimetallic water-stable lanthanide coordination polymers as luminescent probes for detecting cations, anions and organic solvent molecules.

    PubMed

    Wang, Huarui; Qin, Jianhua; Huang, Chao; Han, Yanbing; Xu, Wenjuan; Hou, Hongwei

    2016-08-01

    Eleven water-stable isostructural mono/bimetallic lanthanide coordination polymers (Ln-CPs) {[EuxTb1-x (HL)(H2O)3]·H2O}n (x = 1.0 (1), 0.9 (3), 0.8 (4), 0.7 (5), 0.6 (6), 0.4 (7), 0.3 (8), 0.2 (9), 0.1 (10), 0.05 (11), 0 (2), H4L = 5,5'-(1H-2,3,5-triazole-1,4-diyl)diisophthalic acid) with uncoordinated Lewis basic triazole sites within the pores were prepared. The Ln-CPs represented by 1 showed a rapid and drastic emission quenching induced by external Fe(3+) and Cr(3+) cations and CrO4(2-) and CO3(2-) anions in aqueous solution. In addition, because of the comparable emission intensities of Eu(3+) and Tb(3+) ions, bimetallic CP 8 can be used as a ratiometric luminescent sensor for organic solvent molecules. Moreover, the luminescent color of the 8 sensor in pyridine and in other guest solvents undergoes obvious changes that can be clearly distinguished by the naked eye. PMID:27443408

  17. A disposable evanescent wave fiber optic sensor coated with a molecularly imprinted polymer as a selective fluorescence probe.

    PubMed

    Ton, Xuan-Anh; Acha, Victor; Bonomi, Paolo; Tse Sum Bui, Bernadette; Haupt, Karsten

    2015-02-15

    We have developed a disposable evanescent wave fiber optic sensor by coating a molecularly imprinted polymer (MIP) containing a fluorescent signaling group on a 4-cm long polystyrene optical waveguide. The MIP is composed of a naphthalimide-based fluorescent monomer, which shows fluorescence enhancement upon binding with carboxyl-containing molecules. The herbicide 2,4-dichlorophenoxyacetic acid and the mycotoxin citrinin were used as model analytes. The coating of the MIP was either performed ex-situ, by dip-coating the fiber with MIP particles synthesized beforehand, or in-situ by evanescent-wave photopolymerization on the fiber. The sensing element was interrogated with a fiber-coupled spectrofluorimeter. The fiber optic sensor detects targets in the low nM range and exhibits specific and selective recognition over structural analogs and non-related carboxyl-containing molecules. This technology can be extended to other carboxyl-containing analytes, and to a broader spectrum of targets using different fluorescent monomers.

  18. Probing adsorption of polyacrylamide-based polymers on anisotropic Basal planes of kaolinite using quartz crystal microbalance.

    PubMed

    Alagha, Lana; Wang, Shengqun; Yan, Lujie; Xu, Zhenghe; Masliyah, Jacob

    2013-03-26

    Quartz crystal microbalance with dissipation (QCM-D) was applied to investigate the adsorption characteristics of polyacrylamide-based polymers (PAMs) on anisotropic basal planes of kaolinite. Kaolinite basal planes were differentiated by depositing kaolinite nanoparticles (KNPs) on silica and alumina sensors in solutions of controlled pH values. Adsorption of an in-house synthesized organic-inorganic Al(OH)3-PAM (Al-PAM) as an example of cationic hybrid PAM and a commercially available partially hydrolyzed polyacrylamide (MF1011) as an example of anionic PAM was studied. Cationic Al-PAM was found to adsorb irreversibly and preferentially on tetrahedral silica basal planes of kaolinite. In contrast, anionic MF1011 adsorbed strongly on aluminum-hydroxy basal planes, while its adsorption on tetrahedral silica basal planes was weak and reversible. Adsorption study revealed that both electrostatic attraction and hydrogen-bonding mechanisms contribute to adsorption of PAMs on kaolinite. The adsorbed Al-PAM layer was able to release trapped water overtime and became more compact, while MF1011 film became more dissipative as backbones stretched out from kaolinite surface with minimal overlapping. Experimental results obtained from this study provide clear insights into the phenomenon that governs flocculation-based solid-liquid separation processes using multicomponent flocculants of anionic and cationic nature.

  19. Probing solvation decay length in order to characterize hydrophobicity-induced bead-bead attractive interactions in polymer chains.

    PubMed

    Das, Siddhartha; Chakraborty, Suman

    2011-08-01

    In this paper, we quantitatively demonstrate that exponentially decaying attractive potentials can effectively mimic strong hydrophobic interactions between monomer units of a polymer chain dissolved in aqueous solvent. Classical approaches to modeling hydrophobic solvation interactions are based on invariant attractive length scales. However, we demonstrate here that the solvation interaction decay length may need to be posed as a function of the relative separation distances and the sizes of the interacting species (or beads or monomers) to replicate the necessary physical interactions. As an illustrative example, we derive a universal scaling relationship for a given solute-solvent combination between the solvation decay length, the bead radius, and the distance between the interacting beads. With our formalism, the hydrophobic component of the net attractive interaction between monomer units can be synergistically accounted for within the unified framework of a simple exponentially decaying potential law, where the characteristic decay length incorporates the distinctive and critical physical features of the underlying interaction. The present formalism, even in a mesoscopic computational framework, is capable of incorporating the essential physics of the appropriate solute-size dependence and solvent-interaction dependence in the hydrophobic force estimation, without explicitly resolving the underlying molecular level details.

  20. Probing adsorption of polyacrylamide-based polymers on anisotropic Basal planes of kaolinite using quartz crystal microbalance.

    PubMed

    Alagha, Lana; Wang, Shengqun; Yan, Lujie; Xu, Zhenghe; Masliyah, Jacob

    2013-03-26

    Quartz crystal microbalance with dissipation (QCM-D) was applied to investigate the adsorption characteristics of polyacrylamide-based polymers (PAMs) on anisotropic basal planes of kaolinite. Kaolinite basal planes were differentiated by depositing kaolinite nanoparticles (KNPs) on silica and alumina sensors in solutions of controlled pH values. Adsorption of an in-house synthesized organic-inorganic Al(OH)3-PAM (Al-PAM) as an example of cationic hybrid PAM and a commercially available partially hydrolyzed polyacrylamide (MF1011) as an example of anionic PAM was studied. Cationic Al-PAM was found to adsorb irreversibly and preferentially on tetrahedral silica basal planes of kaolinite. In contrast, anionic MF1011 adsorbed strongly on aluminum-hydroxy basal planes, while its adsorption on tetrahedral silica basal planes was weak and reversible. Adsorption study revealed that both electrostatic attraction and hydrogen-bonding mechanisms contribute to adsorption of PAMs on kaolinite. The adsorbed Al-PAM layer was able to release trapped water overtime and became more compact, while MF1011 film became more dissipative as backbones stretched out from kaolinite surface with minimal overlapping. Experimental results obtained from this study provide clear insights into the phenomenon that governs flocculation-based solid-liquid separation processes using multicomponent flocculants of anionic and cationic nature. PMID:23398356

  1. 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.

  2. Application of (13)C and (15)N stable isotope probing to characterize RDX degrading microbial communities under different electron-accepting conditions.

    PubMed

    Cho, Kun-Ching; Lee, Do Gyun; Fuller, Mark E; Hatzinger, Paul B; Condee, Charles W; Chu, Kung-Hui

    2015-10-30

    This study identified microorganisms capable of using the explosive hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) or its metabolites as carbon and/or nitrogen sources under different electron-accepting conditions using (13)C and (15)N stable isotope probing (SIP). Mesocosms were constructed using groundwater and aquifer solids from an RDX-contaminated aquifer. The mesocosms received succinate as a carbon source and one of four electron acceptors (nitrate, manganese(IV), iron(III), or sulfate) or no additional electron acceptor (to stimulate methanogenesis). When RDX degradation was observed, subsamples from each mesocosm were removed and amended with (13)C3- or ring-(15)N3-, nitro-(15)N3-, or fully-labeled (15)N6-RDX, followed by additional incubation and isolation of labeled nucleic acids. A total of fifteen 16S rRNA sequences, clustering in α- and γ-Proteobacteria, Clostridia, and Actinobacteria, were detected in the (13)C-DNA fractions. A total of twenty seven sequences were derived from different (15)N-DNA fractions, with the sequences clustered in α- and γ-Proteobacteria, and Clostridia. Interestingly, sequences identified as Desulfosporosinus sp. (in the Clostridia) were not only observed to incorporate the labeled (13)C or (15)N from labeled RDX, but also were detected under each of the different electron-accepting conditions. The data suggest that (13)C- and (15)N-SIP can be used to characterize microbial communities involved in RDX biodegradation, and that the dominant pathway of RDX biodegradation may differ under different electron-accepting conditions. PMID:25935409

  3. 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.

  4. Differential degradation rates in vivo and in vitro of biocompatible poly(lactic acid) and poly(glycolic acid) homo- and co-polymers for a polymeric drug-delivery microchip.

    PubMed

    Grayson, Amy C R; Voskerician, Gabriela; Lynn, Aaron; Anderson, James M; Cima, Michael J; Langer, Robert

    2004-01-01

    The biocompatibility and biodegradation rate of component materials are critical when designing a drug-delivery device. The degradation products and rate of degradation may play important roles in determining the local cellular response to the implanted material. In this study, we investigated the biocompatibility and relative biodegradation rates of PLA, PGA and two poly(lactic-co-glycolic acid) (PLGA) polymers of 50:50 mol ratio, thin-film component materials of a drug-delivery microchip developed in our laboratory. The in vivo biocompatibility and both in vivo and in vitro degradation of these materials were characterized using several techniques. Total leukocyte concentration measurements showed normal acute and chronic inflammatory responses to the PGA and low-molecular-weight PLGA that resolved by 21 days, while the normal inflammatory responses to the PLA and high-molecular-weight PLGA were resolved but at slower rates up to 21 days. These results were paralleled by thickness measurements of fibrous capsules surrounding the implants, which showed greater maturation of the capsules for the more rapidly degrading materials after 21 days, but less mature capsules of sustained thicknesses for the PLA and high-molecular-weight PLGA up to 49 days. Gel-permeation chromatography of residual polymer samples confirmed classification of the materials as rapidly or slowly degrading. These materials showed thinner fibrous capsules than have been reported for other materials by our laboratory and have suitable biocompatibility and biodegradation rates for an implantable drug-delivery device.

  5. Radiation-induced reactions in polymer films

    NASA Astrophysics Data System (ADS)

    Biscoglio, Michael Benedict

    Since the 1950's, there has been a considerable interest in the effects of ionizing radiation on the physical properties of polymer systems. Radiation induced chemical changes that were found to be helpful in producing specialty polymers, but also potentially harmful by degrading the physical performance of the material. Therefore, solute molecules, which act as excited state quenchers, and free radical scavengers, have been incorporated into the polymers in order to regulate the crosslinking, scission and desaturation reactions. This work is focused on using spectroscopic techniques to characterize the physical properties of polymeric media and the reactions occurring within them following pulsed radiolysis. This is done primarily by using arene doped polymer films which have highly absorbing excited states and radical ions that are easily monitored by transient studies. The probes are used to characterize the polymeric microenvironment, to monitor reaction rates, and to interfere in the radical reactions. Photophysical and photochemical characterization of partially crystalline polyethylene complements data previously obtained by conventional physical techniques for polymer characterization. Probe molecules are excluded from crystalline zones and distributed in a networked structure of amorphous zones. Upon high energy radiolysis, it is found that polyolefin systems efficiently donate all radical ions and excited states to the solute molecules, even when the energy is absorbed within the polymer crystalline zones. Studies of the subsequent reactions of the solute excited states and radical ions reveal information about their long term effectiveness as protectants. It is found that highly excited states formed by the recombination of solute radical ions are energetic enough to cause dissociation of halo-arenes. Also, arenes are found to become attached to the polymer chain through a polymer-aryl radical intermediate. These intermediates have been isolated and

  6. A polyoxometalate-based inorganic-organic hybrid polymer constructed from silver-Schiff base building block and Keggin-type cluster: Synthesis, crystal structure and photocatalytic performance for the degradation of rhodamine B.

    PubMed

    Li, Lei; Cheng, Meng; Bai, Yan; An, Bing; Dang, Dongbin

    2015-11-01

    One polyoxometalate-based inorganic-organic hybrid polymer [Ag3L4(PMo12O40)(CH3OH)]·CH3OH (1), where L is N,N'-bis(furan-2-ylmethylene)hydrazine, has been synthesized at room temperature and structurally characterized by infrared spectroscopy, ultraviolet-visible spectroscopy, elemental analysis, X-ray powder diffraction and X-ray single-crystal crystallography. The structure of 1 exhibits a crystalline one-dimensional polymer constructed by the connections of Keggin-type [PMo12O40](3-) anions and [Ag3L4](3+) units, in which each Ag(I) center adopted a distorted square pyramidal environment. The spectroscopic experiments show that polymer 1 not only is potential semiconductor materials but also displays the obvious photocatalytic performance for the degradation of rhodamine B.

  7. Branched polyesters based on poly[vinyl-3-(dialkylamino)alkylcarbamate-co-vinyl acetate-co-vinyl alcohol]-graft-poly(D,L-lactide-co-glycolide): effects of polymer structure on in vitro degradation behaviour.

    PubMed

    Unger, Florian; Wittmar, Matthias; Morell, Frank; Kissel, Thomas

    2008-05-01

    Branched polyesters of the general structure poly[vinyl-3-(dialkylamino)alkylcarbamate-co-vinyl acetate-co-vinyl alcohol]-graft-poly(D,L-lactide-co-glycolide) have shown potential for nano- and micro-scale drug delivery systems. Here the in vitro degradation behaviour with a special emphasis on elucidating structure-property relationships is reported. Effects of type and degree of amine substitution as well as PLGA side chain length were considered. In a first set of experiment, the weight loss of solvent cast films of defined size from 19 polymers was measured as a function of incubation in phosphate buffer (pH 7.4) at 37 degrees C over a time of 21 days. A second study was initiated focusing on three selected polymers in a similar set up, but with additional observation of pH influences (pH 2 and pH 9) and determination of water uptake (swelling) and molecular weights during degradation. Scanning electron micrographs have been recorded at selected time points to characterize film specimens morphologically after degradation. Our investigations revealed the potential to influence the degradation of this polymer class by the degree of amine substitution, higher degrees leading to faster erosion. The erosion rate could further be influenced by the type of amine functionality, DEAPA-modified polyesters degrading as fast as or slightly faster than DMAPA-modified polyesters and these degrading faster than DEAEA-PVA-g-PLGA. As a third option the degradation rate could be modified by the PLGA side chain length, shorter side chains leading to faster erosion. As compared to linear PLGA, remarkably shorter degradation times could be achieved by grafting short PLGA side chains onto amine-modified PVA backbones. Erosion times from less than 5 days to more than 4 weeks could be realized by selecting the type of amine functionality, the degree of amine substitution and the PLGA side chain length at the time of synthesis. In addition, the pathway of hydrolytic degradation can be

  8. 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.

  9. 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.

  10. Analysis of Synthetic Polymers.

    ERIC Educational Resources Information Center

    Smith, Charles G.; And Others

    1989-01-01

    Reviews techniques for the characterization and analysis of synthetic polymers, copolymers, and blends. Includes techniques for structure determination, separation, and quantitation of additives and residual monomers; determination of molecular weight; and the study of thermal properties including degradation mechanisms. (MVL)

  11. 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...

  12. 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

    Lerch, Thomas Z; Dignac, Marie-France; Barriuso, Enrique; Mariotti, André

    2011-10-01

    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 [(13)C]2,4-D, [(13)C]glucose, or mixtures of both substrates alternatively labeled with (13)C. 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 (13)C-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.

  13. 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.

  14. Probing effect of solvent concentration on glass transition and sub-Tg structural relaxation in polymer solvent mixtures: The case of polystyrene-toluene system

    NASA Astrophysics Data System (ADS)

    Pierleoni, Davide; Scherillo, Giuseppe; Minelli, Matteo; Mensitieri, Giuseppe; Doghieri, Ferruccio

    2016-05-01

    A novel experimental method for the analysis of volume relaxation induced by solvents in glassy polymers is presented. A gravimetric technique is used to evaluate the isothermal solvent mass uptake at controlled increasing/decreasing solvent pressure at constant rate. Fundamental properties of the solvent/polymer system can be obtained directly, and models can be applied, combining both nonequilibrium thermodynamics and mechanics of volume relaxation contribution. The fundamental case of polystyrene and toluene mixtures are thus accounted for, and various experimental conditions have been explored, varying the temperature, and spanning over different pressure increase/decrease rates. The results obtained allowed to evaluate the isothermal second order transition induced by solvent sorption, as well as the determination of the effect of the pressure rate. Therefore, this work proposes a new standard for the characterization and the understanding of the relaxational behavior of glassy polymers.

  15. 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.

  16. 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.

  17. Targeted Protein Degradation of Outer Membrane Decaheme Cytochrome MtrC Metal Reductase in Shewanella oneidensis MR-1 Measured Using Biarsenical Probe CrAsH-EDT2

    SciTech Connect

    Xiong, Yijia; Chen, Baowei; Shi, Liang; Fredrickson, Jim K.; Bigelow, Diana J.; Squier, Thomas C.

    2011-10-14

    Development of efficient microbial biofuel cells requires an ability to exploit interfacial electron transfer reactions to external electron acceptors, such as metal oxides; such reactions occur in the facultative anaerobic gram-negative bacterium Shewanella oneidensis MR-1 through the catalytic activity of the outer membrane decaheme c-type cytochrome MtrC. Central to the utility of this pathway to synthetic biology is an understanding of cellular mechanisms that maintain optimal MtrC function, cellular localization, and renewal by degradation and resynthesis. In order to monitor trafficking to the outer membrane, and the environmental sensitivity of MtrC, we have engineered a tetracysteine tag (i.e., CCPGCC) at its C-terminus that permits labeling by the cell impermeable biarsenical fluorophore, carboxy-FlAsH (CrAsH) of MtrC at the surface of living Shewanella oneidensis MR-1 cells. In comparison, the cell permeable reagent FlAsH permits labeling of the entire population of MtrC, including proteolytic fragments resulting from incorrect maturation. We demonstrate specific labeling by CrAsH of engineered MtrC which is dependent on the presence of a functional type-2 secretion system (T2S), as evidenced by T2S system gspD or gspG deletion mutants which are incapable of CrAsH labeling. Under these latter conditions, MtrC undergoes proteolytic degradation to form a large 35-38 kDa fragment; this degradation product is also resolved during normal turnover of the CrAsH-labeled MtrC protein. No MtrC protein is released into the medium during turnover, suggesting the presence of cellular turnover systems involving MtrC reuptake and degradation. The mature MtrC localized on the outer membrane is a long-lived protein, with a turnover rate of 0.043 hr-1 that is insensitive to O2 concentration. Maturation of MtrC is relatively inefficient, with substantial rates of turnover of the immature protein prior to export to the outer membrane (i.e., 0.028 hr-1) that are consistent

  18. Step-by-step thermal transformations of a new porous coordination polymer [(H2O)5CuBa(Me2mal)2]n (Me2mal2-=dimethylmalonate): Thermal degradation to barium cuprate

    NASA Astrophysics Data System (ADS)

    Zauzolkova, Natalya; Dobrokhotova, Zhanna; Lermontov, Anatoly; Zorina, Ekaterina; Emelina, Anna; Bukov, Mikhail; Chernyshev, Vladimir; Sidorov, Aleksey; Kiskin, Mikhail; Bogomyakov, Artem; Lytvynenko, Anton; Kolotilov, Sergey; Velikodnyi, Yuriy; Kovba, Maksim; Novotortsev, Vladimir; Eremenko, Igor

    2013-01-01

    The reactions of CuSO4·5H2O, dimethylmalonic acid and Ba(OH)2·H2O (Cu: H2Me2mal: Ba=1: 2: 2) in aqueous and aqueous-ethanol solutions (H2O: EtOH=1: 1) resulted in formation of 3D-porous coordination polymers [(H2O)3(μ-H2O)2CuBa(μ3-Me2mal)(Me2mal)]n (1) and [(μ-H2O)CuBa(μ3-Me2mal)(μ4-Me2mal)]n (2), respectively. It has been shown that compound 2 was an intermediate in the thermal degradation of compound 1. Thorough studies of solid-state thermolysis of 1 and 2 allowed to detect formation of coordination polymer [CuBa(μ4-Me2mal)(μ5-Me2mal)]n (3), structure of which was determined by X-ray powder diffraction. It has been found that the channels in polymer 3 were accessible for guest molecules (MeOH). Theoretical estimation of methanol diffusion barrier was carried out. Complete solid-phase thermolysis of 1 and 2 leads to a mixture of BaCuO2, BaCO3, and CuO. Special conditions for obtaining of a crystalline phase of pure cubic BaCuO2 were determined.

  19. 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.

  20. Photo-crosslinked fabrication of novel biocompatible and elastomeric star-shaped inositol-based polymer with highly tunable mechanical behavior and degradation.

    PubMed

    Xie, Meihua; Ge, Juan; Xue, Yumeng; Du, Yuzhang; Lei, Bo; Ma, Peter X

    2015-11-01

    Biodegradable and star-shaped polymers with highly tunable structure and properties have attracted much attention in recent years for potential biomedical applications, due to their special structure. Here, inositol-based star-shaped poly-L-lactide-poly(ethylene glycol) (INO-PLLA-PEG) biomedical polymer implants were for the first time synthesized by a facile photo-crosslinking method. This biomaterials show controlled elastomeric mechanical properties (~18 MPa in tensile strength, ~200 MPa in modulus, ~200% in elongation), biodegradability and osteoblasts biocompatibility. These results make INO-PLLA-PEG implants highly promising for bone tissue regeneration and drug delivery applications. PMID:26253207

  1. 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.

  2. Chemical State Mapping of Degraded B4C Control Rod Investigated with Soft X-ray Emission Spectrometer in Electron Probe Micro-analysis

    PubMed Central

    Kasada, R.; Ha, Y.; Higuchi, T.; Sakamoto, K.

    2016-01-01

    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. PMID:27161666

  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

    2016-01-01

    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. PMID:27161666

  4. 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.

  5. 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.

  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

    2014-11-01

    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. Physical Organic Chemistry of Supramolecular Polymers

    PubMed Central

    Serpe, Michael J.; Craig, Stephen L.

    2008-01-01

    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. PMID:17279638

  8. Thermal stability and degradation of chitosan modified by benzophenone

    NASA Astrophysics Data System (ADS)

    Diab, M. A.; El-Sonbati, A. Z.; Bader, D. M. D.

    2011-09-01

    N-(biphenylmethylidenyl) chitosan polymer was prepared, characterized and thermal stability was compared with chitosan. Thermal degradation products of the modified polymer were identified by GC-MS technique. It seems that the mechanism of degradation of the prepared polymer is characterized by formation of low molecular weight radicals, followed by random scission mechanism along the backbond chain.

  9. 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.

  10. 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.

  11. 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.

  12. Stimuli-responsive polymer films.

    PubMed

    Zhai, Lei

    2013-09-01

    Stimuli-responsive polymer films undergo interesting structural and property changes upon external stimuli. Their applications have extended from smart coatings to controlled drug release, smart windows, self-repair and other fields. This tutorial review summarizes non-covalent bonding, reversible reactions and responsive molecules that have played important roles in creating stimuli-responsive systems, and presents the recent development of three types of responsive polymer systems: layer-by-layer polymer multilayer films, polymer brushes, and self-repairing polymer films, with a discussion of their response mechanism. Future research efforts include comprehensive understanding of the response mechanism, producing polymer systems with controlled response properties regarding single or multiple external signals, combining polymer film fabrication with nanotechnology, improving the stability of polymer films on substrates, and evaluating the toxicity of the degradation products. PMID:23749141

  13. Nonlinear optical studies of polymer interfaces

    SciTech Connect

    Shen, Y.R. |

    1993-11-01

    Second-order nonlinear optical processes can be used as effective surface probes. They can provide some unique opportunities for studies of polymer interfaces. Here the author describes two examples to illustrate the potential of the techniques. One is on the formation of metal/polymer interfaces. The other is on the alignment of liquid crystal films by mechanically rubbed polymer surfaces.

  14. Simple and Sensitive Molecularly Imprinted Polymer - Mn-Doped ZnS Quantum Dots Based Fluorescence Probe for Cocaine and Metabolites Determination in Urine.

    PubMed

    Chantada-Vázquez, María Pilar; Sánchez-González, Juan; Peña-Vázquez, Elena; Tabernero, María Jesús; Bermejo, Ana María; Bermejo-Barrera, Pilar; Moreda-Piñeiro, Antonio

    2016-03-01

    A new molecularly imprinted polymer (MIP)-based fluorescent artificial receptor has been prepared by anchoring a selective MIP for cocaine (COC) on the surface of polyethylene glycol (PEG) modified Mn-doped ZnS quantum dots (QDs). The prepared material combines the high selectivity attributed to MIPs and the sensitive fluorescent property of the Mn-doped ZnS QDs. Simple and low cost methods have therefore been optimized for assessing cocaine abuse in urine by monitoring the fluorescence quenching when the template (COC) and also metabolites from COC [benzoylecgonine (BZE) and ecgonine methyl ester (EME)] are present. Fluorescence quenching was not observed when performing experiments with other drugs of abuse (and their metabolites) or when using nonimprinted polymer (NIP)-coated QDs. Under optimized operating conditions (1.5 mL of 200 mg L(-1) MIP-coated QDs solution, pH 5.5, and 15 min before fluorescence scanning) two analytical methods were developed/validated. One of the procedures (direct method) consisted of urine sample 1:20 dilution before fluorescence measurements. The method has been found to be fast, precise, and accurate, but the standard addition technique for performing the analysis was required because of the existence of matrix effect. The second procedure performed a solid phase extraction (SPE) first, avoiding matrix effect and allowing external calibration. The limits of detection of the methods were 0.076 mg L(-1) (direct method) and 0.0042 mg L(-1) (SPE based method), which are lower than the cutoff values for confirmative conclusions regarding cocaine abuse. PMID:26857857

  15. 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...

  16. The influence of different coordination environments on one-dimensional Cu(ii) coordination polymers for the photo-degradation of organic dyes.

    PubMed

    Hussain, Navid; Bhardwaj, Vimal K

    2016-05-01

    Three new Cu(ii) coordination polymers, namely, {[Cu3(L(1))(NO3)2(DMF)(H2O)]·3(DMF)}n (), [Cu3(L(1))(Cl)2(DMF)2]n () and [Cu3(L(2))(NO3)4(H2O)4]n (), were synthesized from pyridine-2,6-dicarbohydrazide based imine linked tritopic ligands. All the complexes were characterized using elemental analysis, IR, UV-vis spectroscopy and ESI-MS. The solid state structures of complexes were determined using single crystal X-ray crystallography. The complexes contain trinuclear copper units connected through different anions that lead to the formation of one dimensional (ID) chain structures. Depending upon the anion of the copper salt and donor atoms of the ligands used in complexation, a small variation in the structures was observed. In complex , the trinuclear copper units are connected by phenoxo-bridging (μ2-O(-)) along with one coordinated water molecule, whereas complex is connected through chloride bridging (μ2-Cl) and complex is connected through nitrate ions (μ-[O-N-O]) along with four water molecules. Photo-catalytic activities of the synthesized complexes () were investigated. All the complexes were found to be photo-catalytically active; however, the distinct coordination environment of the metal ions (i.e. difference in the coordinated water molecules and donor sites of ligands) played a significant role in the catalytic activities. Therefore, this study presents comparative photo-catalytic studies of different coordination environments of metal ions in one-dimensional Cu(ii) coordination polymers. The results provide a potential pathway for the rational design of more efficient photo-catalysts. PMID:27054292

  17. 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.

  18. 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.

  19. 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

  20. 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...

  1. 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...

  2. 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.

  3. 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.

  4. Probing long-range carrier-pair spin–spin interactions in a conjugated polymer by detuning of electrically detected spin beating

    PubMed Central

    van Schooten, Kipp J.; Baird, Douglas L.; Limes, Mark E.; Lupton, John M.; Boehme, Christoph

    2015-01-01

    Weakly coupled electron spin pairs that experience weak spin–orbit interaction can control electronic transitions in molecular and solid-state systems. Known to determine radical pair reactions, they have been invoked to explain phenomena ranging from avian magnetoreception to spin-dependent charge-carrier recombination and transport. Spin pairs exhibit persistent spin coherence, allowing minute magnetic fields to perturb spin precession and thus recombination rates and photoreaction yields, giving rise to a range of magneto-optoelectronic effects in devices. Little is known, however, about interparticle magnetic interactions within such pairs. Here we present pulsed electrically detected electron spin resonance experiments on poly(styrene-sulfonate)-doped poly(3,4-ethylenedioxythiophene) (PEDOT:PSS) devices, which show how interparticle spin–spin interactions (magnetic-dipolar and spin-exchange) between charge-carrier spin pairs can be probed through the detuning of spin-Rabi oscillations. The deviation from uncoupled precession frequencies quantifies both the exchange (<30 neV) and dipolar (23.5±1.5 neV) interaction energies responsible for the pair's zero-field splitting, implying quantum mechanical entanglement of charge-carrier spins over distances of 2.1±0.1 nm. PMID:25868686

  5. 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

  6. 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

    2016-08-01

    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. PMID:27403761

  7. Development of aliphatic biodegradable photoluminescent polymers

    PubMed Central

    Yang, Jian; Zhang, Yi; Gautam, Santosh; Liu, Li; Dey, Jagannath; Chen, Wei; Mason, Ralph P.; Serrano, Carlos A.; Schug, Kevin A.; Tang, Liping

    2009-01-01

    None of the current biodegradable polymers can function as both implant materials and fluorescent imaging probes. The objective of this study was to develop aliphatic biodegradable photoluminescent polymers (BPLPs) and their associated cross-linked variants (CBPLPs) for biomedical applications. BPLPs are degradable oligomers synthesized from biocompatible monomers including citric acid, aliphatic diols, and various amino acids via a convenient and cost-effective polycondensation reaction. BPLPs can be further cross-linked into elastomeric cross-linked polymers, CBPLPs. We have shown representatively that BPLP-cysteine (BPLP-Cys) and BPLP-serine (BPLP-Ser) offer advantages over the traditional fluorescent organic dyes and quantum dots because of their preliminarily demonstrated cytocompatibility in vitro, minimal chronic inflammatory responses in vivo, controlled degradability and high quantum yields (up to 62.33%), tunable fluorescence emission (up to 725 nm), and photostability. The tensile strength of CBPLP-Cys film ranged from 3.25 ± 0.13 MPa to 6.5 ± 0.8 MPa and the initial Modulus was in a range of 3.34 ± 0.15 MPa to 7.02 ± 1.40 MPa. Elastic CBPLP-Cys could be elongated up to 240 ± 36%. The compressive modulus of BPLP-Cys (0.6) (1:1:0.6 OD:CA:Cys) porous scaffold was 39.60 ± 5.90 KPa confirming the soft nature of the scaffolds. BPLPs also possess great processability for micro/nano-fabrication. We demonstrate the feasibility of using BPLP-Ser nanoparticles (“biodegradable quantum dots”) for in vitro cellular labeling and noninvasive in vivo imaging of tissue engineering scaffolds. The development of BPLPs and CBPLPs represents a new direction in developing fluorescent biomaterials and could impact tissue engineering, drug delivery, bioimaging. PMID:19506254

  8. Hazardous-waste degradation by wood-degrading fungi

    SciTech Connect

    Glaser, J.A.

    1992-01-01

    The persistence and toxicity of many hazardous waste constituents indicates that the environment has limited capacity to degrade such materials. The competence and presence of degrading organisms significantly effects one's ability to treat and detoxify these hazardous waste chemicals. Competence is often specified by the ability of the organisms to convert toxic chemicals to non toxic entities and most desirably to carbon dioxide. A wood degrading fungus, Phanerochaete chrysosporium has been investigated to determine its role as a degrader of toxic waste materials. Due to its widely recognized ability to degrade lignin, a persistent biogenic polymer, and the non specific enzyme systems supporting such activity, it was thought to have great promise as a toxic waste degrader.

  9. 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

    2015-01-01

    , 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.

  10. 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.

  11. 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

  12. Bioabsorbable polymers in medicine: an overview.

    PubMed

    Vert, Michel

    2009-12-15

    Today the domains of life-respecting, degradable therapeutic materials and devices are among the most attractive areas in polymer science. Increasing attention is being paid to polymeric compounds that can be bioresorbable, i.e., degradable and ideally excreted or bio-assimilated - suitable to treat human diseases or trauma that require therapeutic assistance for a limited period of time, namely the healing period. Basically, biopolymers are of interest because of their inherent biodegradability. However, other characteristics limit their applications in the human body. Artificial polymers, i.e., polymers of non-natural origin, can be degradable in vivo and thus serve in time-limited biomedical or pharmacological therapy. The potential of these degradable polymers is discussed with respect to bioresorbability, with a special attention to polymers of the poly (α-hydroxy acid) type.

  13. Ion implantation in polymers

    NASA Astrophysics Data System (ADS)

    Wintersgill, M. C.

    1984-02-01

    An introductory overview will be given of the effects of ion implantation on polymers, and certain areas will be examined in more detail. Radiation effects in general and ion implantation in particular, in the field of polymers, present a number of contrasts with those in ionic crystals, the most obvious difference being that the chemical effects of both the implanted species and the energy transfer to the host may profoundly change the nature of the target material. Common effects include crosslinking and scission of polymer chains, gas evolution, double bond formation and the formation of additional free radicals. Research has spanned the chemical processes involved, including polymerization reactions achievable only with the use of radiation, to applied research dealing both with the effects of radiation on polymers already in commercial use and the tailoring of new materials to specific applications. Polymers are commonly divided into two groups, in describing their behavior under irradiation. Group I includes materials which form crosslinks between molecules, whereas Group II materials tend to degrade. In basic research, interest has centered on Group I materials and of these polyethylene has been studied most intensively. Applied materials research has investigated a variety of polymers, particularly those used in cable insulation, and those utilized in ion beam lithography of etch masks. Currently there is also great interest in enhancing the conducting properties of polymers, and these uses would tend to involve the doping capabilities of ion implantation, rather than the energy deposition.

  14. 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.

  15. Atomic step-and-terrace surface of polyimide sheet for advanced polymer substrate engineering.

    PubMed

    Tan, G; Shimada, K; Nozawa, Y; Kaneko, S; Urakami, T; Koyama, K; Komura, M; Matsuda, A; Yoshimoto, M

    2016-07-22

    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. PMID:27284690

  16. 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.

  17. 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.

  18. 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.

  19. Synthetic polymers from readily available monosaccharides.

    PubMed

    Galbis, J A; García-Martín, M G

    2010-01-01

    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.

  20. Spectroscopic and Intensity Modulated Photocurrent Imaging of Polymer/Fullerene Solar Cells.

    PubMed

    Gao, Yongqian; Wise, Adam J; Thomas, Alan K; Grey, John K

    2016-01-13

    Molecular spectroscopic and intensity modulated photocurrent spectroscopy (IMPS) imaging techniques are used to map morphology-dependent charge recombination in organic polymer/fullerene solar cells. IMPS uses a small (∼10%) sinusoidal modulation of an excitation light source and photocurrent responses are measured while modulation frequencies are swept over several decades (∼1 Hz-20 kHz). Solar cells consisting of either poly(3-hexylthiophene) (P3HT) and poly(2-methoxy-5-(3'-7'-dimethyloctyloxy)-1,4-phenylenevinylene) (MDMO-PPV) blended with a soluble fullerene derivative, [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) are used as targets. The morphologies of these polymer/fullerene systems are distinctly different due to PCBM miscibility in various polymer conformers. IMPS responses of both blend solar cells show unique morphology-dependent charge generation, transport and extraction signatures that can be spatially correlated to microscopic variations in local composition and packing by constructing IMPS images along with corresponding molecular spectroscopic imaging over the same scan area. We find that boundaries separating enriched polymer and fullerene domains promote nongeminate charge recombination appearing as positive phase shifts in the IMPS response. These zones are susceptible to degradation and we propose the approaches herein can be used to probe material and device degradation in situ under various conditions, such as oxygen content, temperature and ionizing radiation.

  1. Biomedical Applications of Biodegradable Polymers

    PubMed Central

    Ulery, Bret D.; Nair, Lakshmi S.; Laurencin, Cato T.

    2011-01-01

    Utilization of polymers as biomaterials has greatly impacted the advancement of modern medicine. Specifically, polymeric biomaterials that are biodegradable provide the significant advantage of being able to be broken down and removed after they have served their function. Applications are wide ranging with degradable polymers being used clinically as surgical sutures and implants. In order to fit functional demand, materials with desired physical, chemical, biological, biomechanical and degradation properties must be selected. Fortunately, a wide range of natural and synthetic degradable polymers has been investigated for biomedical applications with novel materials constantly being developed to meet new challenges. This review summarizes the most recent advances in the field over the past 4 years, specifically highlighting new and interesting discoveries in tissue engineering and drug delivery applications. PMID:21769165

  2. 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.

  3. 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.

  4. Nanoscale Study of Polymer Dynamics.

    PubMed

    Keshavarz, Masoumeh; Engelkamp, Hans; Xu, Jialiang; Braeken, Els; Otten, Matthijs B J; Uji-I, Hiroshi; Schwartz, Erik; Koepf, Matthieu; Vananroye, Anja; Vermant, Jan; Nolte, Roeland J M; De Schryver, Frans; Maan, Jan C; Hofkens, Johan; Christianen, Peter C M; Rowan, Alan E

    2016-01-26

    The thermal motion of polymer chains in a crowded environment is anisotropic and highly confined. Whereas theoretical and experimental progress has been made, typically only indirect evidence of polymer dynamics is obtained either from scattering or mechanical response. Toward a complete understanding of the complicated polymer dynamics in crowded media such as biological cells, it is of great importance to unravel the role of heterogeneity and molecular individualism. In the present work, we investigate the dynamics of synthetic polymers and the tube-like motion of individual chains using time-resolved fluorescence microscopy. A single fluorescently labeled polymer molecule is observed in a sea of unlabeled polymers, giving access to not only the dynamics of the probe chain itself but also to that of the surrounding network. We demonstrate that it is possible to extract the characteristic time constants and length scales in one experiment, providing a detailed understanding of polymer dynamics at the single chain level. The quantitative agreement with bulk rheology measurements is promising for using local probes to study heterogeneity in complex, crowded systems.

  5. Nanoscale Study of Polymer Dynamics.

    PubMed

    Keshavarz, Masoumeh; Engelkamp, Hans; Xu, Jialiang; Braeken, Els; Otten, Matthijs B J; Uji-I, Hiroshi; Schwartz, Erik; Koepf, Matthieu; Vananroye, Anja; Vermant, Jan; Nolte, Roeland J M; De Schryver, Frans; Maan, Jan C; Hofkens, Johan; Christianen, Peter C M; Rowan, Alan E

    2016-01-26

    The thermal motion of polymer chains in a crowded environment is anisotropic and highly confined. Whereas theoretical and experimental progress has been made, typically only indirect evidence of polymer dynamics is obtained either from scattering or mechanical response. Toward a complete understanding of the complicated polymer dynamics in crowded media such as biological cells, it is of great importance to unravel the role of heterogeneity and molecular individualism. In the present work, we investigate the dynamics of synthetic polymers and the tube-like motion of individual chains using time-resolved fluorescence microscopy. A single fluorescently labeled polymer molecule is observed in a sea of unlabeled polymers, giving access to not only the dynamics of the probe chain itself but also to that of the surrounding network. We demonstrate that it is possible to extract the characteristic time constants and length scales in one experiment, providing a detailed understanding of polymer dynamics at the single chain level. The quantitative agreement with bulk rheology measurements is promising for using local probes to study heterogeneity in complex, crowded systems. PMID:26688072

  6. 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. PMID:26312436

  7. 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.

  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. 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.

  10. 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.

  11. 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.

  12. Regulation of Coal Polymer Degradation by Fungi

    SciTech Connect

    Irvin, R.L.; Bumpus, J.A.

    1997-04-30

    Previous studies in our laboratory used a spectrophotometric assay to study biomimetic solubilization of leonardite by sodium oxalate. It was found, however, that in extended incubations of several days, this assay resulted in overestimation of the percent of leonardite that was solubilized. This problem did not appear to be significant for short term incubations (ie., up to -24 h) and was circumvented in long term incubations by using a gravimetric assay to assay for solubilization. In other studies during this reporting period we examined oxalate production by P. chrysosporium and T. versicolor grown in Fahreus-Reinhammar medium in agitated pelleted culture. It was found that in this system concentrations of oxalate are produced that are much lower than those that would be optimal for leonardite solubilization.

  13. Polysilylether: A Degradable Polymer from Biorenewable Feedstocks.

    PubMed

    Cheng, Chen; Watts, Annabelle; Hillmyer, Marc A; Hartwig, John F

    2016-09-19

    The synthesis of polysilylethers (PSEs) using a monomer derived from a biorenewable feedstock is reported. The AB-type monomer was synthesized from undecenoic acid through hydrosilylation and reduction, and the polymerization was catalyzed by earth-abundant metal salts. High-molar-mass products were achieved, and the degree of polymerization was controlled by varying the amount of an AA-type monomer in the reaction. The PSEs possess good thermal stability and a low glass-transition temperature (Tg ≈-67 °C). To demonstrate the utility of the PSEs, polyurethanes were synthesized from low-molar-mass hydroxy-telechelic PSEs. PMID:27572134

  14. 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.

  15. 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.

  16. 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.

  17. Biodegradable polymers for the environment.

    PubMed

    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.

  18. Photoaddressable Polymers

    NASA Astrophysics Data System (ADS)

    Bieringer, T.

    Polymers are the perfect materials for a variety of applications in almost every field of technical as well as human life. Because of their macromolecular architecture there are a lot of degrees of freedom in the synthesis of polymers. Owing to the change of their functional composition, they can be tailored even for quite difficult demands. Since a whole industry deals with the processing of polymers, cheap production lines have been developed for almost every polymer. This is the reason why not only the molecular composition but even the price of polymers has been optimized. Therefore these materials can be considered as encouraging components even in highly sophisticated areas of applications.

  19. Understanding API-polymer proximities in amorphous stabilized composite drug products using fluorine-carbon 2D HETCOR solid-state NMR.

    PubMed

    Abraham, Anuji; Crull, George

    2014-10-01

    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.

  20. 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...

  1. Conductivity Probe

    NASA Technical Reports Server (NTRS)

    2008-01-01

    The Thermal and Electrical Conductivity Probe (TECP) for NASA's Phoenix Mars Lander took measurements in Martian soil and in the air.

    The needles on the end of the instrument were inserted into the Martian soil, allowing TECP to measure the propagation of both thermal and electrical energy. TECP also measured the humidity in the surrounding air.

    The needles on the probe are 15 millimeters (0.6 inch) long.

    The Phoenix Mission is led by the University of Arizona, Tucson, on behalf of NASA. Project management of the mission is by NASA's Jet Propulsion Laboratory, Pasadena, Calif. Spacecraft development is by Lockheed Martin Space Systems, Denver.

  2. Laboratory test of cooling power of polymer quenchants

    SciTech Connect

    Narazaki, M.; Kogawara, M.; Shirayori, A.; Fuchizawa, S.

    1996-12-31

    The effects of shape, size and material of probe on the cooling curves in polymer quenching are studied experimentally. The strong influence of the probe shape and the high sensitivity of silver probes are confirmed. It is clarified that the agitation of polymer quenchants and the use of cylindrical probes with hemispherical ends result in excellent reproducibility. Besides, calculating the heat transfer coefficient and/or heat flux from the cooling curve data of the silver probe is very easy because of the probe temperature uniformity. It is concluded that the cooling curve test using a cylindrical silver probe with hemispherical ends and a forced connection bath is more suitable for determining the cooling power of aqueous polymer solutions.

  3. 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...

  4. 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,…

  5. 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.

  6. Advanced Polymer For Multilayer Insulating Blankets

    NASA Technical Reports Server (NTRS)

    Haghighat, R. Ross; Shepp, Allan

    1996-01-01

    Polymer resisting degradation by monatomic oxygen undergoing commercial development under trade name "Aorimide" ("atomic-oxygen-resistant imidazole"). Intended for use in thermal blankets for spacecraft in low orbit, useful on Earth in outdoor applications in which sunlight and ozone degrades other plastics. Also used, for example, to make threads and to make films coated with metals for reflectivity.

  7. Polymer adsorption

    NASA Astrophysics Data System (ADS)

    Joanny, Jean-Francois

    2008-03-01

    The aim of this talk is to review Pierre-Gilles deGennes' work on polymer adsorption and the impact that it has now in our understanding of this problem. We will first present the self-consistent mean-field theory and its applications to adsorption and depletion. De Gennes most important contribution is probably the derivation of the self-similar power law density profile for adsorbed polymer layers that we will present next, emphasizing the differences between the tail sections and the loop sections of the adsorbed polymers. We will then discuss the kinetics of polymer adsorption and the penetration of a new polymer chain in an adsobed layer that DeGennes described very elegantly in analogy with a quantum tunneling problem. Finally, we will discuss the role of polymer adsorption for colloid stabilization.

  8. 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.

  9. 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.

  10. 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

  11. FTIR study of degradation products of aliphatic polyesters carbon fibres composites

    NASA Astrophysics Data System (ADS)

    Pamuła, Elżbieta; Błażewicz, Marta; Paluszkiewicz, Czesława; Dobrzyński, Piotr

    2001-09-01

    Biodegradable polymer composites based on polylactides and polyglycolides constitute a group of materials characterised by good biocompatibility. They are considered in tissue engineering as scaffolds for cells proliferation and controlled tissue regeneration. Two types of biodegradable polymers possessing different chemical structure, molecular weights and crystallinity degrees and two composite materials made up of them and carbon fibres were analysed in this study. The samples were incubated in aqueous media for 8 weeks and analysed by means of Fourier transform infrared spectroscopy in the attenuated total reflection mode (FTIR-ATR). Infrared spectroscopy enabled identification of degradation products and estimation of the influence of carbon fibres on hydrolytic degradation of analysed polymers. Analysis of the infrared spectra showed that hydrolytic degradation process depends on chemical structure, molecular weight and crystallinity of polymers. Catalytic effect of carbon fibres at the initial stage of polymer degradation was observed. Further degradation is dependent on the properties of polymer.

  12. 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…

  13. 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.

  14. Exploring bacterial lignin degradation.

    PubMed

    Brown, Margaret E; Chang, Michelle C Y

    2014-04-01

    Plant biomass represents a renewable carbon feedstock that could potentially be used to replace a significant level of petroleum-derived chemicals. One major challenge in its utilization is that the majority of this carbon is trapped in the recalcitrant structural polymers of the plant cell wall. Deconstruction of lignin is a key step in the processing of biomass to useful monomers but remains challenging. Microbial systems can provide molecular information on lignin depolymerization as they have evolved to break lignin down using metalloenzyme-dependent radical pathways. Both fungi and bacteria have been observed to metabolize lignin; however, their differential reactivity with this substrate indicates that they may utilize different chemical strategies for its breakdown. This review will discuss recent advances in studying bacterial lignin degradation as an approach to exploring greater diversity in the environment. PMID:24780273

  15. 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.

  16. 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.

  17. Soft stylus probes for scanning electrochemical microscopy.

    PubMed

    Cortés-Salazar, Fernando; Träuble, Markus; Li, Fei; Busnel, Jean-Marc; Gassner, Anne-Laure; Hojeij, Mohamad; Wittstock, Gunther; Girault, Hubert H

    2009-08-15

    A soft stylus microelectrode probe has been developed to carry out scanning electrochemical microscopy (SECM) of rough, tilted, and large substrates in contact mode. It is fabricated by first ablating a microchannel in a polyethylene terephthalate thin film and filling it with a conductive carbon ink. After curing the carbon track and lamination with a polymer film, the V-shaped stylus was cut thereby forming a probe, with the cross section of the carbon track at the tip being exposed either by UV-photoablation machining or by blade cutting followed by polishing to produce a crescent moon-shaped carbon microelectrode. The probe properties have been assessed by cyclic voltammetry, approach curves, and line scans over electrochemically active and inactive substrates of different roughness. The influence of probe bending on contact mode imaging was then characterized using simple patterns. Boundary element method simulations were employed to rationalize the distance-dependent electrochemical response of the soft stylus probes. PMID:19630394

  18. Thermal stability of sulfonated polymers

    SciTech Connect

    Audibert, A.; Argillier, J.F.

    1995-11-01

    Polyacrylamides which are used in oil applications i.e. polymer flooding and water based muds, are hydrolyzed versus time and temperature. This leads to a lack of tolerance towards electrolyte contamination and to a rapid degradation inducing a loss of their properties. Modifications of polyacrylamide structure have been proposed to postpone their thermal stability to higher temperatures. Monomers such as acrylamido methylpropane sulfonate (AMPS) or sulfonated styrene/maleic anhydride can be used to prevent acrylamide comonomer from hydrolysis. The aim of this work is to study under controlled conditions, i.e. anaerobic atmosphere, neutral pH, the stability of sulfonated polymers in order to distinguish between hydrolysis and radical degradation reactions. It has been observed that up to 100 C, the AMPS group is stable and protects the acrylamide function from hydrolysis up to 80%. At higher temperature, even the hydrolysis of the AMPS group occurs, giving acrylate and {beta},{beta} dimethyl taurine, with a kinetics that depends on temperature and time. Degradation in terms of molecular weight then occurs indicating that it follows a radical decarboxylation reaction. It can be limited either by the use of free radical scavenger or when the polymer is in the presence of a mineral phase such as bentonite. These results provide valuable data for the determination of the limits of use of sulfonated copolymers and guidelines for optimizing chemical structure of sulfonated polymers used in water based formulation, in particular to enhance their thermal stability.

  19. Degradation mechanisms and accelerated aging test design

    SciTech Connect

    Clough, R L; Gillen, K T

    1985-01-01

    The fundamental mechanisms underlying the chemical degradation of polymers can change as a function of environmental stress level. When this occurs, it greatly complicates any attempt to use accelerated tests for predicting long-term material degradation behaviors. Understanding how degradation mechanisms can change at different stress levels facilitates both the design and the interpretation of aging tests. Oxidative degradation is a predominant mechanism for many polymers exposed to a variety of different environments in the presence of air, and there are two mechanistic considerations which are widely applicable to material oxidation. One involves a physical process, oxygen diffusion, as a rate-limiting step. This mechanism can predominate at high stress levels. The second is a chemical process, the time-dependent decomposition of peroxide species. This leads to chain branching and can become a rate-controlling factor at lower stress levels involving time-scales applicable to use environments. The authors describe methods for identifying the operation of these mechanisms and illustrate the dramatic influence they can have on the degradation behaviors of a number of polymer types. Several commonly used approaches to accelerated aging tests are discussed in light of the behaviors which result from changes in degradation mechanisms. 9 references, 4 figures.

  20. 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.

  1. Polymer nanolithography

    NASA Astrophysics Data System (ADS)

    Vance, Jennifer M.

    Nanolithography involves making patterns of materials with at least one dimension less than 100 nanometers. Surprisingly, writable CDs can provide polymer nanostructures for pennies a piece. Building on work previously done in the Drain lab, with an inherited home-built oven press, this research will explore the relationships between polymer chemical reactivity, polymer printing, and material surface energies. In addition, a relatively inexpensive entry point into high school and undergraduate education in nanolithography is presented. The ability to pattern cheaply at the nanoscale and microscale is necessary and attractive for many technologies towards biosensors, organic light emitting diodes, identification tags, layered devices, and transistors.

  2. 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...

  3. Synthetic biodegradable functional polymers for tissue engineering: a brief review

    PubMed Central

    BaoLin, GUO; MA, Peter X.

    2015-01-01

    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. PMID:25729390

  4. 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

  5. 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)

  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. 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,...

  8. Interfacial force microscopy: Application to polymer surfaces

    SciTech Connect

    HOUSTON,JACK E.; WINTER,R.M.

    2000-05-16

    Scanning-probe microscopies (SPM) are presently widely used in remarkably diverse applications and, as evidenced by this symposium these techniques are rapidly expanding into the important areas of polymer surfaces and interfaces. The Atomic Force Microscope (AFM) is presently the most widely used of the scanning-probe techniques. However, the AFM's range of application suffers from an inherent mechanical instability in its deflection force sensor. The instability problem has been overcome by the development of the Interfacial Force Microscope (IFM), which utilizes a force-feedback sensor concept. In the following, the authors present several examples of polymer applications to illustrate the utility of the IFM sensor concept.

  9. 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.

  10. Imine Hydrogels with Tunable Degradability

    PubMed Central

    Boehnke, Natalie; Cam, Cynthia; Bat, Erhan; Segura, Tatiana; Maynard, Heather D.

    2015-01-01

    A shortage of available organ donors has created a need for engineered tissues. In this context, polymer-based hydrogels that break down inside the body are often used as constructs for growth factors and cells. Herein, we report imine cross-linked gels where degradation is controllable by the introduction of mixed imine cross-links. Specifically, hydrazide-functionalized poly(ethylene glycol) (PEG) reacts with aldehyde-functionalized PEG (PEG-CHO) to form hydrazone linked hydrogels that degrade quickly in media. The time to degradation can be controlled by changing the structure of the hydrazide group or by introducing hydroxylamines to form non-reversible oxime linkages. Hydrogels containing adipohydrazide-functionalized PEG (PEG-ADH) and PEG-CHO were found to degrade more rapidly than gels formed from carbodihydrazide-functionalized PEG (PEG-CDH). Incorporating oxime linkages via aminooxy-functionalized PEG (PEG-AO) into the hydrazone cross-linked gels further stabilized the hydrogels. This imine crosslinking approach should be useful for modulating the degradation characteristics of 3D cell culture supports for controlled cell release. PMID:26061010

  11. Synthesis, Biodegradability, and Biocompatibility of Lysine Diisocyanate–Glucose Polymers

    PubMed Central

    ZHANG, JIAN-YING; BECKMAN, ERIC J.; HU, JING; YANG, GUO-GUANG; AGARWAL, SUDHA; HOLLINGER, JEFFREY O.

    2016-01-01

    The success of a tissue-engineering application depends on the use of suitable biomaterials that degrade in a timely manner and induce the least immunogenicity in the host. With this purpose in mind, we have attempted to synthesize a novel nontoxic biodegradable lysine diisocyanate (LDI)-and glucose-based polymer via polymerization of highly purified LDI with glucose and its subsequent hydration to form a spongy matrix. The LDI–glucose polymer was degradable in aqueous solutions at 37, 22, and 4°C, and yielded lysine and glucose as breakdown products. The degradation products of the LDI–glucose polymer did not significantly affect the pH of the solution. The physical properties of the polymer were found to be adequate for supporting cell growth in vitro, as evidenced by the fact that rabbit bone marrow stromal cells (BMSCs) attached to the polymer matrix, remained viable on its surface, and formed multilayered confluent cultures with retention of their phenotype over a period of 2 to 4 weeks. These observations suggest that the LDI–glucose polymer and its degradation products were nontoxic in vitro. Further examination in vivo over 8 weeks revealed that subcutaneous implantation of hydrated matrix degraded in vivo three times faster than in vitro. The implanted polymer was not immunogenic and did not induce antibody responses in the host. Histological analysis of the implanted polymer showed that LDI–glucose polymer induced a minimal foreign body reaction, with formation of a capsule around the degrading polymer. The results suggest that biodegradable peptide-based polymers can be synthesized, and may potentially find their way into biomedical applications because of their biodegradability and biocompatibility. PMID:12459056

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. Polymers in the gut compress the colonic mucus hydrogel.

    PubMed

    Datta, Sujit S; Preska Steinberg, Asher; Ismagilov, Rustem F

    2016-06-28

    Colonic mucus is a key biological hydrogel that protects the gut from infection and physical damage and mediates host-microbe interactions and drug delivery. However, little is known about how its structure is influenced by materials it comes into contact with regularly. For example, the gut abounds in polymers such as dietary fibers or administered therapeutics, yet whether such polymers interact with the mucus hydrogel, and if so, how, remains unclear. Although several biological processes have been identified as potential regulators of mucus structure, the polymeric composition of the gut environment has been ignored. Here, we demonstrate that gut polymers do in fact regulate mucus hydrogel structure, and that polymer-mucus interactions can be described using a thermodynamic model based on Flory-Huggins solution theory. We found that both dietary and therapeutic polymers dramatically compressed murine colonic mucus ex vivo and in vivo. This behavior depended strongly on both polymer concentration and molecular weight, in agreement with the predictions of our thermodynamic model. Moreover, exposure to polymer-rich luminal fluid from germ-free mice strongly compressed the mucus hydrogel, whereas exposure to luminal fluid from specific-pathogen-free mice-whose microbiota degrade gut polymers-did not; this suggests that gut microbes modulate mucus structure by degrading polymers. These findings highlight the role of mucus as a responsive biomaterial, and reveal a mechanism of mucus restructuring that must be integrated into the design and interpretation of studies involving therapeutic polymers, dietary fibers, and fiber-degrading gut microbes.

  17. Tacticity-induced changes in the micellization and degradation properties of poly(lactic acid)-block-poly(ethylene glycol) copolymers.

    PubMed

    Agatemor, Christian; Shaver, Michael P

    2013-03-11

    Poly(lactic acid)-block-poly(ethylene glycol) copolymers (PLA-b-PEG) featuring varying tacticities (atactic, heterotactic, isotactic) in the PLA block were synthesized and investigated for their micellar stability, degradation, and thermal properties. Utilizing tin(II) bis(2-ethylhexanoate), aluminum salan, and aluminum salen catalysts, the copolymers were synthesized through the ring-opening polymerization of d-, l-, rac-, or a blend of l- and rac-lactide using monomethoxy-poly(ethylene glycol) as a macroinitiator. The critical micelle concentration, which reflects the micellar stability, was probed using a fluorescence spectroscopic method with pyrene as the probe. The copolymers were degraded in a methanolic solution of 1,5,7-triaza-bicyclo[4.4.0]dec-5-ene and the degradation was measured by (1)H NMR spectroscopic and gel permeation chromatographic analyses. Differential scanning calorimetry and thermogravimetric analysis provided information on the thermal properties of the copolymers. Atactic and heterotactic microstructures in the PLA block resulted in lower micellar stability, as well as faster degradation and shorter erosion time compared to polymers with high isotactic enchainment (Pm). By modification of the Pm, micellar stability, degradation, and erosion rates of the copolymers can be tuned to specific biomedical applications. Interestingly, while tin(II) bis(2-ethylhexanoate) and aluminum salan-catalyzed PLA-b-PEG copolymers exhibited similar micellization behavior, the aluminum salen-catalyzed PLA-b-PEG exhibited unique behavior at high micelle concentration in the presence of the pyrene probe. This unique behavior can be attributed to the disintegration of the micelles through the interactions of long isotactic stereoblock segments. PMID:23402292

  18. 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.

  19. 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.

  20. Indirect Calibration In Electron-Probe Microanalysis

    NASA Technical Reports Server (NTRS)

    Terepka, F. M.; Vijaykumar, M.; Tewari, S. N.

    1992-01-01

    Technique for indirect calibration in electron-probe microanalysis reduces number of measurements needed without significantly degrading precision of measurement data. Advantageous when many analyses must be performed; for example, determining varying chemical composition at many positions across specimen of multicomponent alloy. Time spent acquiring data reduced considerably.

  1. 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

  2. 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.

  3. Controlled drug release and hydrolysis mechanism of polymer-magnetic nanoparticle composite.

    PubMed

    Yang, Fang; Zhang, Xiaoxian; Song, Lina; Cui, Huating; Myers, John N; Bai, Tingting; Zhou, Ying; Chen, Zhan; Gu, Ning

    2015-05-13

    Uniform and multifunctional poly(lactic acid) (PLA)-nanoparticle composite has enormous potential for applications in biomedical and materials science. A detailed understanding of the surface and interface chemistry of these composites is essential to design such materials with optimized function. Herein, we designed and investigated a simple PLA-magnetic nanoparticle composite system to elucidate the impact of nanoparticles on the degradation of polymer-nanoparticle composites. In order to have an in-depth understanding of the mechanisms of hydrolysis in PLA-nanoparticle composites, degradation processes were monitored by several surface sensitive techniques, including scanning electron microscopy, contact angle goniometry, atomic force microscopy, and sum frequency generation spectroscopy. As a second-order nonlinear optical technique, SFG spectroscopy was introduced to directly probe in situ chemical nature at the PLA-magnetic nanoparticle composite/aqueous interface, which allowed for the delineation of molecular mechanisms of various hydrolysis processes for degradation at the molecular level. The best PLA-NP material, with a concentration of 20% MNP in the composite, was found to enhance the drug release rate greater than 200 times while maintaining excellent controlled drug release characteristics. It was also found that during hydrolysis, various crystalline-like PLA domains on the surfaces of PLA-nanoparticle composites influenced various hydrolysis behaviors of PLA. Results from this study provide new insight into the design of nanomaterials with controlled degradation and drug release properties, and the underlined molecular mechanisms. The methodology developed in this study to characterize the polymer-nanoparticle composites is general and widely applicable.

  4. Controlled drug release and hydrolysis mechanism of polymer-magnetic nanoparticle composite.

    PubMed

    Yang, Fang; Zhang, Xiaoxian; Song, Lina; Cui, Huating; Myers, John N; Bai, Tingting; Zhou, Ying; Chen, Zhan; Gu, Ning

    2015-05-13

    Uniform and multifunctional poly(lactic acid) (PLA)-nanoparticle composite has enormous potential for applications in biomedical and materials science. A detailed understanding of the surface and interface chemistry of these composites is essential to design such materials with optimized function. Herein, we designed and investigated a simple PLA-magnetic nanoparticle composite system to elucidate the impact of nanoparticles on the degradation of polymer-nanoparticle composites. In order to have an in-depth understanding of the mechanisms of hydrolysis in PLA-nanoparticle composites, degradation processes were monitored by several surface sensitive techniques, including scanning electron microscopy, contact angle goniometry, atomic force microscopy, and sum frequency generation spectroscopy. As a second-order nonlinear optical technique, SFG spectroscopy was introduced to directly probe in situ chemical nature at the PLA-magnetic nanoparticle composite/aqueous interface, which allowed for the delineation of molecular mechanisms of various hydrolysis processes for degradation at the molecular level. The best PLA-NP material, with a concentration of 20% MNP in the composite, was found to enhance the drug release rate greater than 200 times while maintaining excellent controlled drug release characteristics. It was also found that during hydrolysis, various crystalline-like PLA domains on the surfaces of PLA-nanoparticle composites influenced various hydrolysis behaviors of PLA. Results from this study provide new insight into the design of nanomaterials with controlled degradation and drug release properties, and the underlined molecular mechanisms. The methodology developed in this study to characterize the polymer-nanoparticle composites is general and widely applicable. PMID:25881356

  5. 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.

  6. Polymers at Surfaces and Interfaces

    NASA Astrophysics Data System (ADS)

    Tsige, Mesfin

    2015-03-01

    Interfaces between solids, liquids, and gases play an important role in a wide range of practical applications and have been a subject of scientific interest since Poisson showed in 1831 that the order parameter of liquids near interfaces must deviate considerably from its bulk value. In particular, polymers at surfaces and interfaces have been a subject of extensive theoretical, experimental and computational studies for a long time due to their use in many diverse applications ranging from antifouling coatings to flexible electronic devices. Understanding the structure and thermodynamic properties of polymers at surfaces and interfaces is thus an area of fundamental and current technological interest. Although encouraging experimental progress has been made over the years in understanding the molecular structure of polymers in contact with various environments, selectively probing their structure and dynamics at surfaces and interfaces has been extremely difficult. Computer simulations, especially molecular dynamics (MD) simulations, have proven over the years to be an invaluable tool in providing molecular details at interfaces that are usually lacking in the experimental data. In this talk, I'll give an overview of some previous simulation efforts to understand the structure and dynamics of polymers at surfaces and buried interfaces. I will conclude by presenting our current and ongoing work on combining ab initio calculations and MD simulations with Sum Frequency Generation (SFG) Spectroscopy to study polymer surfaces. This approach demonstrates the future role of MD in surface science. Work supported by NSF (DMR0847580 and DMR1410290) and Petroleum Research Fund of the American Chemical Society.

  7. Polymer Science.

    ERIC Educational Resources Information Center

    Frank, Curtis W.

    1979-01-01

    Described is a series of four graduate level courses in polymer science, offered or currently in preparation, at Stanford University. Course descriptions and a list of required and recommended texts are included. Detailed course outlines for two of the courses are presented. (BT)

  8. Functional polymers

    SciTech Connect

    Wegner, G.

    2000-01-01

    Improving the existing polymer materials and the designing of model polymers need fundamental insights into the structure and dynamics over a large range of length and time scales. Consequently, a host of quite different methods needs to be applied to gain insights into the molecular and supramolecular structures and interactions that determine the performance of these materials. Supramolecular structures derived from shape persistent (stiff) macromolecules are used as examples to demonstrate the correlation between chemical structure, order phenomena and performance in applications concerning advanced or developing technologies: organic light emitting diodes (OLEDs) and separator membranes in lithium based batteries and fuel cells. Polymers are also important as additives in the manufacture and the processing of other materials. The design of block copolymers to control the nucleation and growth of inorganic particles precipitating from aqueous solutions (mineralization) is discussed as well as the use of block copolymers to optimize the processing of ceramic pieces and objects. Finally, the modification of surfaces by polymers including aspects of biocompatibility is discussed. Some remarks concerning the importance of recent developments and advances in synthesis of macromolecular materials are also given.

  9. 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.

  10. 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.

  11. Recovery of petroleum with chemically treated high molecular weight polymers

    SciTech Connect

    Gibb, C.L.; Rhudy, J.S.

    1980-11-18

    Plugging of reservoirs with high molecular weight polymers, e.g. Partially hydrolyzed polyacrylamide, is overcome by chemically treating a polymer having an excessively high average molecular weight prior to injection into a reservoir with an oxidizing chemical, e.g. sodium hypochlorite, and thereafter incorporating a reducing chemical, e.g., sodium sulfite, to stop degradation of the polymer when a desired lower average molecular weight and flooding characteristics are attained.

  12. 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 natura