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Sample records for imide oligomers endcapped

  1. Imide Oligomers Endcapped with Phenylethynl Phthalic Anhydrides and Polymers Therefrom

    NASA Technical Reports Server (NTRS)

    Hergenrother, Paul M. (Inventor); Smith, Joseph G., Jr. (Inventor)

    1998-01-01

    Controlled molecular weight phenylethynyl terminated imide oligomers (PETIs) have been prepared by the cyclodehydration of precursor phenylethynyl terminated amic acid oligomers. Amino terminated amic acid oligomers are prepared from the reaction of dianhydride(s) with an excess of diamine(s) and subsequently endcapped with phenylethynyl phthalic anhydride(s) (PEPA). The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone or N.N-dimethylacetamide under nitrogen at room temperature. The amic acid oligomers are subsequently cyclodehydrated either thermally or cheznicauy to the corresponding imide oligomers. Direct preparation of PETIs from the reaction of dianhydxide(s) with an excess of diamine(s) and endcapped with phenylethynyl phthalic anhydride(s) has been performed in m-cresol. Phenylethynyl phthalic anhydrides are synthesized by the palladium catalyzed reaction of phenylacetylene with bromo substituted phthalic anhydrides in triethylamine. These new materials exhibit excellent properties and are potentially useful as adhesives, coatings, films, moldings and composite matrices.

  2. Imide oligomers endcapped with phenylethynyl phthalic anhydrides and polymers therefrom

    NASA Technical Reports Server (NTRS)

    Hergenrother, Paul M. (Inventor); Smith, Jr., Joseph G. (Inventor)

    1996-01-01

    Controlled molecular weight phenylethynyl terminated imide oligomers (PETIs) have been prepared by the cyclodehydration of precursor phenylethynyl terminated amic acid oligomers. Amino terminated amic acid oligomers are prepared from the reaction of dianhydride(s) with an excess of diamine(s) and subsequently endcapped with phenylethynyl phthalic anhydride(s) (PEPA). The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone or N,N-dimethylacetamide under nitrogen at room temperature. The amic acid oligomers are subsequently cyclodehydrated either thermally or chemically to the corresponding imide oligomers. Direct preparation of PETIs from the reaction of dianhydride(s) with an excess of diamine(s) and endcapped with phenylethynyl phthalic anhydride(s) has been performed in m-cresol. Phenylethynyl phthalic anhydrides are synthesized by the palladium catalyzed reaction of phenylacetylene with bromo substituted phthalic anhydrides in triethylamine. These new materials exhibit excellent properties and are potentially useful as adhesives, coatings, films, moldings and composite matrices.

  3. Phenylethynyl terminated imide oligomers

    NASA Technical Reports Server (NTRS)

    Hergenrother, Paul M. (Inventor); Bryant, Robert G. (Inventor); Jensen, Brian J. (Inventor); Havens, Stephen J. (Inventor)

    1995-01-01

    Four phenylethynyl amine compounds - 3 and 4-aminophenoxy-4'-phenylethynylbenzophenone, and 3 and 4-amino-4'-phenylethynylbenzophenone - were readily prepared and were used to endcap imide oligomers. Phenylethynyl-terminated amide acid oligomers and phenylethynyl-terminated imide oligomers with various molecular weights and compositions were prepared and characterized. These oligomers were cured at 300 to 400 C to provide crosslinked polyimides with excellent solvent resistance, high strength and modulus, and good high temperature properties. Adhesive panels, composites, films, and moldings from these phenylethynyl terminated imide oligomers gave excellent mechanical performance.

  4. Characterization of geometric isomers of Norbornene end-capped imides

    NASA Technical Reports Server (NTRS)

    Young, P. R.; Chang, A. C.

    1983-01-01

    Three geometric isomers from the thermal isomerization of methylene-4,4' bis(endo-N-phenylbicyclo/2.2.1/hept-2-ene-5,6-di carboximide) (I) were chromatographically separated and isolated in order to investigate the thermal cure of norbornene end-capped imide oligomers, which display considerable promise for use in various aerospace adhesive and composite applications. Endo-endo (I), endo-exo (II), and exo-exo (III) configurations were assigned to each compound based on the results of NMR spectroscopy. Several chromatographic, spectroscopic, and thermal techniques were then used to characterize these three isomers which serve as model compounds for norbornene end-capped polyimides. It was found that each compound thermally isomerized to an equilibrium mixture of all three compounds prior to cure. It is proposed that these compounds react by different mechanisms in air and nitrogen.

  5. Liquid crystalline thermosets from ester, ester-imide, and ester-amide oligomers

    NASA Technical Reports Server (NTRS)

    Dingemans, Theodorous J. (Inventor); Weiser, Erik S. (Inventor); St. Clair, Terry L. (Inventor)

    2005-01-01

    Main chain thermotropic liquid crystal esters, ester-imides, and ester-amides were prepared from AA, BB, and AB type monomeric materials and were end-capped with phenylacetylene, phenylmaleimide, or nadimide reactive end-groups. The resulting reactive end-capped liquid crystal oligomers exhibit a variety of improved and preferred physical properties. The end-capped liquid crystal oligomers are thermotropic and have, preferably, molecular weights in the range of approximately 1000-15,000 grams per mole. The end-capped liquid crystal oligomers have broad liquid crystalline melting ranges and exhibit high melt stability and very low melt viscosities at accessible temperatures. The end-capped liquid crystal oligomers are stable for up to an hour in the melt phase. These properties make the end-capped liquid crystal oligomers highly processable by a variety of melt process shape forming and blending techniques including film extrusion, fiber spinning, reactive injection molding (RIM), resin transfer molding (RTM), resin film injection (RFI), powder molding, pultrusion, injection molding, blow molding, plasma spraying and thermo-forming. Once processed and shaped, the end-capped liquid crystal oligomers were heated to further polymerize and form liquid crystalline thermosets (LCT). The fully cured products are rubbers above their glass transition temperatures. The resulting thermosets display many properties that are superior to their non-end-capped high molecular weight analogs.

  6. Solvent free low-melt viscosity imide oligomers and thermosetting polymide composites

    NASA Technical Reports Server (NTRS)

    Chuang, Chun-Hua (Inventor)

    2012-01-01

    .[.This invention relates to the composition and a solvent-free process for preparing novel imide oligomers and polymers specifically formulated with effective amounts of a dianhydride such as 2,3,3',4-biphenyltetra carboxylic dianydride (a-BPDA), at least one aromatic diamine and an endcapped of 4-phenylethynylphthalic anhydride (PEPA) or nadic anhydride to produce imide oligomers that possess a low-melt viscosity of 1-60 poise at 260-280.degree. C. When the imide oligomer melt is cured at about 371.degree. C. in a press or autoclave under 100-500 psi, the melt resulted in a thermoset polyimide having a glass transition temperature (T.sub.g) equal to and above 310.degree. C. A novel feature of this process is that the monomers; namely the dianhydrides, diamines and the endcaps, are melt processable to form imide oligomers at temperatures ranging between 232-280.degree. C. (450-535.degree. F.) without any solvent. These low-melt imide oligomers can be easily processed by resin transfer molding (RTM), vacuum-assisted resin transfer molding (VARTM) or the resin infusion process with fiber preforms e.g. carbon, glass or quartz preforms to produce polyimide matrix composites with 288-343.degree. C. (550-650.degree. F.) high temperature performance capability..]. .Iadd.This invention relates to compositions and a solvent-free reaction process for preparing imide oligomers and polymers specifically derived from effective amounts of dianhydrides such as 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA), at least one aromatic polyamine and an end-cap such as 4-phenylethynyphthalic anhydride (PEPA) or nadic anhydride to produce imide oligomers that possess a low-melt viscosity of 1-60 poise at 260.degree. C.-280.degree. C..Iaddend.

  7. Liquid Crystalline Thermosets from Ester, Ester-imide, and Ester-amide Oligomers

    NASA Technical Reports Server (NTRS)

    Dingemans, Theodorus J. (Inventor); Weiser, Erik S. (Inventor); St. Clair, Terry L. (Inventor)

    2009-01-01

    Main chain thermotropic liquid crystal esters, ester-imides, and ester-amides were prepared from AA, BB, and AB type monomeric materials and end-capped with phenylacetylene, phenylmaleimide, or nadimide reactive end-groups. The end-capped liquid crystal oligomers are thermotropic and have, preferably, molecular weights in the range of approximately 1000-15,000 grams per mole. The end-capped liquid crystaloligomers have broad liquid crystalline melting ranges and exhibit high melt stability and very low melt viscosities at accessible temperatures. The end-capped liquid crystal oli-gomers are stable forup to an hour in the melt phase. They are highly processable by a variety of melt process shape forming and blending techniques. Once processed and shaped, the end-capped liquid crystal oigomers were heated to further polymerize and form liquid crystalline thermosets (LCT). The fully cured products are rubbers above their glass transition temperatures.

  8. Liquid Crystalline Thermosets from Ester, Ester-Imide, and Ester-Amide Oligomers

    NASA Technical Reports Server (NTRS)

    Dingemans, Theodornus J. (Inventor); Weiser, Erik S. (Inventor); SaintClair, Terry L. (Inventor)

    2005-01-01

    Main chain thermotropic liquid crystal esters, ester-imides, and ester-amides were prepared from AA, BB, and AB type monomeric materials and were end-capped with phenylacetylene, phenylmaleimide, or nadimide reactive end-groups. The resulting reactive end-capped liquid crystal oligomers exhibit a variety of improved and preferred physical properties. The end-capped liquid crystal oligomers are thermotropic and have, preferably, molecular weights in the range of approximately 1000-15,OOO grams per mole. The end-capped liquid crystal oligomers have broad liquid crystalline melting ranges and exhibit high melt stability and very low melt viscosities at accessible temperatures. The end-capped liquid crystal oligomers are stable for up to an hour in the melt phase. These properties make the end-capped liquid crystal oligomers highly processable by a variety of melt process shape forming and blending techniques including film extrusion, fiber spinning, reactive injection molding (RIM), resin transfer molding (RTM), resin film injection (RFI), powder molding, pultrusion, injection molding, blow molding, plasma spraying and thermo-forming. Once processed and shaped, the end- capped liquid crystal oligomers were heated to further polymerize and form liquid crystalline thermosets (LCT). The fully cured products are rubbers above their glass transition temperatures. The resulting thermosets display many properties that are superior to their non-end-capped high molecular weight analogs.

  9. Solvent Free Low-Melt Viscosity Imide Oligomers And Thermosetting Polyimide Composites

    NASA Technical Reports Server (NTRS)

    Chuang, CHun-Hua (Inventor)

    2006-01-01

    This invention relates to the composition and a solvent-free process for preparing novel imide oligomers and polymers specifically formulated with effective amounts of a dianhydride such as 2,3,3',4-biphenyltetra carboxylic dianydride (a-BPDA), at least one aromatic diamine' and an endcapped of 4-phenylethynylphthalic anhydride (PEPA) or nadic anhydride to produce imide oligomers that possess a low-melt viscosity of 1-60 poise at 260-280" C. When the imide oligomer melt is cured at about 371 C. in a press or autoclave under 100-500 psi, the melt resulted in a thermoset polyimide having a glass transition temperature (T(sub g)) equal to and above 310 C. A novel feature of this process is that the monomers; namely the dianhydrides, diamines and the endcaps, are melt processable to form imide oligomers at temperatures ranging between 232-280 C. (450-535 F) without any solvent. These low-melt imide oligomers can be easily processed by resin transfer molding (RTM), vacuum-assisted resin transfer molding (VARTM) or the resin infusion process with fiber preforms e.g. carbon, glass or quartz preforms to produce polyimide matrix composites with 288-343C (550-650 F) high temperature performance capability.

  10. Preparation and applications of a variety of fluoroalkyl end-capped oligomer/hydroxyapatite composites.

    PubMed

    Takashima, Hiroki; Iwaki, Ken-Ichi; Furukuwa, Rika; Takishita, Katsuhisa; Sawada, Hideo

    2008-04-15

    A variety of fluoroalkyl end-capped oligomers were applied to the preparation of fluorinated oligomer/hydroxyapatite (HAp) composites (particle size: 38-356 nm), which exhibit a good dispersibility in water and traditional organic solvents. These fluoroalkyl end-capped oligomer/HAp composites were easily prepared by the reactions of disodium hydrogen phosphate and calcium chloride in the presence of self-assembled molecular aggregates formed by fluoroalkyl end-capped oligomers in aqueous solutions. In these fluorinated HAp composites thus obtained, fluoroalkyl end-capped acrylic acid oligomers and 2-methacryloyloxyethanesulfonic acid oligomer/HAp nanocomposites afforded transparent colorless solutions toward water; however, fluoroalkyl end-capped N,N-dimethylacrylamide oligomer and acryloylmorpholine oligomer were found to afford transparent colorless solutions with trace amounts of white-colored HAp precipitants under similar conditions. HAp could be encapsulated more effectively into fluorinated 2-methacryloyloxyethanesulfonic acid oligomeric aggregate cores to afford colloidal stable fluorinated oligomer/HAp composites, compared to that of fluorinated acrylic acid oligomers. These fluorinated oligomer/HAp composites were applied to the surface modification of glass and PVA to exhibit a good oleophobicity imparted by fluorine. HAp formation was newly observed on the modified polyethylene terephthalate film surface treated with fluorinated 2-methacryloyloxyethanesulfonic acid oligomers and acrylic acid oligomer/HAp composites by soaking these films into the simulated body fluid.

  11. Imide Oligomers Containing Pendent and Terminal Phenylethynyl Groups-2

    NASA Technical Reports Server (NTRS)

    Connell, J. W.; Smith, J. G., Jr.; Hergenrother, P. M.

    1998-01-01

    As part of a program to develop high-performance/high-temperature structural resins for aeronautical applications, imide oligomers containing pendent and terminal phenylethynyl groups were prepared, characterized and the cured resins evaluated as composite matrices. The oligomers were prepared at a calculated number-average molecular weight of 5000 g/mol and contained 15-20 mol% pendent phenylethynyl groups. In previous work, an oligomer containing pendent and terminal phenylethynyl groups exhibited a high glass transition temperature (approximately 313 C), and laminates therefrom exhibited high compressive properties, but processability, fracture toughness, microcrack resistance and damage tolerance were less than desired. In an attempt to improve these deficiencies, modifications in the oligomeric backbone involving the incorporation of 1,3-bis(3-aminophenoxy)benzene were investigated as a means of improving processability and toughness without detracting from the high glass transition temperature and high compressive properties. The amide acid oligomeric solutions were prepared in N-methyl-2-pyrrolidinone and were subsequently processed into imide powder, thin films, adhesive tape and carbon fiber prepreg. Neat resin plaques were fabricated from imide powder by compression moulding. The maximum processing pressure was 1.4 MPa and the cure temperature ranged from 350 to 371 C for 1 h for the mouldings, adhesives, films and composites. The properties of the 1,3-bis(3-aniinophenoxy)benzene modified cured imide oligomers containing pendent and terminal phenylethynyl groups are compared with those of previously prepared oligomers containing pendent and terminal phenylethynyl groups of similar composition and molecular weight.

  12. Synthesis of imide/arylene ether copolymers for adhesives and composite matrices

    NASA Technical Reports Server (NTRS)

    Jensen, B. J.; Hergenrother, P. M.; Bass, R. G.

    1991-01-01

    A series of imide/arylene ether copolymers were prepared from the reaction of an amorphous arylene ether oligomer and a semi-crystalline imide oligomer. These copolymers were thermally characterized and mechanical properties were measured. One block copolymer was endcapped and the molecular weight was controlled to provide a material that displayed good compression moldability and attractive adhesion and composite properties.

  13. Curing chemistry of phenylethynyl-terminated imide oligomers: Model compounds, carbon-13 labeling and cure analysis

    NASA Astrophysics Data System (ADS)

    Roberts, Christopher Chad

    1998-11-01

    Phenylethynyl-terminated imide oligomers (PETI) are currently considered the state-of-the-art high performance resins for aerospace applications. The processing of these resins is more facile because of their low molecular weight, but PETI's cure to form a tough, solvent-resistant material. However, the final cure structure was a complete mystery. Hence, the present study was set forth with three essential goals. The determination of the final structure of the crosslinked polymer is of obvious importance. Second, the crosslinking mechanism and controlling factors is also of interest. Lastly, the final structure of the crosslinked polymers was correlated with mechanical and thermal properties, thereby helping to establish the structure-processing-properties relationships for PETI resins. These goals were accomplished by using a combination of synthesis of model compounds synthesis and proposed cure products, sp{13}C labeling of the ethynyl endgroup in PETI's, monitoring of the thermal cure using solid state sp{13}C NMR and ESR and molecular modeling techniques. Phenylethynyl endcapping agents, 4-(phenylethynyl)phthalic anhydride (PEPA) and 3-(phenylethynyl)aniline (3PEA), were synthesized via the palladium-catalyzed coupling of phenylacetylene with 4-bromophthalic anhydride or 3-iodonitrobenzene followed by reduction to 3PEA, respectively. Isolated yields of 41 and 86% for 3PEA and PEPA were obtained, respectively. Model compounds were synthesized from 3PEA and PEPA by reacting with them the appropriate aniline or phthalic anhydride derivative. Model compounds included N-pentafluorophenyl-4-(phenylethynyl)phthalimide (PEPA/F5An), N-(4-trifluoromethyl-phenyl)4-(phenylethynyl)phthalimide (PEPA/F3CAn), N-lbrack 3-(phenylethynyl)phenylrbrack\\ phthalimide (3PEA/PA), N-phenyl-4-(phenylethynyl)phthalimide (PEPA/An), N-(4-phenoxyphenyl)4-(phenylethynyl)phthalimide (PEPA/POAn), and N-(1-naphthyl)-4-(phenylethynyl)phthalimide (PEPA/Anaph). Proposed cure products such as

  14. The Effect of Molecular Weight on the Composite Properties of Cured Phenylethynyl Terminated Imide Oligomers

    NASA Technical Reports Server (NTRS)

    Smith, J. G., Jr.; Connell, J. W.; Hergenrother, P. M.

    1997-01-01

    As part of a program to develop high temperature/high performance structural resins for aeronautical applications, imide oligomers containing terminal phenylethynyl groups with calculated number average molecular weights of 1250, 2500 and 5000 g/mol were prepared, characterized, and evaluated as adhesives and composite matrix resins. The goal of this work was to develop resin systems that are processable using conventional processing equipment into void free composites that exhibit high mechanical properties with long term high temperature durability, and are not affected by exposure to common aircraft fluids. The imide oligomers containing terminal phenylethynyl groups were fabricated into titanium adhesive specimens and IM-7 carbon fiber laminates under 0.1 - 1.4 MPa for 1 hr at 350-371 C. The lower molecular weight oligomers exhibited higher cured Tg, better processability, and better retention of mechanical properties at elevated temperature without significantly sacrificing toughness or damage tolerance than the higher molecular weight oligomer. The neat resin, adhesive and composite properties of the cured polymers will be presented.

  15. Chemistry and properties of imide oligomers containing pendant and terminal phenylethynyl groups

    SciTech Connect

    Smith, J.G. Jr.

    1996-12-31

    As part of a continuing effort to develop high performance/high temperature structural resins for aeronautical applications, oligomers containing latent reactive groups have been under investigation. Material requirements include ease of processability, retention of mechanical properties at elevated temperature, and no loss of mechanical properties after exposure to aircraft fluids such as hydraulic fluid, jet fuel, and cleaning fluids. The phenylethynyl group is an ideal latent reactive group. It has a relatively high cure temperature ({approximately}350{degrees}C) and a large processing window can be obtained with materials possessing the proper glass transition temperature. The thermally cured materials exhibit good retention of mechanical properties at elevated temperatures with no significant loss of properties after exposure to various solvents. To date, the phenylethynyl group has been incorporated either terminal or pendant to a variety of imide oligomers. Upon thermal cure, the phenylethynyl group undergoes chain extension, branching and/or crosslinking; however, the final cured product has not been well defined. As an extension of this work, a series of imide oligomers containing both pendant and terminal phenylethynyl groups (PTPEIs) were prepared as a means to improve retention of mechanical properties at elevated temperature while maintaining processability. The PTPEI oligomers were characterized, thermally cured and the cured polymers evaluated as unoriented thin films and adhesives. The chemistry, physical, and mechanical properties of these materials will be discussed.

  16. New Endcaps for Improved Oxidation Resistance in PMR Polyimides

    NASA Technical Reports Server (NTRS)

    Frimer, Aryeh A.

    2003-01-01

    A polyimide is a polymer composed of alternating units of diamine and dianhydride, linked to each other via an imide bond. PMR polyimides, commonly used in the aerospace industry, are generally capped at each end by an endcap (such as the nadic endcap used in PMR 15) which serves a double function: (1) it limits the number of repeating units and, hence, the average molecular weight of the various polymer chains (oligomers), thereby improving processibility; (2) Upon further treatment (curing), the endcap crosslinks the various oligomer strands into a tough heat-resistant piece. It is this very endcap, so important to processing, that accounts for much of the weight loss in the polymer on aging in air at elevated temperatures. Understanding this degradation provides clues for designing new endcaps to slow down degradation, and prolong the lifetime of the material.

  17. Kinetics of imidization and crosslinking in PMR-polyimide resin

    NASA Technical Reports Server (NTRS)

    Lauver, R. W.

    1977-01-01

    Infrared spectroscopy and differential scanning calorimetry were employed to study the imidization and crosslinking kinetics of norbornenyl-capped, addition-type polyimide resins (designated PMR for polymerization of monomer reactants). The spectral and thermal analyses were performed on resin specimens which had been isothermally aged at temperatures appropriate for imidization (120 to 204 C) and crosslinking (275 to 325 C). Imidization occurs rapidly (approximately 0.01/min) at short times, while at times longer than approximately 0.5 hour, the rate decreases significantly (approximately 0.0001/min). The crosslinking reaction exhibits first order kinetics during the initial portion of the reaction and its rate appears to be limited by the reversion of the norbornenyl Diels-Alder adduct. The total heat evolved per mole of endcap during crosslinking shows an inverse dependence on the molecular weight of the imide prepolymers. This reflects the effect of endcap dilution and decreased mobility of the larger oligomers.

  18. Fluoroalkyl end-capped vinyltrimethoxysilane oligomer/anatase titanium oxide nanocomposites possessing photocatalytic activity even after calcination at 1000°C.

    PubMed

    Guo, Sujuan; Yoshioka, Hiroaki; Kakehi, Hiroshi; Kato, Yoshihiro; Miura, Masashi; Isu, Norifumi; Ameduri, Bruno; Sawada, Hideo

    2012-12-01

    Fluoroalkyl end-capped vinyltrimethoxysilane oligomer [R(F)-(VM)(n)-R(F)] underwent the sol-gel reaction under alkaline conditions in the presence of anatase titanium oxide nanoparticles (an-TiO(2)) in tetrahydrofuran to give the corresponding fluorinated oligomer/anatase titanium oxide nanocomposites [R(F)-(VM-SiO(2))(n)-R(F)/an-TiO(2)]. Crystalline structure of an-TiO(2) in the nanocomposites thus obtained was found to keep completely its structure without phase transformation to rutile even after calcination at 1000°C, although crystalline structure of the original an-TiO(2) nanoparticles underwent a complete phase transformation to the rutile under similar conditions. Interestingly, R(F)-(VM-SiO(2))(n)-R(F)/an-TiO(2) nanocomposites before and after calcination at 1000°C exhibited the similar photocatalytic activity for the decolorization of methylene blue under UV light irradiation.

  19. Copoly(imide siloxane) Abhesive Materials with Varied Siloxane Oligomer Length

    NASA Technical Reports Server (NTRS)

    Wohl, Christoper J.; Atkins, Brad M.; Lin, Yi; Belcher, Marcus A.; Connell, John W.

    2010-01-01

    In this work, low surface energy copoly(imide siloxane)s were synthesized with various siloxane segment lengths. Characterization of these materials revealed that domain formation of the low surface energy component within the matrix was more prevalent for longer siloxane segments as indicated by increased opacity, decreased mechanical properties, and variation of the Tg. Incorporation of siloxanes lowered the polymer s surface energy as indicated by water contact angle values. Topographical modification of these materials by laser ablation patterning further reduced the surface energy, even generating superhydrophobic surfaces. Combined, the contact angle data and particle adhesion testing indicated that copoly(imide siloxane) materials may provide greater mitigation to particulate adhesion than polyimide materials alone. These enhanced surface properties for abhesive applications did result in a reduction of the tensile moduli of the copolymers. It is possible that lower siloxane loading levels would result in retention of the mechanical properties of the polyimide while still affording abhesive surface properties. This hypothesis is currently being investigated. Laser ablation patterning offers further reduction in particle retention as the available surface area for particle adhesion is reduced. Pattern variation and size dependencies are currently being evaluated. For the purposes of lunar dust adhesion mitigation, it is likely that this approach, termed passive due to the lack of input from an external energy source, would not be sufficient to mitigate surface contamination or clean contaminated surfaces for some lunar applications. It is feasible to combine these materials with active mitigation strategies - methods that utilize input from external energy sources - would broaden the applicability of such materials for abhesive purposes. Collaborative efforts along these lines have been initiated with researchers at NASA Kennedy Space Center where experiments

  20. The synthesis, characterization and thermal chemistry of modified norbornenyl PMR endcaps

    NASA Technical Reports Server (NTRS)

    Sukenik, C. N.; Ritchey, W. M.; Malhotra, V.; Varde, U.

    1985-01-01

    As part of a program to further the understanding of the polymerization of Nadic-Endcapped PMR systems, a series of model Norbornenyl-Imides has been synthesized and their thermal behavior explored. Their syntheses and characterizations as well as their rearrangement and polymerization chemistry are described. Monomer isomerization at temperatures as low as 125 C and oligomer formation at somewhat higher temperatures are observed. Approximate relative rates for competing isomerization pathways are established and some information is obtained about the details of oligomer formation. The relationship of this data to current PMR systems is briefly discussed.

  1. Synthesis and cure mechanism characterization of phenylethynyl-terminated imide oligomers

    NASA Astrophysics Data System (ADS)

    Back, Susanna Branion

    Polymer matrix composites (PMC) are being investigated by the Air Force for use in engine applications, which are comprised of an intermediate carbon fiber-reinforced high temperature phenylethynyl-terminated fluorinated polyimide resin. The high-temperature phenylethynyl-terminated fluorinated polyimide resin is prepared from 4-(phenylethynyl)phthalic anhydride (4-PEPA), p-phenylenediamine (p-PDA), and hexafluoroisopropylidene bisphthalic dianhydride (6FDA). In order for these materials to be exploited to their full potential, many fundamental aspects of the polymer system need to be better understood. For this study, the high-temperature cure mechanism, the chemical structures of cure reaction products, and the effect of physical properties of impurities in the 4-PEPA monomer were investigated. A phenylethynyl-terminated imide model compound, N-(3-phenoxybenzene)-4-phenylethynylphthalimide (N-PBPEP), was prepared using both industrial 4-PEPA and recrystallized 4-PEPA. The thermal cure of this low molecular weight compound was studied using a variety of analytical techniques including differential scanning calorimetry, Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), and mass spectrometry (MS). N-PBPEP made from industrial 4-PEPA begins curing 25°C later than N-PBPEP made from recrystallized 4-PEPA, indicating that thermal cure is affected by the purity of the 4-PEPA starting material. Also, both versions form an 830 g/mol dimer with three possible mechanistic pathways.

  2. Copoly(Imide Siloxane) Abhesive Materials with Varied Siloxane Oligomer Length

    NASA Technical Reports Server (NTRS)

    Wohl, Christopher J.; Atkins, Brad M.; Belcher, Marcus A.; Connell, John W.

    2010-01-01

    Incorporation of PDMS moieties into a polyimide matrix lowered the surface energy resulting in enhanced adhesive interactions. Polyimide siloxane materials were generated using amine-terminated PDMS oligomers of different lengths to study changes in surface migration behavior, phase segregation, mechanical, thermal, and optical properties. These materials were characterized using contact angle goniometry, tensile testing, and differential scanning calorimetry. The surface migration behavior of the PDMS component depended upon the siloxane molecular weight as indicated by distinct relationships between PDMS chain length and advancing water contact angles. Similar correlations were observed for percent elongation values obtained from tensile testing, while the addition of PDMS reduced the modulus. High fidelity topographical modification via laser ablation patterning further reduced the polyimide siloxane surface energy. Initial particulate adhesion testing experiments demonstrated that polyimide siloxane materials exhibited greater abhesive interactions relative to their respective homopolyimides.

  3. Low Viscosity Imides Based on Asymmetric Oxydiphthalic Anhydride

    NASA Technical Reports Server (NTRS)

    Chuang, Kathy C.; Criss, Jim M., Jr.; Mintz, Eric A.; Scheiman, Daniel A.; Nguyen, Baochau N.; McCorkle, Linda S.

    2008-01-01

    A series of low-melt viscosity imide resins were prepared from asymmetric oxydiphthalic dianhydride (a-ODPA) and 4-phenylethynylphthalic anhydride as the endcap, along with 3,4' - oxydianiline (3,4' -ODA), 3,4' -methylenedianiline (3,4' -MDA), 3,3' -methylenedianiline (3,3' - MDA) and 3,3'-diaminobenzophenone (3,3'-DABP), using a solvent-free melt process. These imide oligomers displays low-melt viscosities (2-15 poise) at 260-280 C, which made them amenable to low-cost resin transfer molding (RTM) process. The a-ODPA based RTM resins exhibits glass transition temperatures (Tg's) in the range of 265-330 C after postcure at 343 C. The mechanical properties of these polyimide/carbon fiber composites fabricated by RTM will be discussed.

  4. Adhesive and Composite Properties of a New Phenylethynyl Terminated Imide

    NASA Technical Reports Server (NTRS)

    Thompson, C. M.; Connell, J. W.; Hergenrother, P. M.

    2002-01-01

    A relatively new phenylethynyl terminated imide oligomer (PETI) from the reaction of 2,3,',4'- biphenyltetracarboxylic dianhydride, 4,4'-oxydianiline and endcapped with 4- phenylethynylphthalic anhydride at a calculated number average molecular weight of 5000 g/mole was evaluated as an adhesive and composite matrix. The asymmetric dianhydride imparts a low melt viscosity to the oligomer and a high glass transition temperature to the cured resin. Preliminary adhesive work with titanium (6Al-4V) adherend gave good room temperature (RT) tensile shear strengths and excellent retention of RT strength at 260 C. Preliminary composite work using unsized IM7 carbon fiber provided moderate to high mechanical properties. The chemistry, mechanical, and physical properties of the new PETI in neat resin, adhesive and composite form are presented.

  5. NMR Guided Design of Endcaps With Improved Oxidation Resistance

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B.; Frimer, Aryeh A.

    2002-01-01

    A polyimide is a polymer composed of alternating units of diamine and dianhydride, linked to each other via an imide bond. PMR polyimides, commonly used in the aerospace industry, are generally capped at each end by a norbornene endcap which serves a double function: (1) It limits the number of repeating units and, hence, the average molecular weight of the various polymer chains (oligomers), thereby improving processibility; (2) Upon further treatment (curing), the endcap crosslinks the various oligomer strands into a tough heat-resistant piece. Norbornenyl-end capped PMR polyimide resins' are widely used as polymer matrix composite materials for aircraft engine applications,2 since they combine ease of processing with good oxidative stability up to 300 C. PMR resins are prepared by a twestep approach involving the initial formation of oligomeric pre-polymers capped at both ends by a latent reactive end cap. The end cap undergoes cross-linking during higher temperature processing, producing the desired low density, high specific strength materials, as shown for PMR-15.

  6. Lower temperature curing thermoset polyimides utilizing a substituted norbornene endcap

    NASA Technical Reports Server (NTRS)

    Waters, John F.; Sukenik, Chaim N.; Kennedy, Vance O.; Livneh, Mordechai; Youngs, Wiley J.; Sutter, James K.; Meador, Mary A. B.; Burke, Luke A.; Ahn, Myong K.

    1992-01-01

    Methoxycarbonyl bridgehead substituted nadic diacid monomethyl ester, when used as an endcapping monomer, lowered the cure temperature of thermoset PMR polyimides without seriously affecting other desirable properties, such as glass transition temperature and thermal oxidative stability. The C-13 CP/MAS NMR of model compounds was used to follow the cure of resin systems using both the unmodified nadic endcap and the methoxycarbonyl-substituted endcap. Rheological analysis and differential scanning calorimetry DSC also provided evidence for the lower curing nature of the substituted endcap. Two regioisomers of the bridgehead-substituted endcap were isolated, and their chemical structures were elucidated by X-ray crystallography. The model compound and molecular modeling studies conducted ruled out the possibility of regioisomeric imide formation in the substituted endcaps.

  7. Phosphorus-containing imide resins

    NASA Technical Reports Server (NTRS)

    Varma, I. K.; Fohlen, G. M.; Parker, J. A. (Inventor)

    1983-01-01

    Bis- and tris-imides derived from tris (m-aminophenyl) phosphine oxides by reaction with maleic anhydride or its derivatives, and addition polymers of such imides, including a variant in which a mono-imide is condensed with a dianhydride and the product is treated with a further quantity of maleic anhydride. Such monomers or their oligomes may be used to impregnate fibers and fabrics which when cured, are flame resistant. Also an improved method of producing tris (m-aminophenyl) phosphine oxides from the nitro analogues by reduction with hydrazine hydrate using palladized charcoal or Raney nickel as the catalyst is described.

  8. Phenylethynyl endcapping reagents and reactive diluents

    NASA Technical Reports Server (NTRS)

    Jensen, Brian J. (Inventor); Bryant, Robert G. (Inventor); Hergenrother, Paul M. (Inventor)

    1994-01-01

    A phenylethynyl composition which can be used to endcap nucleophilic species is employed in the production of phenylethynyl terminated reactive oligomers exclusively. These phenylethynyl terminated reactive oligomers display unique thermal characteristics, as exemplified by the model compound, 4-phenoxy 4'-phenylethynylbenzophenone, which is relatively stable at 200 C, but reacts at 350 C. In addition, a reactive diluent was prepared which decreases the melt viscosity of the phenylethynyl terminated oligomers and subsequently reacts therewith to increase density of the resulting thermoset. The novelty of this invention resides in the phenylethynyl composition used to terminate a nucleophilic reagent, resulting in the exclusive production of phenylethynyl terminated reactive oligomers which display unique thermal characteristics. A reactive diluent was also employed to decrease the melt viscosity of a phenylethynyl terminated reactive oligomer and to subsequently react therewith to increase the crosslink density of the resulting thermoset. These materials have features which make them attractive candidates for use as composite matrices and adhesives.

  9. Synthesis and Characterization of Modified Phenylethynyl Imides

    NASA Technical Reports Server (NTRS)

    Jensen, B. J.; Chang, A. C.

    1998-01-01

    As an ongoing effort to develop structural adhesives for high-performance aerospace applications, recent work has focused on phenylethynyl terminated imide (PETI) oligomers. The work reported herein involves the synthesis and characterization of a series of phenylethynyl containing oligomers designated LARC(TM) MPEI (modified phenylethynyl imide). These oligomers presumably contain mixtures of linear, branched and star-shaped molecules. The fully imidized polymers exhibited minimum melt viscosities as low as 600 poise at 335 C, significantly lower than equivalent molecular weight linear materials. Ti/Ti lap shear specimens processed at 288 C under 15 psi showed tensile shear strengths as high as approx. 6000 psi and 5200 psi at ambient temperature and 177 C respectively. The chemistry and properties of these new MPEIs are presented and compared with an optimized linear PETI, LARC(TM)PETI-5.

  10. Adhesive Properties of Cured Phenylethynyl Containing Imides

    NASA Technical Reports Server (NTRS)

    Jensen, Brian J.; Chang, Alice C.

    1997-01-01

    Considerable attention has been directed towards acetylene terminated oligomers over the last 20 years' and recent work has focused on phenylethynyl terminated imide (PETI) oligomers. These reactive oligomers possess several features which make them attractive candidates for use as composite matrices and adhesives. The phenylethynyl group can be readily incorporated into many different functionalized oligomers. The reactive oligomers possess relatively low melt viscosities and thermally cure without the evolution of volatile by-products. Once cured, they typically display high glass transition temperatures (Tgs), excellent solvent resistance and high mechanical properties. new modified phenylethynyl-terminated imide (LaRC MPEI) oligomers were synthesized at various molecular weights utilizing a small amount of trifunctional amine. As long as the amount of triamine is relatively small, this approach produces a mixture of linear, star-shaped and branched polymer chains that has lower melt and solution viscosity than an equivalent molecular weight linear phenylethynyl terminated imide oligomers. The work reported herein involves the synthesis and characterization of a copolymer using this approach and the preparation of blends utilizing a phenylethynyl containing reactive plasticizer of lower molecular weight called LaRC LV-121. The chemistry and properties of this new MPEI as well as some blends of MPEI with LV-121, are presented and compared to the linear version, LARC-PETI-5.

  11. Phenylethynyl Terminated Imide (PETI) Composites Made by High Temperature Vartm

    NASA Technical Reports Server (NTRS)

    Ghose, Sayata; Watson, Kent A.; Cano, Roberto J.; Britton, Sean M.; Jensen, Brian J.; Connell, John W.; Herring, Helen M.; Lineberry, Quentin J.

    2010-01-01

    The use of composites as primary structures on aerospace vehicles has increased dramatically over the past decade. As these advanced structures increase in size and complexity, their production costs have grown significantly. A major contributor to these manufacturing costs is the requirement of elevated pressures, during high temperature processing, to create fully consolidated composite parts. Recently, NASA Langley has licensed a series of low viscosity Phenyl Ethynyl Terminated Imide, PETI, oligomers that possess a wide processing window to allow for Resin Transfer Molding, RTM, processing. These resins, PETI-8 and PETI-330, demonstrate void fractions of approx.1% under elevated pressure consolidation. However, when used with a standardized thermal curing cycle in a High Temperature Vacuum Assisted RTM (HT-VARTM) process, they display undesirable void contents in excess of 7%. It was determined previously that under the thermal cycles used for laminate fabrication, the phenylethynyl endcap underwent degradation leading to volatile evolution. Modifications to the processing cycle used in the laminate fabrication have reduced the void content significantly (typically less than 3%) for carbon fiber biaxially woven fabric. For carbon fiber uniaxial fabric, void contents of less than 2% have been obtained using both PETI-8 and PETI-330. The resins were infused into carbon fiber preforms at 260 C and cured between 316 C and 371 C. Photomicrographs of the panels were taken and void contents were determined by acid digestion. Mechanical properties of the panels were determined at both room and elevated temperatures. These include short beam shear and flexure tests. The results of this work are presented herein.

  12. Perylene imides for organic photovoltaics: yesterday, today, and tomorrow.

    PubMed

    Li, Chen; Wonneberger, Henrike

    2012-02-02

    Perylene imides have been an object of research for 100 years and their derivatives are key n-type semiconductors in the field of organic electronics. While perylene diimides have been applied in many electronic and photonic devices, their use can be traced back to the first efficient organic solar cell. By functionalizing different positions of the in total 12 positions (four peri, four bay, and four ortho-positions) on the perylene core, perylene imides with significantly different optical, electronic and morphological properties may be prepared. Perylene imides and their derivatives have been used in several types of organic photovoltaics, including flat-, and bulk-heterojunction devices as well as dye-sensitized solar cells. Additionally perylene imides-based copolymers or oligomers play an important role in single junction devices. In this review, the relationship between the photovoltaic performance and the structure of perylene imides is discussed.

  13. Cooled turbine vane with endcaps

    DOEpatents

    Cunha, Frank J.; Schiavo, Jr., Anthony L.; Nordlund, Raymond Scott; Malow, Thomas; McKinley, Barry L.

    2002-01-01

    A turbine vane assembly which includes an outer endcap having a plurality of generally straight passages and passage segments therethrough, an inner endcap having a plurality of passages and passage segments therethrough, and a vane assembly having an outer shroud, an airfoil body, and an inner shroud. The outer shroud, airfoil body and inner shroud each have a plurality of generally straight passages and passage segments therethrough as well. The outer endcap is coupled to the outer shroud so that outer endcap passages and said outer shroud passages form a fluid circuit. The inner endcap is coupled to the inner shroud so that the inner end cap passages and the inner shroud passages from a fluid circuit. Passages in the vane casting are in fluid communication with both the outer shroud passages and the inner shroud passages. Passages in the outer endcap may be coupled to a cooling system that supplies a coolant and takes away the heated exhaust.

  14. Addition Curing Thermosets Endcapped with 4-Amino (2.2) Paracyclophane

    NASA Technical Reports Server (NTRS)

    Waters, John F.; Sutter, James K.; Meador, Mary A. B.; Baldwin, Larry J.; Meador, Michael A.

    1991-01-01

    A new family of addition curing polyimides were prepared that contained 4-amino (2.2)-paracyclophane as the endcap. An improved synthesis of the endcap 4-amino-(2.2) cyclophane was accomplished increasing the yield to 60 percent and simplifying the procedure. DSC and rheological analysis of endcapped polyimide oligomers confirmed that the onset for polymerization of the ethylene bridge was 250 C. C-13 CP/MAS NMR was used to determine the structural changes of the oligomers after thermal treatment. The cyclophane capped polyimides were successfully compression molded to form void free neat resin specimens. Tg's as high as 353 C were obtained by thermomechanical analysis for postcured samples. Preliminary thermal stability studies suggest that these resins have a high onset of decomposition ranging from 549 to 567 C.

  15. Adhesive Properties of Cured Phenylethynyl containing Imides

    NASA Technical Reports Server (NTRS)

    Chang, Alice C.

    1997-01-01

    As part of a program to develop structural adhesives for high performance aerospace applications, several phenylethynyl containing oligomer blends of Larc(TM) MPEI and a reactive plasticizer designated LaRC LV-1 21 were prepared and evaluated. The fully imidized blends exhibited minimum melt viscosity as low as 1000 poise at 371 C. Ti/Ti lap shear specimens fabricated at 316 C under 15 psi gave RT strength of approx. 4300 psi and no change in strength was observed at 177 C. The chemistry and properties of this new MPEI as well as some blends of MPEI with LV-121 are presented and compared to the linear version, LARC(TM)-PETI-5.

  16. Phosphorus-containing imide resins

    NASA Technical Reports Server (NTRS)

    Varma, I. K.; Fohlen, G. M.; Parker, J. A. (Inventor)

    1984-01-01

    Flame-resistant reinforced bodies are disclosed which are composed of reinforcing fibers, filaments or fabrics in a cured body of bis- and tris-imide resins derived from tris(m-aminophenyl) phosphine oxides by reaction with maleic anhydride or its derivatives, or of addition polymers of such imides, including a variant in which a mono-imide is condensed with a dianhydride and the product is treated with a further quantity of maleic anhydride.

  17. Organic-Inorganic Hybrids Using Novel Phenylethynyl Imide Silanes

    NASA Technical Reports Server (NTRS)

    Park, C.; Lowther, S. E.; Smith, J. G., Jr.

    2001-01-01

    In this presentation, polyimide-silica hybrids using novel phenylethynyl imide silanes are reported. The phenylethynyl group is present in the organic precursor as either a pendent or an end group to bond chemically with the polyimide adhesive containing phenylethynyl groups during processing, while the silane group of the organic precursor would chemically react with the inorganic precursor through oxane bond formation. The chemical compositions of these novel hybrids were examined using X-ray mapping modes of scanning electron microscopy (SEM), which revealed a silicon gradient interphase between the high surface energy substrate and the polyimide adhesive. Novel aromatic phenylethynyl imide silanes (APEISs) and pendent phenylethynyl imide oligomeric disilanes (PPEIDSs) have been synthesized, and sol-gel solutions containing the new silanes, a phenylethynyl terminated imide oligomer (PETI-5), and an inorganic precursor were formulated to develop a gradient hybrid interphase between a titanium alloy and the adhesive. Two different sol-gel systems were investigated to develop organic-inorganic hybrids. Hybrid I was composed of an organic precursor containing both phenylethynyl and silane groups (PPEIDS) and an inorganic precursor. Functional group concentrations were controlled by the variation of the molecular weight of the imide backbone of PPEIDS. Hybrid II was composed of organic and inorganic precursors and a coupling agent containing both phenylethynyl and silane groups. Morphology and chemical composition of the hybrid interphase between the inorganic substrate and the adhesive were investigated, and the bond strength and durability were evaluated using lap shear tests at various conditions. The assessment of how the bonding at an interface is affected by various sol-gel solution compositions and environments is reported.

  18. Synthesis of Hetero-bifunctional, End-Capped Oligo-EDOT Derivatives.

    PubMed

    Spicer, Christopher D; Booth, Marsilea A; Mawad, Damia; Armgarth, Astrid; Nielsen, Christian B; Stevens, Molly M

    2017-01-12

    Conjugated oligomers of 3,4-ethylenedioxythiophene (EDOT) are attractive materials for tissue engineering applications and as model systems for studying the properties of the widely used polymer poly(3,4-ethylenedioxythiophene). We report here the facile synthesis of a series of keto-acid end-capped oligo-EDOT derivatives (n = 2-7) through a combination of a glyoxylation end-capping strategy and iterative direct arylation chain extension. Importantly, these structures not only represent the longest oligo-EDOTs reported but are also bench stable, in contrast to previous reports on such oligomers. The constructs reported here can undergo subsequent derivatization for integration into higher-order architectures, such as those required for tissue engineering applications. The synthesis of hetero-bifunctional constructs, as well as those containing mixed-monomer units, is also reported, allowing further complexity to be installed in a controlled manner. Finally, we describe the optical and electrochemical properties of these oligomers and demonstrate the importance of the keto-acid in determining their characteristics.

  19. High Temperature VARTM of Phenylethynyl Terminated Imides

    NASA Technical Reports Server (NTRS)

    Ghose, Sayata; Cano, Roberto J.; Watson, Kent A.; Britton, Sean M.; Jensen, Brian J.; Connell, John W.; Herring, Helen M.; Linberry, Quentin J.

    2009-01-01

    Depending on the part type and quantity, fabrication of composite structures using vacuum assisted resin transfer molding (VARTM) can be more affordable than conventional autoclave techniques. Recent efforts have focused on adapting VARTM for the fabrication of high temperature composites. Due to their low melt viscosity and long melt stability, certain phenylethynyl terminated imides (PETI) can be processed into composites using high temperature VARTM (HT-VARTM). However, one of the disadvantages of the current HT-VARTM resin systems has been the high porosity of the resultant composites. For aerospace applications, the desired void fraction of less than 2% has not yet been achieved. In the current study, two PETI resins, LaRC PETI-330 and LaRC PETI-8 have been used to make test specimens using HT-VARTM. The resins were infused into ten layers of IM7-6K carbon fiber 5-harness satin fabric at 260 C or 280 C and cured at temperature up to 371 C. Initial runs yielded composites with high void content, typically greater than 7% by weight. A thermogravimetric-mass spectroscopic study was conducted to determine the source of volatiles leading to high porosity. It was determined that under the thermal cycle used for laminate fabrication, the phenylethynyl endcap was undergoing degradation leading to volatile evolution. This finding was unexpected as high quality composite laminates have been fabricated under higher pressures using these resin systems. The amount of weight loss experienced during the thermal cycle was only about 1% by weight, but this leads to a significant amount of volatiles in a closed system. By modifying the thermal cycle used in laminate fabrication, the void content was significantly reduced (typically 3% or less). The results of this work are presented herein.

  20. High Temperature VARTM of Phenylethynyl Terminated Imides

    NASA Technical Reports Server (NTRS)

    Cano, Roberto J.; Britton, Sean M.; Jensen, Brian J.; Connell, John W.; Herring, Helen M.; Linberry, Quentin J.; Ghose, Sayata; Watson, Kent A.

    2009-01-01

    Fabrication of composite structures using vacuum assisted resin transfer molding (VARTM) is generally more affordable than conventional autoclave techniques. Recent efforts have focused on adapting VARTM for the fabrication of high temperature composites. Due to their low melt viscosity and long melt stability, certain phenylethynyl terminated imides (PETI) can be processed into composites using high temperature VARTM (HT-VARTM). However, one of the disadvantages of the current HT-VARTM resin systems has been the high porosity of the resultant composites. For aerospace applications, the desired void fraction of less than 2% has not yet been achieved. In the current study, two PETI resins, LaRC PETI-330 and LaRC PETI-8 have been used to make test specimens using HT-VARTM. The resins were infused into ten layers of IM7-6K carbon fiber 5-harness satin fabric at 260 C or 280 C and cured at 371 C. Initial runs yielded composites with high void content, typically greater than 7% by weight. A thermogravimetric-mass spectroscopic study was conducted to determine the source of volatiles leading to high porosity. It was determined that under the thermal cycle used for laminate fabrication, the phenylethynyl endcap was undergoing degradation leading to volatile evolution. By modifying the thermal cycle used in laminate fabrication, the void content was reduced significantly (typically approximately 3%). Densities of the composites were determined using a density gradient column and the glass transition temperatures of the cured composites were measured by dynamic mechanical analysis. Photomicrographs of the panels were taken and void contents were determined by acid digestion. The results of this work are presented herein.

  1. Cure Chemistry of Phenylethynyl Terminated Oligomers

    NASA Technical Reports Server (NTRS)

    Wood, Karen H.; Orwoll, Robert A.; Young, Philip R.; Jensen, Brian J.; McNair, Harold M.

    1997-01-01

    The ability to process high performance polymers into quality, void-free composites has been significantly advanced using oligomers terminated with reactive groups which cure or crosslink at elevated temperature without the evolution of volatile byproducts. Several matrix resin systems of considerable interest to the aerospace community utilize phenylethynyl-terminated imide (PETI) technology to achieve this advantage. The present paper addresses the cure chemistry of PETI oligomers. The thermal cure of a low molecular weight model compound was studied using a variety of analytical techniques including differential scanning calorimetry, Fourier transform infrared spectroscopy, and liquid chromatography-mass spectroscopy. The studies indicate an extremely complex cure process. Many stable products were isolated and this paper reports current work on identification of those products. The intent of this research is to provide fundamental insight into the molecular structure of the cured PETI engineering materials so that performance and durability can be more fully assessed.

  2. Synthesis, Characterization, Topographical Modification, and Surface Properties of Copoly(Imide Siloxane)s

    NASA Technical Reports Server (NTRS)

    Wohl, Christopher J.; Atkins, Brad M.; Belcher, Marcus A.; Connell, John W.

    2012-01-01

    Novel copoly(imide siloxane)s were synthesized from commercially available aminopropyl terminated siloxane oligomers, aromatic dianhydrides, and diamines. This synthetic approach produced copolymers with well-defined siloxane blocks linked with imide units in a random fashion. The copoly(amide acid)s were characterized by solution viscosity and subsequently used to cast thin films followed by thermal imidization in an inert atmosphere. Thin films were characterized using contact angle goniometry, attenuated total reflection Fourier transform infrared spectroscopy, confocal and optical microscopy, and tensile testing. Adhesion of micronsized particles was determined quantitatively using a sonication device. The polydimethylsiloxane (PDMS) moieties lowered the copolymer surface energy due to migration of siloxane moieties to the film s surface, resulting in a notable reduction in particle adhesion. A further reduction in particle adhesion was achieved by introducing topographical features on a scale of several to tens of microns by a laser ablation technique.

  3. [Immunomodulatory drugs (IMiDs)].

    PubMed

    Oshima, Kumi; Ichinohe, Tatsuo

    2014-06-01

    Immunomodulatory drugs (IMiDs) are a new class of anti-inflammatory and antineoplastic agents that have structural and functional similarities with their prototype compound, thalidomide. Although thalidomide and its derivatives, lenalidomide and pomalidomide, are widely used as an essential component in the treatment of selected hematologic neoplasms including multiple myeloma, the precise mechanisms by which these agents exert anti-tumor effects have yet to be clarified. Recently, a component of E3 ubiquitin ligase complex, cereblon (CRBN), has been identified as a direct molecular target for anti-neoplastic activities of IMiDs. CRBN has also been shown to be involved in IMiDs-mediated T-cell co-stimulation and cytokine production. Further studies are necessary to elucidate the CRBN-related molecular pathways that are essential for antitumor and immunomodulatory activities of IMiDs.

  4. Phosphorus-containing imide resins

    NASA Technical Reports Server (NTRS)

    Varma, I. K.; Fohlen, G. M.; Parker, J. A. (Inventor)

    1985-01-01

    Cured polymers of bis and tris-imides derived from tris(m-aminophenyl) phosphine oxides by reaction with maleic anhydride or its derivatives, and addition polymers of such imides, including a variant in which a monoimide is condensed with a dianhydride and the product is treated with a further quantity of maleic anhydride prior to curing are disclosed and claimed. Such polymers are flame resistant. Also disclosed are an improved method of producing tris(m-aminophenyl) phosphine oxides from the nitro analogues by reduction with hydrazine hydrate using palladized charcoal or Raney nickel as the catalyst and fiber reinforced cured resin composites.

  5. Ceramic pressure housing with metal endcaps

    DOEpatents

    Downing, J.P. Jr.; DeRoos, B.G.; Hackman, D.J.

    1995-06-27

    A housing is disclosed for the containment of instrumentation in a high pressure fluid environment that consists of a metallic endcap and ceramic cylinder bonded together. The improvement comprises a structure which results in the improved sealing of said housing as the fluid pressure increases. The cylindrical ceramic tube and endcap are dimensioned such that mechanical failure does not occur when exposed to the desired external operating pressures which includes up to 36,000 feet of water. The housing is designed to withstand the external operating pressures without being subject to mechanical failure or excessive deformation which results in the loss of pressure housing integrity via cracking or deformation of the ceramic tube, deformation of the endcap, or from failure of the bonding agent. 9 figs.

  6. Ceramic pressure housing with metal endcaps

    DOEpatents

    Downing, Jr., John P.; DeRoos, Bradley G.; Hackman, Donald J.

    1995-01-01

    A housing for the containment of instrumentation in a high pressure fluid environment that consists of a metallic endcap and ceramic cylinder bonded together. The improvement comprises a structure which results in the improved sealing of said housing as the fluid pressure increases. The cylindrical ceramic tube and endcap are dimensioned such that mechanical failure does not occur when exposed to the desired external operating pressures which includes up to 36,000 feet of water. The housing is designed to withstand the external operating pressures without being subject to mechanical failure or excessive deformation which results in the loss of pressure housing integrity via cracking or deformation of the ceramic tube, deformation of the endcap, or from failure of the bonding agent.

  7. One-Step Synthesis of Precursor Oligomers for Organic Photovoltaics: A Comparative Study between Polymers and Small Molecules.

    PubMed

    Li, Wei; Wang, Daojuan; Wang, Suhao; Ma, Wei; Hedström, Svante; James, David Ian; Xu, Xiaofeng; Persson, Petter; Fabiano, Simone; Berggren, Magnus; Inganäs, Olle; Huang, Fei; Wang, Ergang

    2015-12-16

    Two series of oligomers TQ and rhodanine end-capped TQ-DR were synthesized using a facile one-step method. Their optical, electrical, and thermal properties and photovoltaic performances were systematically investigated and compared. The TQ series of oligomers were found to be amorphous, whereas the TQ-DR series are semicrystalline. For the TQ oligomers, the results obtained in solar cells show that as the chain length of the oligomers increases, an increase in power conversion efficiency (PCE) is obtained. However, when introducing 3-ethylrhodanine into the TQ oligomers as end groups, the PCE of the TQ-DR series of oligomers decreases as the chain length increases. Moreover, the TQ-DR series of oligomers give much higher performances compared to the original amorphous TQ series of oligomers owing to the improved extinction coefficient (ε) and crystallinity afforded by the rhodanine. In particular, the highly crystalline oligomer TQ5-DR, which has the shortest conjugation length shows a high hole mobility of 0.034 cm(2) V(-1) s(-1) and a high PCE of 3.14%, which is the highest efficiency out of all of the six oligomers. The structure-property correlations for all of the oligomers and the TQ1 polymer demonstrate that structural control of enhanced intermolecular interactions and crystallinity is a key for small molecules/oligomers to achieve high mobilities, which is an essential requirement for use in OPVs.

  8. Imide Modified Epoxy Matrix Resin.

    DTIC Science & Technology

    1981-02-01

    the bisimide amine cured epoxies (IME’s) were considerably lower than the state-of-the-art epoxies . The strain-to-failure of the control resin system ...nine epoxy resin systems which were prepared from tetraglycidyl methylenedianiline (MY 720) cured with a stoichiometric quantity of bisimide-amine and...graphite imide modified cured epoxy resin composites. The designation for each material is also listed in Table 1. The composition of each resin system

  9. Imide/arylene ether copolymers

    NASA Technical Reports Server (NTRS)

    Jensen, Brian J. (Inventor); Hergenrother, Paul M. (Inventor); Bass, Robert G. (Inventor)

    1992-01-01

    Imide/arylene ether block copolymers are prepared by reacting anhydride terminated poly(amic acids) with amine terminated poly(arylene ethers) in polar aprotic solvents and by chemically or thermally cyclodehydrating the resulting intermediate poly(amic acids). The resulting block copolymers have one glass transition temperature or two, depending upon the particular structure and/or the compatibility of the block units. Most of these block copolymers form tough, solvent resistant films with high tensile properties.

  10. Crystalline Imide/Arylene Ether Copolymers

    NASA Technical Reports Server (NTRS)

    Jensen, Brian J.; Hergenrother, Paul M.; Bass, Robert G.

    1991-01-01

    Series of imide/arylene ether block copolymers prepared by using arylene ether blocks to impart low melt viscosity, and imide blocks to provide high strength and other desirable mechanical properties. Work represents extension of LAR-14159 on imide/arylene ether copolymers in form of films, moldings, adhesives, and composite matrices. Copolymers potentially useful in variety of high-temperature aerospace and microelectronic applications.

  11. An Investigation of Solid-State Amidization and Imidization Reactions in Vapor Deposited Poly (amic acid)

    SciTech Connect

    Anthamatten, M; Letts, S A; Day, K; Cook, R C; Gies, A P; Hamilton, T P; Nonidez, W K

    2004-06-28

    The condensation polymerization reaction of 4,4'-oxydianiline (ODA) with pyromellitic dianhydride (PMDA) to form poly(amic acid) and the subsequent imidization reaction to form polyimide were investigated for films prepared using vapor deposition polymerization techniques. Fourier-transform infrared spectroscopy (FT-IR), thermal analysis, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) of films at different temperatures indicate that additional solid-state polymerization occurs prior to imidization reactions. Experiments reveal that, upon vapor deposition, poly(amic acid) oligomers form that have a number-average molecular weight of about 1500 Daltons. Between 100 - 130 C these chains undergo additional condensation reaction to form slightly higher molecular weight oligomers. Calorimetry measurements show that this reaction is exothermic ({Delta}H {approx} -30 J/g) with an activation energy of about 120 kJ/mol. Experimental reaction enthalpies are compared to results from ab initio molecular modeling calculations to estimate the number of amide groups formed. At higher temperatures (150 - 300 C) imidization of amide linkages occurs as an endothermic reaction ({Delta}H {approx} +120 J/g) with an activation energy of about 130 kJ/mol. Solid-state kinetics were found to depend on reaction conversion as well as the processing conditions used to deposit films.

  12. Imide/Arylene Ether Copolymers

    NASA Technical Reports Server (NTRS)

    Jensen, Brian J.; Hergenrother, Paul M.; Bass, Robert G.

    1991-01-01

    New imide/arylene ether copolymers prepared by reacting anhydride-terminated poly(amic acids) with amine-terminated poly(arylene ethers) in polar aprotic solvents. Each resulting copolymer may have one glass-transition temperature or two, depending on chemical structure and/or compatibility of block units. Most of copolymers form tough, solvent-resistant films with high tensile properties. Films cast from solution tough and flexible, and exhibit useful thermal and mechanical properties. Potentially useful as moldings, adhesives, or composite matrices. Because of flexible arylene ether blocks, these copolymers easier to process than polyimides.

  13. Imide/arylene ether block copolymers

    NASA Technical Reports Server (NTRS)

    Jensen, B. J.; Hergenrother, P. M.; Bass, R. G.

    1991-01-01

    Two series of imide/arylene either block copolymers were prepared using an arylene ether block and either an amorphous or semi-crystalline imide block. The resulting copolymers were characterized and selected physical and mechanical properties were determined. These results, as well as comparisons to the homopolymer properties, are discussed.

  14. Better End-Cap Processing for Oxidation-Resistant Polyimides

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B.; Frimer, Aryeh A.

    2004-01-01

    A class of end-cap compounds that increase the thermo-oxidative stab ility of polyimides of the polymerization of monomeric reactants (PM R) type has been extended. In addition, an improved processing proto col for this class of end-cap compounds has been invented.

  15. Computational design of organometallic oligomers featuring 1,3-metal-carbon bonding and planar tetracoordinate carbon atoms.

    PubMed

    Zhao, Xue-Feng; Yuan, Cai-Xia; Wang, Xiang; Li, Jia-Jia; Wu, Yan-Bo; Wang, Xiaotai

    2016-01-15

    Density functional theory computations (B3LYP) have been used to explore the chemistry of titanium-aromatic carbon "edge complexes" with 1,3-metal-carbon (1,3-MC) bonding between Ti and planar tetracoordinate Cβ . The titanium-coordinated, end-capping chlorides are replaced with OH or SH groups to afford two series of difunctional monomers that can undergo condensation to form oxide- and sulfide-bridged oligomers. The sulfide-linked oligomers have less molecular strain and are more exergonic than the corresponding oxide-linked oligomers. The HOMO-LUMO gap of the oligomers varies with their composition and decreases with growing oligomer chain. This theoretical study is intended to enrich 1,3-MC bonding and planar tetracoordinate carbon chemistry and provide interesting ideas to experimentalists. Organometallic complexes with the TiE2 (E = OH and SH) decoration on the edge of aromatic hydrocarbons have been computationally designed, which feature 1,3-metal-carbon (1,3-MC) bonding between titanium and planar tetracoordinate β-carbon. Condensation of these difunctional monomers by eliminating small molecules (H2O and H2S) produce chain-like oligomers. The HOMO-LUMO gaps of the oligomers decreases with growing oligomer chain, a trend that suggests possible semiconductor properties for oligomers with longer chains.

  16. Corpectomy cage subsidence with rectangular versus round endcaps.

    PubMed

    Deukmedjian, Armen R; Manwaring, Jotham; Le, Tien V; Turner, Alexander W L; Uribe, Juan S

    2014-09-01

    Corpectomy cages with rectangular endcaps utilize the stronger peripheral part of the endplate, potentially decreasing subsidence risk. The authors evaluated cage subsidence during cyclic biomechanical testing, comparing rectangular versus round endcaps. Fourteen cadaveric spinal segments (T12-L2) were dissected and potted at T12 and L2, then assigned to a rectangular (n=7) or round (n=7) endcap group. An L1 corpectomy was performed and under uniform conditions a cage/plate construct was cyclically tested in a servo-hydraulic frame with increasing load magnitude. Testing was terminated if the test machine actuator displacement exceeded 6mm, or the specimen completed cyclic loading at 2400 N. Number of cycles, compressive force and force-cycles product at test completion were all greater in the rectangular endcap group compared with the round endcap group (cycles: 3027 versus 2092 cycles; force: 1943 N versus 1533 N; force-cycles product: 6162kN·cycles versus 3973 kN·cycles), however these differences were not statistically significant (p ⩾ 0.076). After normalizing for individual specimen bone mineral density, the same measures increased to a greater extent with the rectangular endcaps (cycles: 3014 versus 1855 cycles; force: 1944 N versus 1444 N; force-cycles product: 6040 kN·cycles versus 2980 kN·cycles), and all differences were significant (p⩽0.030). The rectangular endcap expandable corpectomy cage displayed increased resistance to subsidence over the round endcap cage under cyclic loading as demonstrated by the larger number of cycles, maximum load and force-cycles product at test completion. This suggests rectangular endcaps will be less susceptible to subsidence than the round endcap design.

  17. Crystalline imide/arylene ether copolymers

    NASA Technical Reports Server (NTRS)

    Jensen, Brian J. (Inventor); Hergenrother, Paul M. (Inventor); Bass, Robert G. (Inventor)

    1995-01-01

    Crystalline imide/arylene ether block copolymers are prepared by reacting anhydride terminated poly(amic acids) with amine terminated poly)arylene ethers) in polar aprotic solvents and chemically or thermally cyclodehydrating the resulting intermediate poly(amic acids). The block copolymers of the invention have one glass transition temperature or two, depending on the particular structure and/or the compatibility of the block units. Most of these crystalline block copolymers for tough, solvent resistant films with high tensile properties. While all of the copolymers produced by the present invention are crystalline, testing reveals that copolymers with longer imide blocks or higher imide content have increased crystallinity.

  18. Investigation of intermolecular interactions between single walled nanotubes and conjugated oligomers using the dispersion-corrected DFT methods

    NASA Astrophysics Data System (ADS)

    Lagowski, Jolanta B.; Aljohani, Suad; Khan, M. Zahidul H.; Zhao, Yuming

    The area of carbon nanotubes (CNT)-polymer composites has been progressing rapidly in recent years. Pure CNT and CNT-polymer composites have many useful (industry related) properties: ranging from electronic electrical conductivity to superior strength. However the full potential of using CNTs as reinforcements (in say a polymer matrix) has been severely limited because of complications associated with the dispersion of CNTs. CNTs tend to entangle with each other forming materials that have properties that fall short of the expectations. The goal of this work is to identify the type of conjugated oligomers that are best suited for the dispersion of single walled CNT (SWCNT). For this purpose, various methods of dispersion corrected density functional theory (DFT-D/B97D, /WB97XD, /CAM-B3LYP) have been used to investigate the interaction between the SWCNT and the organic conjugated oligomers with different end groups (aldehyde (ALD) and dithiafulvenyl (DTF)). We investigate the effect of intermolecular interactions on the structure, polarity and energetics of the oligomers and SWCNT combinations. The comparison of results obtained using different DFT approximations is made. Our results show that DFT-endcapped oligomer interact more strongly with CNT than ALD-endcapped oligomer. The financial support from NSERC, SACBC and Memorial University and the computational resources from Compute Canada were received.

  19. Imide modified epoxy matrix resins

    NASA Technical Reports Server (NTRS)

    Scola, D. A.; Pater, R. H.

    1981-01-01

    High char yield epoxy using novel bisimide amines (BIA's) as curing agents with a state of the art epoxy resin was developed. Stoichiometric quantities of the epoxy resin and the BIA's were studied to determine the cure cycle required for preparation of resin specimens. The bisimide cured epoxies were designated IME's (imide modified epoxy). The physical, thermal and mechanical properties of these novel resins were determined. The levels of moisture absorption exhibited by the bisimide amine cured expoxies (IME's) were considerably lower than the state of the art epoxies. The strain-to-failure of the control resin system was improved 25% by replacement of DDS with 6F-DDS. Each BIA containing resin exhibited twice the char yield of the control resin MY 720/DDS. Graphite fiber reinforced control (C) and IME resins were fabricated and characterized. Two of the composite systems showed superior properties compared to the other Celion 6000/IME composite systems and state of the art graphite epoxy systems. The two systems exhibited excellent wet shear and flexural strengths and moduli at 300 and 350 F.

  20. Imide modified epoxy matrix resins

    NASA Technical Reports Server (NTRS)

    Scola, D. A.

    1984-01-01

    The results of a program designed to develop tough imide modified epoxy resins cured by bisimide amine (BIA) hardeners are described. State-of-the-art epoxides MY720 and DER383 were used, and four bismide amines were evaluated. These were the BIA's derived from the 6F anhydride (4,4'-(hexafluoroisopropylidene) bis(phthalic anhydride) and the diamines 3,3'-diaminodiphynyl sulfone, 4,4'-oxygianiline, 4,4'-methylene dianiline, and 1,12-dodecane diamine. A key intermediate, designated 6F anhydride, is required for the synthesis of the bisimide amines. Reaction parameters to synthesize a precursor to the 6F anhydride (6FHC) in high yields were investigated. The catalyst trifluoromethane sulfonic acid was studied. Although small scale runs yielded the 6FHC in 50 percent yield, efforts to ranslate these results to a larger scale synthesis gave the 6FHC in only 9 percent yield. Results show that the concept of using bisimide amine as curing agents to improve the toughness properties of epoxies is valid.

  1. Monofunctional hyperbranched ethylene oligomers.

    PubMed

    Wiedemann, Thomas; Voit, Gregor; Tchernook, Alexandra; Roesle, Philipp; Göttker-Schnetmann, Inigo; Mecking, Stefan

    2014-02-05

    The neutral κ(2)N,O-salicylaldiminato Ni(II) complexes [κ(2)N,O-{(2,6-(3',5'-R2C6H3)2C6H3-N═C(H)-(3,5-I2-2-O-C6H2)}]NiCH3(pyridine)] (1a-pyr, R = Me; 1b-pyr, R = Et; 1c-pyr, R = iPr) convert ethylene to hyperbranched low-molecular-weight oligomers (Mn ca. 1000 g mol(-1)) with high productivities. While all three catalysts are capable of generating hyperbranched structures, branching densities decrease significantly with the nature of the remote substituent along Me > Et > iPr and oligomer molecular weights increase. Consequently, only 1a-pyr forms hyperbranched structures over a wide range of reaction conditions (ethylene pressure 5-30 atm and 20-70 °C). An in situ catalyst system achieves similar activities and identical highly branched oligomer microstructures, eliminating the bottleneck given by the preparation and isolation of Ni-Me catalyst precursor species. Selective introduction of one primary carboxylic acid ester functional group per highly branched oligoethylene molecule was achieved by isomerizing ethoxycarbonylation and alternatively cross metathesis with ethyl acrylate followed by hydrogenation. The latter approach results in complete functionalization and no essential loss of branched oligomer material and molecular weight, as the reacting double bonds are close to a chain end. Reduction yielded a monoalcohol-functionalized oligomer. Introduction of one reactive epoxide group per branched oligomer occurs completely and selectively under mild conditions. All reaction steps involved in oligomerization and monofunctionalization are efficient and readily scalable.

  2. Finite element analysis of the SDC barrel and endcap calorimeters

    SciTech Connect

    Guarino, V.; Hill, N.; Nasiakta, J.

    1992-03-11

    In designing the SCD barrel and endcap calorimeters, the inter-module connecting forces must be known in order to determine the required size and number of connecting links between modules, and in order to understand how individual modules will be affected by these forces when assembled to form a full barrel and endcap. The connecting forces were found by analyzing three-dimensional Finite Element Models of both the barrel and endcap. This paper is divided into two parts, the first part will describe in detail the results of the barrel analysis and the second part will describe the results obtained from the endcap analysis. A similar approach was used in constructing the models for both analysis.

  3. Process of end-capping a polyimide system

    NASA Technical Reports Server (NTRS)

    Stclair, T. L.; Burks, H. D. (Inventor)

    1985-01-01

    A process of endcapping a polyimide system with an endcapping agent in order to achieve a controlled decrease in molecular weight and melt viscosity along with predictable fracture resistance of the molded products is disclosed. The uncapped system is formed by combining an equimolar ratio of 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride (BDSDA) and 1,-bis (aminophenoxy) benzene (APB) dissolved in bis (2-methoxyethyl)ether. The endcapped system is formed by dissolving APB in bis-(2-methoxyethyl)ether, adding the BDSDA. By varying the amount of endcapping from 0 to 4%, molecular weight is decreased from 13,900 to 8660. At a processing temperature of 250 C, there is a linear relationship between molecular weight and viscosity, with the viscosity decreasing by two orders of magnitude as the molecular weight decreased from 13,900 to 8660.

  4. Phenylethynyl amine

    NASA Technical Reports Server (NTRS)

    Hergenrother, Paul M. (Inventor); Bryant, Robert G. (Inventor); Jensen, Brian J. (Inventor); Havens, Stephen J. (Inventor)

    1997-01-01

    Four phenylethynyl amine compounds--3 and 4-aminophenoxy-4'-phenylethynylbenzophenone, and 3 and 4-amino-4'-phenylethynylbenzophenone--were readily prepared and were used to endcap imide oligomers. Phenylethynyl-terminated amide acid oligomers and phenylethynyl-terminated imide oligomers with various molecular weights and compositions were prepared and characterized. These oligomers were cured at 300.degree. C. to 400.degree. C. to provide crosslinked polyimides with excellent solvent resistance, high strength and modulus and good high temperature properties. Adhesive panels, composites, films and moldings from these phenylethynyl terminated imide oligomers gave excellent mechanical performance.

  5. Molecular-Weight-Controlled, End-Capped Polybenzimidazoles

    NASA Technical Reports Server (NTRS)

    Connell, John W.; Hergenrother, Paul M.; Smith, Joseph G., Jr.

    1993-01-01

    Novel molecular-weight-controlled end-capped poly(arylene ether benzimidazole)s (PAEBI's) prepared by nucleophilic displacement reaction of di(hydroxyl)benzimidazole monomers with activated aromatic dihalides. Polymers prepared at various molecular weights by upsetting stoichiometry of monomers and end-capped with monohydroxybenzimidazole. Exhibit favorable physical and mechanical properties, improved solubility in polar aprotic solvents and better compression moldability. Potential applications as adhesives, coatings, films, fibers, membranes, moldings, and composite matrix resins.

  6. Imide modified epoxy matrix resins

    NASA Technical Reports Server (NTRS)

    Scola, D. A.

    1982-01-01

    Results of a program designed to develop tough imide modified epoxy (IME) resins cured by bisimide amine (BIA) hardeners are presented. State of the art epoxy resin, MY720, was used. Three aromatic bisimide amines and one aromatic aliphatic BIA were evaluated. BIA's derived from 6F anhydride (3,3 prime 4,4 prime-(hexafluoro isopropyl idene) bis (phthalic anhydride) and diamines, 3,3 prime-diam nodiphenyl sulfone (3,3 prime-DDS), 4,4 prime-diamino diphenyl sulfone (4,4 prime-DDS), 1.12-dodecane diamine (1,12-DDA) were used. BIA's were abbreviated 6F-3,3 prime-DDS, 6F-4,4 prime-DDS, 6F-3,3 prime-DDS-4,4 prime DDS, and 6F-3,3 prime-DDS-1,12-DDA corresponding to 6F anhydride and diamines mentioned. Epoxy resin and BIA's (MY720/6F-3,3 prime-DDS, MY720/6F-3,3 prime-DDS-4,4 prime-DDS, MY720/6F-3,3 prime-DDS-1,12-DDA and a 50:50 mixture of a BIA and parent diamine, MY720/6F-3,3 prime-DDS/3,3 prime-DDS, MY720/6F-3,3 prime-DDS-4,4 prime-DDS/3,3 prime-DDS, MY720/6F-3,3 prime-DDS-1,12-DDA/3,3 prime-DDS were studied to determine effect of structure and composition. Effect of the addition of two commercial epoxies, glyamine 200 and glyamine 100 on the properties of several formulations was evaluated. Bisimide amine cured epoxies were designated IME's (imide modified epoxy). Physical, thermal and mechanical properties of these resins were determined. Moisture absorption in boiling water exhibited by several of the IME's was considerably lower than the state of the art epoxies (from 3.2% for the control and state of the art to 2.0 wt% moisture absorption). Char yields are increased from 20% for control and state of the art epoxies to 40% for IME resins. Relative toughness characteristics of IME resins were measured by 10 deg off axis tensile tests of Celion 6000/IME composites. Results show that IME's containing 6F-3,3 prime-DDS or 6F-3,3 prime-DDS-1,12-DDA improved the "toughness" characteristics of composites by about 35% (tensile strength), about 35% (intralaminar shear

  7. Partially imidized, water-soluble polymeric amides. I. Partially imidized polyacrylamide and polymethacrylamide

    SciTech Connect

    Shepitka, J.S.; Case, C.E.; Donaruma, L.G.; Hatch, M.J.; Kilmer, N.H.; Khune, G.D.; Martin, F.D.; Ward, J.S.; Wilson, K.V.

    1983-12-01

    Five to six million molecular weight polyacrylamide and polymethacrylamides of comparable post-alkaline hydrolysis viscosities were imidized by dissolution and heating in 6N HCl. After alkaline hydrolysis, the imidized polymers demonstrated significantly better retention of viscosity to 2% NaCl than did similar partially hydrolyzed polymers. Viscosities in 0.01% NaCl and resistance to shear were not markedly affected by this modification. It is assumed that this improved performance in brine is the result of chain stiffening due to intrachain imide rings. 2 figures, 2 tables.

  8. Phenylethynyl terminated reactive oligomer

    NASA Technical Reports Server (NTRS)

    Bryant, Robert G. (Inventor); Jensen, Brian J. (Inventor); Hergenrother, Paul M. (Inventor)

    1995-01-01

    A composition of matter having the general structure: ##STR1## (wherein X is F, Cl, or NO.sub.2, and Y is CO, SO.sub.2 or C(CF.sub.3).sub.2) is employed to terminate a nucleophilic reagent, resulting in the exclusive production of phenylethynyl terminated reactive oligomers which display unique thermal characteristics. A reactive diluent having the general structure: ##STR2## (wherein R is any aliphatic or aromatic moiety) is employed to decrease the melt viscosity of a phenylethynyl terminated reactive oligomer and to subsequently react therewith to provide a thermosetting material of enhanced density. These materials have features which make them attractive candidates for use as composite matrices and adhesives.

  9. High Temperature VARTM of Phenylethynyl Terminated Imides

    NASA Technical Reports Server (NTRS)

    Ghose, Sayata; Watson, Kent A.; Cano, Roberto J.; Britton, Sean M.; Jensen, Brian J.; Connell, John W.; Herring, Helen M.; Linberry, Quentin J.

    2009-01-01

    LaRC phenylethynyl terminated imide (PETI) resins were processed into composites using high temperature vacuum assisted resin transfer molding (VARTM). Although initial runs yielded composites with high void content, process modifications reduced voids to <3%. Photomicrographs were taken and void contents and T(sub g)s of the panels were determined.

  10. Functional end-capped conducting poly (3,4-ethylenedioxythiophene)

    NASA Astrophysics Data System (ADS)

    Sabatini, V.; Farina, H.; Ortenzi, Marco A.

    2016-05-01

    Methacrylate-terminated Poly(3,4-Ethylenedioxythiophene) (PEDOT) polymers with controlled degree of polymerization were successfully prepared by direct oxidative polycondensation between Ethylenedioxythiophene (EDOT) and a cross-linkable methacrylate end-capper monomer, obtained via Friedel Crafts acylation starting from EDOT and Methacryloyl chloride. The new polymer was synthesized in order to overcome the well-known technical problems of PEDOT, i.e. difficult processability and patterning, due to its poor solubility in common organic and inorganic solvents. The chemical structure and the degree of polymerization of the end-capped polymers were determined by 1H NMR spectra. A new synthesis of Methacrylate end-capped PEDOT with controlled degree of polymerization, soluble in common organic and chlorinated solvents and with improved conductivity, 210 S/cm, was performed. This method includes: direct oxidative polycondensation of 3,4-Ethylenedioxythiophene (EDOT) in the presence of a cross-linkable end-capper, i.e. Methacrylate end-capped EDOT prepared via Friedel Crafts acylation with Methacryloyl chloride and oxidant species, i.e. ferric sulfate. Furthermore, the oxidative polycondensation of EDOT monomer and Methacrylate end-capped EDOT in the presence of Sulfonated Polyethersulfone (SPES)- characterized by different degree of Sulfonation (DS)- as dopant agent was performed, leading to functional end-capped conducting PEDOT, easy to process and pattern, with conductivity of 210 S/cm, 50 S/cm higher than the one of commercial PEDOT.

  11. Polyphenylene ethers with imide linking groups

    NASA Technical Reports Server (NTRS)

    St.clair, T. L.; Burks, H. D. (Inventor)

    1984-01-01

    Novel polyphenylene ethers with imide linking units are disclosed. These polymers incorporate the solvent and thermal resistance of polyimides and the processability of polyphenylene ethers. Improved physical properties over those of the prior art are obtained by incorporating meta linked ethers and/or polyphenylene oxides into the polymer backbone. A novel process for making polymers of this type is also disclosed. The process is unique in that the expected need of high process temperatures and/or special atmospheres are eliminated.

  12. Cyclic Imide Dioxime: Formation and Hydrolytic Stability

    SciTech Connect

    Kang, S.O.; Vukovic, Sinisa; Custelcean, Radu; Hay, Benjamin

    2012-01-01

    Poly(acrylamidoximes) play an important role in the uranium extraction from seawater. The present work reports solution studies of simple analogs to address the formation and stability of two binding sites present in these polymers, open-chain amidoximes and cyclic imide dioximes, including: 1) conditions that maximize the formation of the cyclic form, 2) existence of a base-induced conversion from open-chain to cyclic form, and 3) degradation under acid and base conditions.

  13. Prototype of time digitizing system for BESIII endcap TOF upgrade

    NASA Astrophysics Data System (ADS)

    Cao, Ping; Sun, Wei-Jia; Ji, Xiao-Lu; Fan, Huan-Huan; Wang, Si-Yu; Liu, Shu-Bin; An, Qi

    2014-04-01

    The prototype of a time digitizing system for the BESIII endcap TOF (ETOF) upgrade is introduced in this paper. The ETOF readout electronics has a distributed architecture. Hit signals from the multi-gap resistive plate chamber (MRPC) are signaled as LVDS by front-end electronics (FEE) and are then sent to the back-end time digitizing system via long shield differential twisted pair cables. The ETOF digitizing system consists of two VME crates, each of which contains modules for time digitization, clock, trigger, fast control, etc. The time digitizing module (TDIG) of this prototype can support up to 72 electrical channels for hit information measurement. The fast control (FCTL) module can operate in barrel or endcap mode. The barrel FCTL fans out fast control signals from the trigger system to the endcap FCTLs, merges data from the endcaps and then transfers to the trigger system. Without modifying the barrel TOF (BTOF) structure, this time digitizing architecture benefits from improved ETOF performance without degrading the BTOF performance. Lab experiments show that the time resolution of this digitizing system can be lower than 20 ps, and the data throughput to the DAQ can be about 92 Mbps. Beam experiments show that the total time resolution can be lower than 45 ps.

  14. Controlled molecular weight poly(arylene ether benzimidazole)s endcapped with benzimidazole and acetylene groups

    SciTech Connect

    Smith, J.G. Jr.; Connell, J.W.; Hergenrother, P.M.

    1993-12-31

    As a continuation of work on poly(arylene ether benzimidazole)s (PAEBIs), a series of controlled molecular weight polymers endcapped with benzimidazole, ethynyl, and phenylethynyl groups were prepared at stoichiometric imbalances of 7 and 10 mole percent and characterized. Earlier work with benzimidazole endcapped PAEBIs prepared at stoichiometric imbalances as high as 7 mole percent has shown very good retention of thin film properties up to 232{degrees}C. Ethynyl and phenylethynyl endcapped PAEBIs, air cured to 330{degrees}C, exhibited increases in Tgs of {approximately}20-30{degrees}C with respect to benzimidazole endcapped PAEBIs. Thin film properties for the ethynyl and phenylethynyl endcapped PAEBIs were similar to benzimidazole endcapped PAEBIs up to 232{degrees}C. Ethynyl and phenylethynyl endcapped PAEBI films tested at 250{degrees}C exhibited good retention of tensile properties.

  15. CMS Hadron Endcap Calorimeter Upgrade Studies for Super-LHC

    NASA Astrophysics Data System (ADS)

    Bilki, Burak; CMS HCAL Collaboration

    2011-04-01

    When the Large Hadron Collider approaches Super-LHC conditions above a luminosity of 1034cm-2s-1, the scintillator tiles of the CMS Hadron Endcap calorimeters will lose their efficiencies. As a radiation hard solution, the scintillator tiles are planned to be replaced by quartz plates. In order to improve the efficiency of the photodetection, various methods were investigated including radiation hard wavelength shifters, p-terphenyl or 4% gallium doped zinc oxide. We constructed a 20 layer calorimeter prototype with pTp coated plates of size 20 cm × 20 cm, and tested the hadronic and the electromagnetic capabilities at the CERN H2 beam-line. The beam tests revealed a substantial light collection increase with pTp or ZnO:Ga deposited quartz plates. Here we report on the current R&D for a viable endcap calorimeter solution for CMS with beam tests and radiation damage studies.

  16. Tests and developments of the PANDA Endcap Disc DIRC

    NASA Astrophysics Data System (ADS)

    Etzelmüller, E.; Belias, A.; Dzhygadlo, R.; Gerhardt, A.; Götzen, K.; Kalicy, G.; Krebs, M.; Lehmann, D.; Nerling, F.; Patsyuk, M.; Peters, K.; Schepers, G.; Schmitt, L.; Schwarz, C.; Schwiening, J.; Traxler, M.; Zühlsdorf, M.; Britting, A.; Eyrich, W.; Lehmann, A.; Pfaffinger, M.; Uhlig, F.; Düren, M.; Föhl, K.; Hayrapetyan, A.; Kröck, B.; Merle, O.; Rieke, J.; Schmidt, M.; Cowie, E.; Keri, T.; Achenbach, P.; Cardinali, M.; Hoek, M.; Lauth, W.; Schlimme, S.; Sfienti, C.; Thiel, M.

    2016-04-01

    The PANDA experiment at the future Facility for Antiproton and Ion Research (FAIR) requires excellent particle identification. Two different DIRC detectors will utilize internally reflected Cherenkov light of charged particles to enable the separation of pions and kaons up to momenta of 4 GeV/c. The Endcap Disc DIRC will be placed in the forward endcap of PANDA's central spectrometer covering polar angles between 5° and 22°. Its final design is based on MCP-PMTs for the photon detection and an optical system made of fused silica. A new prototype has been investigated during a test beam at CERN in May 2015 and first results will be presented. In addition a new synthetic fused silica material by Nikon has been tested and was found to be radiation hard.

  17. Imide photodissociation investigated by X-ray absorption spectroscopy.

    PubMed

    Johnson, Phillip S; Cook, Peter L; Liu, Xiaosong; Yang, Wanli; Bai, Yiqun; Abbott, Nicholas L; Himpsel, F J

    2012-06-21

    X-ray absorption spectroscopy is used to investigate the photodissociation of the imides PMDI (pyromellitic diimide) and SSMCC (sulfosuccinimidyl 4-(N-maleimidomethyl) cyclohexane-1-carboxylate). PMDI contains only one type of imide, and its photodissociation can be explained by a simple conversion from imide to a mix of imine and nitrile after desorption of the oxygens from the imide. SSMCC contains two different imides. One reacts like PMDI, the other in a more complex multistep process. Eventually, N(2) is formed in the bulk of the sample at high radiation density. The sequence of reactions is inferred from the π* peaks in total electron yield and fluorescence yield absorption spectra at the N 1s and O 1s edges. First-order rate equations are used to model the evolution of the peak areas versus radiation dose.

  18. Thin gap gas chambers for the DELPHI endcaps

    SciTech Connect

    Adam, W.; Hrubec, J.

    1996-12-31

    Thin Gap Gas Chambers have been proposed for an upgrade of the endcaps of the DELPHI detector at LEP. Two full size chambers have been built and a study of the optimal operating conditions has been carried out. In this paper the main construction parameters are discussed and test results will be given. Tests of the electronic readout were performed and the general feasibility of the detector is demonstrated.

  19. Laser rods with undoped, flanged end-caps for end-pumped laser applications

    DOEpatents

    Meissner, Helmuth E.; Beach, Raymond J.; Bibeau, Camille; Sutton, Steven B.; Mitchell, Scott; Bass, Isaac; Honea, Eric

    1999-01-01

    A method and apparatus for achieving improved performance in a solid state laser is provided. A flanged, at least partially undoped end-cap is attached to at least one end of a laserable medium. Preferably flanged, undoped end-caps are attached to both ends of the laserable medium. Due to the low scatter requirements for the interface between the end-caps and the laser rod, a non-adhesive method of bonding is utilized such as optical contacting combined with a subsequent heat treatment of the optically contacted composite. The non-bonded end surfaces of the flanged end-caps are coated with laser cavity coatings appropriate for the lasing wavelength of the laser rod. A cooling jacket, sealably coupled to the flanged end-caps, surrounds the entire length of the laserable medium. Radiation from a pump source is focussed by a lens duct and passed through at least one flanged end-cap into the laser rod.

  20. 78 FR 57285 - 2,5-Furandione, Polymer With Ethenylbenzene, Hydrolyzed, 3-(Dimethylamino)propyl Imide, Imide...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-09-18

    ... AGENCY 40 CFR Part 180 2,5-Furandione, Polymer With Ethenylbenzene, Hydrolyzed, 3- (Dimethylamino)propyl...-furandione, polymer with ethenylbenzene, hydrolyzed, 3-(dimethylamino)propyl imide, imide with polyethylene... permissible level for residues of 2,5-furandione, polymer with ethenylbenzene, hydrolyzed, 3- ]...

  1. Chemistry of Processible Acetylene-Terminated Imides

    DTIC Science & Technology

    1983-08-01

    and consultations in DSC -TGA analyses, FT-IR spectroscopy, NMR spectrometry, and HPLC-GPC analyses were provided by Mr. Philip G. Magallanes, Mr. Herman...11 Differential Scanning Calorimetry ( DSC ) for HR600P (Lot M1126-1) ........ 15 12 Differential Scanning Calorimetry ( DSC ) Curves for Thermid 600 and H...17 14 Gel Permeation Chromatogram for HR605P (Lot M1126-33A) .............. 18 15 Differential Scanning Calorimetry ( DSC ) for HR602P Oligomer (M1126-42

  2. Diamines Containing Pendent Phenylethynyl Groups

    NASA Technical Reports Server (NTRS)

    Connell, John W. (Inventor); Smith, Joseph G., Jr. (Inventor); Hergenrother, Paul M. (Inventor)

    1997-01-01

    Controlled molecular weight imide oligomers and co-oligomers containing pendent phenylethynyl groups (PEPIs) and endcapped with nonreactive or phenylethynyl groups have been prepared by the cyclodehydration of the precursor amide acid oligomers or co-oligomers containing pendent phenylethynyl groups and endcapped with nonreactive or phenylethynyl groups. The amine terminated amide acid oligomers or co-oligomers are prepared from the reaction of dianhydride(s) with an excess of diamine(s) and diamine containing pendent phenylethynyl groups and subsequently endcapped with a phenylethynyl phthalic anhydride or monofunctional anhydride. The anhydride terminated amide acid oligomers and co-oligomers are prepared from the reaction of diamine(s) and diamine containing pendent phenylethynyl group(s) with an excess of dianhydride(s) and subsequently endcapped with a phenylethynyl amine or monofunctional amine. The polymerizations are carried out in polar aprotic solvents such as and N,N-dimethylacetamide under nitrogen at room temperature. The amide acid oligomers or co-oligomers are subsequently cyclodehydrated either thermally or chemically to the corresponding imide oligomers. The polymers and copolymers prepared from these materials exhibit a unique and unexpected combination of properties that includes higher glass transition temperatures after curing and higher retention of neat resin, adhesive and carbon fiber reinforced mechanical properties at temperatures up to 204 C under wet conditions without sacrificing melt flow behavior and processability as compared to similar materials. These materials are useful as adhesives, coatings, films, moldings, and composite matrices.

  3. Synthesis and Properties of Phenylethynyl-Terminated, Star-Branched, Phenylquinoxaline Oligomers

    NASA Technical Reports Server (NTRS)

    Ooi, I. H.; Hergenrother, P. M.; Harris, F. W.

    2000-01-01

    The primary objective of this work was to prepare readily melt and solution processable phenylquinoxaline (PQ) oligomers that could be thermally crosslinked to solvent-resistant resins. Thus, a mixture of 2-(4-hydroxyphenyl)-3-phenyl-6-fluoroquinoxaline and 3-(4-hydroxyphenyl)-2-phenyl-6-fluoroquinoxaline (HPFQ) was used to prepare star-branched PQ oligomers end-capped with 4-fluoro-4-phenylethynylbenzophenone (FPEB). 1,1,1-Tris(4-hydroxyphenyl)ethane (THPE) was used as the branching unit. The oligomer number-average molecular weights (M (bar) (sub n) S) as determined by size exclusion chromatography (SEC) were close to the calculated values of 2922, 4698, 6474, and 13,578 g/mol, and their intrinsic viscosities ranged from 0.16 to 0.57 dl/g (m-cresol at 30 C). The oligomers, which were quite soluble in common organic solvents, had glass transition temperatures (T (sub g) S) that ranged from 181 to 233 C (DSC, DELTA T = 20 C/min). They also underwent an exothermic cure with maxima from 377 to 443 C. The T (sub g) S of the cured oligomers ranged from 259 to 284 C depending on the oligomer M (bar) (sub n) and the curing conditions. The oligomers had low melt viscosities, e.g. an oligomer (SPQ-46) with an M (bar) (sub n) of 4816 g/mol (SEC) had a melt viscosity of 150 Pa s at 348 C. A cured thin film of SPQ-46, which was insoluble in common organic solvents, had a room temperature (RT) tensile strength of 100 MPa, a RT modulus of 2358 MPa, and a RT elongation of 5.9%. A cured sample of SPQ-46 displayed a RT titanium-titanium lap shear tensile strength of 35.2 MPa. SPQ-46/carbon fiber(IM-7) composites, were prepared that displayed a RT flexural strength of 1902 MPa, a RT modulus of 1.38 GPa and a RT open hole compressive strength of 433 MPa.

  4. 21 CFR 177.2450 - Polyamide-imide resins.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... than 500 parts per million. Residual monomers are determined by gas chromatography (the gas chromatography method titled “Amide-Imide Polymer Analysis—Analysis of Monomer Content,” is incorporated...

  5. 21 CFR 177.2450 - Polyamide-imide resins.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... than 500 parts per million. Residual monomers are determined by gas chromatography (the gas chromatography method titled “Amide-Imide Polymer Analysis—Analysis of Monomer Content,” is incorporated...

  6. 21 CFR 177.2450 - Polyamide-imide resins.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... than 500 parts per million. Residual monomers are determined by gas chromatography (the gas chromatography method titled “Amide-Imide Polymer Analysis—Analysis of Monomer Content,” is incorporated...

  7. 21 CFR 177.2450 - Polyamide-imide resins.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... than 500 parts per million. Residual monomers are determined by gas chromatography (the gas chromatography method titled “Amide-Imide Polymer Analysis—Analysis of Monomer Content,” is incorporated...

  8. Process for preparing phthalocyanine polymer from imide containing bisphthalonitrile

    NASA Technical Reports Server (NTRS)

    Achar, Bappalige N. (Inventor); Fohlen, George M. (Inventor); Parker, John A. (Inventor)

    1987-01-01

    Imide-linked bisphthalonitrile compounds are prepared by combining a dicyano aromatic diamine and an organic dianhydride to produce an amic acid linked bisphthalonitrile compound. The amic acid linked bisphthalonitrile compound is dehydrocyclized to produce the imide-linked bisphthalonitrile compounds. The imide-linked bisphthalonitrile compounds may be polymerized to produce a phythalocyanine polymer by heating the imide-linked bisphthalonitrile compound, either alone or in the presence of a metal powder or a metal salt. These compounds are useful in the coating, laminating and molding arts. The polymers are useful in composite matrix resins where increased fire resistance, toughness and resistance to moisture are required, particularly as secondary structures in aircraft and spacecraft.

  9. Preparation and properties of silane-endcapped polyimide adhesives

    NASA Technical Reports Server (NTRS)

    Maudgal, S.; St. Clair, T. L.

    1984-01-01

    Silane-endcapped polyimide high temperature adhesive formulations were prepared by reacting anhydride-terminated poly(amic acid), obtained from benzophenonetetracarboxylic dianhydride and a diamine (3,3'-, 3,4'- or 4,4'-diaminodiphenylmethane and 3,3', 3,4'- or 4,4'-diaminobenzophenone) with varying amounts of gama-aminopropyltriethoxysilane in dimethylacetamide. Resin properties were evaluated by torsional braid analysis and thermogravimetric analysis. Lap shear strengths of some of the adhesive bonds were determined at room temperature and at 177 C before and after ageing at 200 C for 2500 h and after boiling in water for 72 h.

  10. Substituted Cyclohexene Endcaps for Polymers with Thermal-Oxidative Stability

    NASA Technical Reports Server (NTRS)

    2005-01-01

    This invention relates to polyimides having improved thermal-oxidative stability, to the process of preparing said polyimides, and the use of polyimide prepolymers in the preparation of prepregs and composites. The polyimides are particularly usefull in the preparation of fiber-reinforced, high-temperature composites for use in various engine parts including inlets, fan ducts, exit flaps and other parts of high speed aircraft. The polyimides are derived from the polymerization of effective amounts of at least one tetracarboxylic dianhydride, at least one polyamine and a novel dicarboxylic endcap having the formula presented.

  11. Targeting Cancer with Antisense Oligomers

    SciTech Connect

    Hnatowich, DJ

    2008-10-28

    With financial assistance from the Department of Energy, we have shown definitively that radiolabeled antisense DNAs and other oligomers will accumulate in target cancer cells in vitro and in vivo by an antisense mechanism. We have also shown that the number of mRNA targets for our antisense oligomers in the cancer cell types that we have investigated so far is sufficient to provide and antisense image and/or radiotherapy of cancer in mice. These studies have been reported in about 10 publications. However our observation over the past several years has shown that radiolabeled antisense oligomers administered intravenously in their native and naked form will accumulate and be retained in target xenografts by an antisense mechanism but will also accumulate at high levels in normal organs such as liver, spleen and kidneys. We have investigated unsuccessfully several commercially available vectors. Thus the use of radiolabeled antisense oligomers for the imaging of cancer must await novel approaches to delivery. This laboratory has therefore pursued two new paths, optical imaging of tumor and Auger radiotherapy. We are developing a novel method of optical imaging tumor using antisense oligomers with a fluorophore is administered while hybridized with a shorter complementary oligomer with an inhibitor. In culture and in tumored mice that the duplex remains intact and thus nonfluorescent until it encounters its target mRNA at which time it dissociates and the antisense oligomer binds along with its fluorophore to the target. Simultaneous with the above, we have also observed, as have others, that antisense oligomers migrate rapidly and quantitatively to the nucleus upon crossing cell membranes. The Auger electron radiotherapy path results from this observation since the nuclear migration properties could be used effectively to bring and to retain in the nucleus an Auger emitting radionuclide such as 111In or 125I bound to the antisense oligomer. Since the object becomes

  12. The backward end-cap for the PANDA electromagnetic calorimeter

    NASA Astrophysics Data System (ADS)

    Capozza, L.; Maas, F. E.; Noll, O.; Rodriguez Pineiro, D.; Valente, R.

    2015-02-01

    The PANDA experiment at the new FAIR facility will cover a broad experimental programme in hadron structure and spectroscopy. As a multipurpose detector, the PANDA spectrometer needs to ensure almost 4π coverage of the scattering solid angle, full and accurate multiple-particle event reconstruction and very good particle identification capabilities. The electromagnetic calorimeter (EMC) will be a key item for many of these aspects. Particle energies ranging from some MeVs to several GeVs have to be measured with a relative resolution of 1% ⊕ 2%/√E/GeV . It will be a homogeneous calorimeter made of PbWO4 crystals and will be operated at -25°C, in order to improve the scintillation light yield. With the exception of the very forward section, the light will be detected by large area avalanche photodiodes (APDs). The current pulses from the APDs will be integrated, amplified and shaped by ASIC chips which were developed for this purpose. The whole calorimeter has been designed in three sections: a forward end-cap, a central barrel and a backward end-cap (BWEC). In this contribution, a status report on the development of the BWEC is presented.

  13. Creation of coating surfaces possessing superhydrophobic and superoleophobic characteristics with fluoroalkyl end-capped vinyltrimethoxysilane oligomeric nanocomposites having biphenylene segments.

    PubMed

    Goto, Yuki; Takashima, Hiroki; Takishita, Katsuhisa; Sawada, Hideo

    2011-10-15

    Fluoroalkyl end-capped vinyltrimethoxysilane oligomeric nanocomposites having biphenylene units [R(F)-(VM-SiO(2))(n)-R(F)/Ar-SiO(2)] were prepared by the sol-gel reaction of the corresponding oligomer [R(F)-(VM)(n)-R(F)] with 4,4'-bis(triethoxysilyl)-1,1'-biphenyl [Ar-Si(OEt)(3)] under alkaline conditions. R(F)-(VM-SiO(2))(n)-R(F)/Ar-SiO(2) nanocomposites were applied to the surface modification of PMMA to exhibit not only a good oleophobicity imparted by fluorine but also a fluorescent emission ability on the surface. Methanol sol solutions of R(F)-(VM-SiO(2))(n)-R(F)/Ar-SiO(2) nanocomposites were effective for the surface modification of glass through the dipping technique to exhibit good oleophobicity with superhydrophobicity on the modified glass surface. On the other hand, 1,2-dichloroethane sol solutions enabled R(F)-(VM-SiO(2))(n)-R(F)/Ar-SiO(2) nanocomposites to exhibit both superhydrophobic and superoleophobic characteristics on the modified surface through dipping the glass in these sol solutions.

  14. Phenylethynyl End-Capping Reagents And Reactive Diluents

    NASA Technical Reports Server (NTRS)

    Bryant, Robert G.; Jensen, Brian J.; Hergenrother, Paul M.

    1994-01-01

    Compounds containing phenylethynyl group serve as thermally reactive polymer end caps and reactive diluents. Useful in preparation of adhesives, composite matrices, and molding compounds. These reagents transform arylene ether oligomers and polymers into readily processable reactive materials that convert thermally to thermosets. Compounds synthesized for subsequent use in making thermoset polymers. Phenylethynyl group found to offer several unexpected advantages over ethynyl-based analog.

  15. Recent Results From The ATLAS Endcap Combined Test Beam

    SciTech Connect

    Schacht, Peter

    2006-10-27

    The ATLAS detector at the LHC at CERN is entering the last phase of construction, with the ATLAS calorimeter passing already the first steps of commissioning. The endcap region in the range of pseudorapidity 2.4 < |{eta}| < 4.0 is a particular complex one, with the electromagnetic, hadronic and forward calorimeters. In a dedicated beam run this region has been studied using the individual calorimeter modules. The set-up was as close as possible to the real ATLAS calorimeter, including all details like inactive support material structures. The goal is to validate the MC simulation for the different regions and to cross check the intercalibration of the various calorimeters. Electron and pion data have been taken in an energy range 6 < E < 200 GeV with special emphasis on lateral and vertical scans to study the transition regions in detail.

  16. CMS HCAL Endcap Simulations for the High Luminosity LHC

    NASA Astrophysics Data System (ADS)

    Pedro, Kevin

    2013-04-01

    The long-term high luminosity upgrade to the LHC will increase the levels of radiation affecting the CMS calorimeters. By the end of Phase 2, parts of the electromagnetic and hadronic endcap calorimeters could receive up to 10 MRad of radiation. A model of the radiation damage to HCAL, which has been implemented in the CMS fast simulation, will be described. The effects of radiation on physics capabilities with jets will be presented, with the most important effect coming from scaling of photodetector noise due to recalibration. In addition, a standalone Geant4 simulation with a simplified geometry can be used to test configurations with new radiation-hard ECALs. Results for pion response and resolution with new configurations will be shown.

  17. New organic semiconductors with imide/amide-containing molecular systems.

    PubMed

    Liu, Zitong; Zhang, Guanxin; Cai, Zhengxu; Chen, Xin; Luo, Hewei; Li, Yonghai; Wang, Jianguo; Zhang, Deqing

    2014-10-29

    Due to their high electron affinities, chemical and thermal stabilities, π-conjugated molecules with imide/amide frameworks have received considerable attentions as promising candidates for high-performance optoelectronic materials, particularly for organic semiconductors with high carrier mobilities. The purpose of this Research News is to give an overview of recent advances in development of high performance imide/amide based organic semiconductors for field-effect transistors. It covers naphthalene diimide-, perylene diimide- and amide-based conjugated molecules and polymers for organic semiconductors.

  18. Counterion condensation on heparin oligomers.

    PubMed

    Minsky, Burcu Baykal; Atmuri, Anand; Kaltashov, Igor A; Dubin, Paul L

    2013-04-08

    The electropherogram of native heparin shows a broad distribution of mobilities μ, which truncates abruptly at a notably high μ = 4.7 × 10(-4) cm(2) V(-1) s(-1). This highly skewed mobility distribution is also found for the 20-saccharide chain, which shows from mass spectrometry a more uniform (symmetrical) with respect to sulfation level. Since a partially degraded heparin exhibits oligomer peaks with μ> 5 × 10(-4) cm(2) V(-1) s(-1) (appearing to escape the limitation of the mobility value for native heparin), we examined the electrophoretic behavior of chain-length monodisperse heparin oligomers. Their mobilities varied inversely with the logarithm of the contour length, L, for L from 3 to 10 nm and reached an asymptotic limit for L > 20 nm. The generality of this effect was indicated by similar behavior for oligomers of poly(styrene sulfonate). A recent theory of polyelectrolyte end effects (Manning, G. S. Macromolecules2008, 41, 6217-6227), in which chain termini exhibit reduced counterion condensation was found to quantitatively account for these results. A qualitative explanation for the anomalously high value of μ of native heparin, 10-20% higher than those seen for synthetic polyelectrolytes of higher linear charge density, is suggested on the basis of similar junction effects (Manning, G. S. Macromolecules2008, 41, 6217-6227), which reduce counterion condensation at the interfaces of regions of high and low sulfation. We suggest that these effects should be considered in models for the biofunctionality of the regulated high and low sulfation (NS/NA) domains of heparan sulfate.

  19. Laser rods with undoped, flanged end-caps for end-pumped laser applications

    DOEpatents

    Meissner, H.E.; Beach, R.J.; Bibeau, C.; Sutton, S.B.; Mitchell, S.; Bass, I.; Honea, E.

    1999-08-10

    A method and apparatus for achieving improved performance in a solid state laser is provided. A flanged, at least partially undoped end-cap is attached to at least one end of a laserable medium. Preferably flanged, undoped end-caps are attached to both ends of the laserable medium. Due to the low scatter requirements for the interface between the end-caps and the laser rod, a non-adhesive method of bonding is utilized such as optical contacting combined with a subsequent heat treatment of the optically contacted composite. The non-bonded end surfaces of the flanged end-caps are coated with laser cavity coatings appropriate for the lasing wavelength of the laser rod. A cooling jacket, sealably coupled to the flanged end-caps, surrounds the entire length of the laserable medium. Radiation from a pump source is focused by a lens duct and passed through at least one flanged end-cap into the laser rod. 14 figs.

  20. Immunomodulatory Drugs (IMiDs) in Multiple Myeloma.

    PubMed

    Raza, Shahzad; Safyan, Rachael A; Suzanne, Lentzsch

    2017-02-13

    Multiple myeloma (MM) is a plasma cell neoplasm that is incurable with conventional therapy. However, the treatment of MM has dramatically changed since the emergence of immunomodulatory drugs and proteasome inhibitors. The improvements in survival are linked to a deeper understanding of the molecular mechanisms of the disease. Thalidomide, although highly active in MM, is associated with considerable toxicity, particularly in older patients. Immunomodulatory drugs (IMiDs) are structural and functional analogues of thalidomide that represent a promising new class of immunomodulators for treatment of a variety of inflammatory, autoimmune, and neoplastic diseases. Lenalidomide, a second generation IMiD, is more potent and has a better toxicity profile than thalidomide. It is commonly used in newly-diagnosed multiple myeloma, relapse refractory myeloma and as maintenance therapy after autologous stem cell transplantation (ASCT). Pomalidomide, a third generation IMiD, is 10 times more potent than lenalidomide and has already shown impressive results in patients who are heavily pre-treated and refractory to both lenalidomide and bortezomib. Here we provide a comprehensive review on IMiDs including molecular mechanisms, recent advances in therapeutic applications and management of toxicities in the treatment of MM.

  1. Molecular organization in perylene tetracarboxylic di-imide solid films

    NASA Astrophysics Data System (ADS)

    Akers, K.; Aroca, R.; Hort, A. M.; Loutfy, R. O.

    The vibrational spectra of thin solid films of three perylene tetracarboxylic di-imide derivatives (phenyl, methyl, and unsubstituted) are reported. A preferred molecular orientation in the evaporated solid films emerged for all three perylene derivatives from the i.r. data. Raman spectra obtained in resonance with the absorption band were characteristic of scattering via a Herzberg—Teller mechanism.

  2. 21 CFR 177.2450 - Polyamide-imide resins.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ...)(1) of this section shall have a solution viscosity of not less than 1.200. Polyamide-imide resins identified in paragraph (a)(2) of this section shall have a solution viscosity of not less than 1.190. Solution viscosity shall be determined by a method titled “Solution Viscosity” which is incorporated...

  3. Thermoset High-Temperature Systems Based on the Homolytic Polymerization of Benzocyclobutene Aromatic Imide Monomers and Oligomers

    DTIC Science & Technology

    1986-06-01

    more reactive form, I.e., o-xylylene (or o-quinodimethane) will be engaged in a Diels - Alder reaction-; otherwise, it will react with itself. On account...EJ.C U "S WORK) SELF CO (ERREDE’S S OWORK) ( DIELS - ALDER ) 1b) EVERY STABLE AT TEMPERATURES BELOW "" 12 oil H2H-ABSTRACTION -C 2 H MOREINTRAMOLECULAR...self-reaction of o-xylylene via a Diels - Alder cycloadditlon will lead to the formation of the spiro-intermediate 11 which is reported to be very

  4. Cross-linked fluoroalkyl end-capped co-oligomeric nanoparticle-encapsulated fullerenea new approach to the surface modification of traditional organic polymers with fullerene-containing nanoparticles.

    PubMed

    Mugisawa, Masaki; Kasai, Remi; Sawada, Hideo

    2009-01-06

    Cross-linked fluoroalkyl end-capped co-oligomeric nanoparticle-encapsulated fullerenes, prepared by deprotecting a fluoroalkyl end-capped isocyanatoethyl methacrylate 2-butanone oxime adduct-1-hydroxy-5-adamantylacrylate co-oligomer in the presence of fullerene, were of well-defined size in the nanometer range (28-82 nm) and exhibited good dispersibility in a variety of solvents such as methanol, ethanol, isopropyl alcohol, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, and 1,2-dichloroethane. Transmission electron microscopy images also showed that these nanocomposites were particles with a mean diameter of 45 nm and that the fullerenes were tightly encapsulated into fluorinated nanoparticle cores. In methanol, these fluorinated nanoparticles emitted fluorescence related to the presence of fullerene and were applied in the surface modification of traditional organic polymers such as poly(methyl methacrylate) (PMMA) to effect good oleophobicity imparted by fluorine on the modified film surfaces. Interestingly, a higher fluorescent intensity of fullerene was observed on the modified PMMA surfaces, although the reverse side of these film surfaces yielded an extremely weak fluorescent intensity. More interestingly, a fluorescence microscopy image of the cross-section of the modified PMMA film showed that encapsulated fullerene was arranged regularly above the modified PMMA film surface.

  5. Photodegradation of polymer-dispersed perylene di-imide dyes

    NASA Astrophysics Data System (ADS)

    Tanaka, Nobuaki; Barashkov, Nikolay; Heath, Jerry; Sisk, Wade N.

    2006-06-01

    Polymer-dispersed perylene di-imide dye photodegradation is investigated by monitoring the fluorescence intensity as a function of 532 nm laser pulses. Anaerobically irradiated polymer-dye films exhibited an accelerated decrease in fluorescence intensity, which was partially recovered upon exposure to oxygen. Decelerated photodegradation rates were observed for perylene di-imide ethanol solutions upon the addition of a singlet oxygen quenching antioxidant. These observations suggest reversible photoreduction and type II photo-oxidation as important photodegradation mechanisms. Type II photo-oxidation for perylene red 532 nm irradiation is supported by a singlet oxygen quantum yield of 0.09±0.03, determined via detection of time-resolved O2 (a1Δg —> X3∑g-) infrared phosphorescence.

  6. Photodegradation of polymer-dispersed perylene di-imide dyes.

    PubMed

    Tanaka, Nobuaki; Barashkov, Nikolay; Heath, Jerry; Sisk, Wade N

    2006-06-01

    Polymer-dispersed perylene di-imide dye photodegradation is investigated by monitoring the fluorescence intensity as a function of 532 nm laser pulses. Anaerobically irradiated polymer-dye films exhibited an accelerated decrease in fluorescence intensity, which was partially recovered upon exposure to oxygen. Decelerated photodegradation rates were observed for perylene di-imide ethanol solutions upon the addition of a singlet oxygen quenching antioxidant. These observations suggest reversible photoreduction and type II photo-oxidation as important photodegradation mechanisms. Type II photo-oxidation for perylene red 532 nm irradiation is supported by a singlet oxygen quantum yield of 0.09+/-0.03, determined via detection of time-resolved O2 (a1delta(g) --> X3sigma(g)-) infrared phosphorescence.

  7. Mixture of cholesterol end-capped polyethylene glycol with DSPC liposomal

    NASA Astrophysics Data System (ADS)

    Sharifi, Soheil

    2015-07-01

    The dynamic of network of self-assembled liposome by end-capped polymer was investigated using dynamic light scattering. The liposome network, physically cross-linked by mixed liposome solutions with three different length scale of cholesterol end-capped polyethylene glycol. The network of liposome is dependent on both the polymer concentration and length scale. In the pure liposome, one motion at low time scale is observed by DLS. In the higher concentration of polymer in liposome, several motion is observed that the fast motion is alpha relaxation and other two slow motion are beta and gamma relaxations. The distance between diffusion coefficient of fast and slow relaxation is increased with increase of length scale of endcapped polymers. The SAXS data is fitted with a Percus-Yevick hard sphere model and it shows that the size of liposome increasing with increase of polymer length scale in the mixture system.

  8. Ru-catalyzed stereoselective addition of imides to alkynes.

    PubMed

    Goossen, Lukas J; Blanchot, Mathieu; Brinkmann, Claus; Goossen, Käthe; Karch, Ralph; Rivas-Nass, Andreas

    2006-12-08

    A catalyst system formed in situ from bis(2-methylallyl)cycloocta-1,5-dieneruthenium(II) ((cod)Ru[met]2), a phosphine, and scandium(III) trifluoromethanesulfonate (Sc(OTf)3) was found to efficiently catalyze the anti-Markovnikov addition of imides to terminal alkynes, allowing mild and atom-economic synthesis of enimides. Depending on the phosphine employed, both the (E)- and the (Z)-isomer can be accessed stereoselectively.

  9. Approaches to New Endcaps for Improved Oxidation Resistance

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B.; Frimer, Aryeh A.

    1999-01-01

    Norbornenyl-end capped PMR polyimide resins are widely used as polymer matrix composite materials for aircraft engine applications, since they combine ease of processing with good oxidative stability up to 300 C. PMR resins are prepared by a two-step approach involving the initial formation of oligomeric pre-polymers capped at both ends by a latent reactive end cap. The end cap undergoes cross-linking during higher temperature processing, producing the desired low density, high specific strength materials, for PMR- 15. The end cap facilitates processing by controlling the molecular weight of the oligomer and allowing flow before it cross-links. However, after cross-linking, this very end cap accounts for much of the weight loss in the polymer on aging in air at elevated temperatures. Understanding this degradation provides clues for designing new end caps to slow down degradation, and prolong the lifetime of the material.

  10. In Situ Poling and Imidization of Amorphous Piezoelectric Polyimides

    NASA Technical Reports Server (NTRS)

    Park, Cheol; Ounaies, Zoubeida; Wise, Kristopher E.; Harrison, Joycelyn S.; Bushnell, Dennis M. (Technical Monitor)

    2002-01-01

    An amorphous piezoelectric polyimide containing polar functional groups has been developed using a combination of experimental and molecular modeling for potential use in high temperature applications. This amorphous polyimide, (Beta-CN)APB/ODPA, has exhibited good thermal stability and piezoelectric response at temperatures up to 150C. Density functional calculations predicted that a partially cured amic acid (open imide ring) possesses a dipole moment four times larger than the fully imidized closed ring. In situ poling and imidization of the partially cured (Beta-CN)APB/ODPA, was studied in an attempt to maximize the degree of dipolar orientation and the resultant piezoelectric response. A positive corona poling was used to minimize localized arcing during poling and to allow use of higher poling fields without dielectric breakdown. The dielectric relaxation strength, remanent polarization, and piezoelectric response were evaluated as a function of the poling profile. The partially cured, corona poled polymers exhibited higher dielectric relaxation strength (delta varepsilon), remanent polarization (Pr) and piezoelectric strain coefficient (d33) than the fully cured, conventionally poled ones.

  11. Discovery of the target for immunomodulatory drugs (IMiDs).

    PubMed

    Ito, Takumi; Ando, Hideki; Handa, Hiroshi

    2016-05-01

    Half a century ago, the sedative thalidomide caused a serious drug disaster because of its teratogenicity and was withdrawn from the market. However, thalidomide, which has returned to the market, is now used for the treatment of leprosy and multiple myeloma (MM) under strict control. The mechanism of thalidomide action had been a long-standing question. We developed a new affinity bead technology and identified cereblon (CRBN) as a thalidomide-binding protein. We found that CRBN functions as a substrate receptor of an E3 cullin-Ring ligase complex 4 (CRL4) and is a primary target of thalidomide teratogenicity. Recently, new thalidomide derivatives, called immunomodulatory drugs (IMiDs), have been developed by Celgene. Among them, lenalidomide (Len) and pomalidomide (Pom) were shown to exert strong therapeutic effects against MM. It was found that Len and Pom both bind CRBN-CRL4 and recruit neomorphic substrates (Ikaros and Aiolos). More recently it was reported that casein kinase 1a (Ck1a) was identified as a substrate for CRBN-CRL4 in the presence of Len, but not Pom. Ck1a breakdown explains why Len is specifically effective for myelodysplastic syndrome with 5q deletion. It is now proposed that binding of IMiDs to CRBN appears to alter the substrate specificity of CRBN-CRL4. In this review, we introduce recent findings on IMiDs.

  12. Pathogenesis of Abeta oligomers in synaptic failure.

    PubMed

    Sivanesan, Senthilkumar; Tan, Aaron; Rajadas, Jayakumar

    2013-03-01

    The soluble Abeta oligomers in brain are highly correlated with memory related synaptic dysfunctions in Alzheimer's disease (AD). However, more recent studies implicate the involvement of Abeta dimers and trimers in memory related AD pathology. Apparently, Abeta oligomers can bind with cellular prion protein at the membrane receptors, forming annular amyloid pores and membrane ion channels to induce aberrant spine cytoskeletal changes. Hence synapse targeting of Abeta oligomers involves activation of many receptors such as N-Methyl-D-aspartate (NMDA), alpha-amino-3- hydroxy-5-methyl-4-isoxazolepropionic acid (AMPA), nicotinic acetylcholine (nAChRs), p75 neurotrophin (p75NTR) following aberrant clustering of metabotropic glutamate receptors (mGluR5) leading to neuronal loss and LTP failure. In particular, NMDA and AMPA receptor activation by soluble amyloid oligomers involves calcium mediated mitochondrial dysfunction, decreased Ca((2+))/calmodulin-dependent protein kinase II (CaMKII) levels at the synapses accompanying dramatic loss of synaptic proteins such as postsynaptic density-95 (PSD-95), dynamin-1 and synaptophysin. This kind of receptor-Abeta oligomer interaction might eventually affect the neuronal membrane integrity by altering dielectric barrier, various synaptic proteins, spine morphology and density and P/Q calcium currents that might provoke a cascade of events leading to neuronal loss and memory failure. In this review, we try to explain in detail the various possible mechanisms that connect Abeta oligomers with synapse damage and memory failure.

  13. Cementitious building material incorporating end-capped polyethylene glycol as a phase change material

    DOEpatents

    Salyer, Ival O.; Griffen, Charles W.

    1986-01-01

    A cementitious composition comprising a cementitious material and polyethylene glycol or end-capped polyethylene glycol as a phase change material, said polyethylene glycol and said end-capped polyethylene glycol having a molecular weight greater than about 400 and a heat of fusion greater than about 30 cal/g; the compositions are useful in making pre-formed building materials such as concrete blocks, brick, dry wall and the like or in making poured structures such as walls or floor pads; the glycols can be encapsulated to reduce their tendency to retard set.

  14. High char imide-modified epoxy matrix resins. [for graphite-epoxy composites

    NASA Technical Reports Server (NTRS)

    Serafini, T. T.; Delvigs, P.; Vannucci, R. D.

    1979-01-01

    The synthesis of a class of bis(imide-amine) curing agents for epoxy matrix resins is discussed. Glass transition temperatures and char yield data of an epoxy cured with various bis(imide-amines) are presented. The room temperature and 350 F mechanical properties, and char yields of unidirectional graphite fiber laminates prepared with conventional epoxy and imide-modified epoxy resins are presented.

  15. Poly(ethylenglycol)dimethylether-lithium bis(trifluoromethanesulfonyl)imide, PEG500DME-LiTFSI, as high viscosity electrolyte for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Bernhard, Rebecca; Latini, Alessandro; Panero, Stefania; Scrosati, Bruno; Hassoun, Jusef

    2013-03-01

    In this paper we report a poly(ethylenglycol)dimethylether-lithium bis(trifluoromethanesulfonyl) imide (PEG500DME-LiTFSI) as high viscosity, safe electrolyte for lithium ion batteries. The high molecular weight of the end-capped ether solvent is reflected as low vapor pressure and excellent thermal stability of the electrolyte, as demonstrated by thermogravimetry, this resulting in remarkable safety content. The electrochemical impedance spectroscopy study of the electrolyte demonstrates a Li-transference number of 0.48, a conductivity of the order of 10-3 S cm-1, and a high interphase stability with the lithium metal, the linear sweep voltammetry indicates an electrochemical stability window extending up to 4.8 V vs. Li/Li+. Furthermore, promising electrochemical performances in terms of reversibility, cycling stability and low charge-discharge polarization are observed using the electrolyte in lithium and in lithium ion batteries using lithium cobalt oxide (LCO) as cathode and titanium dioxide (TiO2) as anode. Hence, this electrolyte is a promising candidate for applications in safe, high performance lithium ion batteries.

  16. Exploring the effect of conducting endcaps on the Princeton MRI Experiment

    NASA Astrophysics Data System (ADS)

    Caspary, Kyle; Gilson, Erik; Goodman, Jeremy; Ji, Hantao; Sloboda, Peter

    2016-10-01

    The magnetorotational instability (MRI) is believed to be the primary mechanism which generates the turbulence required to explain the rapid accretion rates observed in some magnetized accretion disks. The Princeton MRI experiment is a modified Taylor-Couette device which uses GaInSn eutectic as a working fluid to study rotating MHD Flows. Diagnostics include Ultrasound Doppler Velocimetry (UDV) for flow profile measurements and an array of magnetic Hall sensors located on the inner and outer cylinders. Results are presented from experiments with conducting endcaps which were installed in order to increase the saturation amplitude of the MRI signal and the angular momentum coupling to the fluid. The effect of conducting endcaps on Shercliff layer instabilities is examined with a comparison to previous results with insulating endcaps. With sufficient velocity shear and magnetic field strength, the fluid exerts a torque on the conducting endcaps due to a coupling via the magnetic field. The onset criterion of this torque is currently under investigation. Motivated by results from the spectral/finite-element code SFEMaNS, the inner ring speed was varied in order to minimize the contribution to the radial magnetic field measurements from non-MRI sources such as Ekman flows.

  17. Lithium solvation in bis(trifluoromethanesulfonyl)imide-based ionic liquids.

    PubMed

    Lassègues, Jean-Claude; Grondin, Joseph; Talaga, David

    2006-12-28

    The lithium solvation in (1 -x)(EMI-TFSI), xLiTFSI ionic liquids where EMI(+) is the 1-ethyl-3-methylimidazolium cation and TFSI(-) the bis(trifluoromethanesulfonyl)imide anion, is shown by Raman spectroscopy to involve essentially [Li(TFSI)(2)](-) anionic clusters for 0 < x < 0.4, but addition of stoichiometric amounts of solvents S such as oligoethers changes the lithium solvation into [Li(S)(m)](+) cationic clusters; the lithium transference number in TFSI-based ionic liquid electrolytes for lithium batteries should thus be strongly improved.

  18. Functionalized Metallated Cavitands via Imidation and Late-Stage Elaboration

    PubMed Central

    Zhao, Yanchuan

    2015-01-01

    Efficient methods for the preparation of functionalized metallated cavitands are described. Functional groups can be either introduced by an imidation of metal-oxo complexes or by a late-stage elaboration of the imido ligands. By using diversified iminophosphorane (PPh3=NR) reagents, π-conjugated pyrene, redox active ferrocene and polymerizable norbornene moieties were successfully introduced. Furthermore, the iodo and alkynyl groups on the imido ligands are capable of undergoing efficient Sonogashira cross-coupling and copper-catalyzed azide alkyne cycloaddition reactions, thereby providing facile access to complex architectures containing metallated cavitands. PMID:26962300

  19. Lactic acid oligomers (OLAs) as prodrug moieties.

    PubMed

    Kruse, J; Lachmann, B; Lauer, R; Eppacher, S; Noe, C R

    2013-02-01

    In this paper we propose the use of lactic acid oligomers (OLAs) as prodrug moieties. Two synthetic approaches are presented, on the one hand a non selective oligomerisation of lactic acid and on the other hand a block synthesis to tetramers of lactic acid. Dimers of lactic acid were investigated with respect to their plasma stability and their adsorption to albumine. Ibuprofen was chosen as the first drug for OLAylation. The ester 19 of LA(1)-ibuprofen was evaluated with respect to the degradation to human plasma and the adsorption to albumine. All results indicate that lactic acid oligomers are promising prodrug moieties.

  20. Immune‐mediated inflammatory diseases (IMIDs) and biologic therapy: a medical revolution

    PubMed Central

    Kuek, Annabel; Hazleman, Brian L; Östör, Andrew J K

    2007-01-01

    Targeted biologic therapies have revolutionised treatment of immune‐mediated inflammatory diseases (IMIDs) due to their efficacy, speed of onset and tolerability. The discovery that clinically unrelated conditions, such as rheumatoid arthritis and Crohn's disease, share similar immune dysregulation has led to a shift in the management of IMIDs from one of organ‐based symptom relief to mechanism‐based treatment. The fact that anticytokine therapy has been effective in treating multiple orphan inflammatory conditions confirms the IMID paradigm. In this review we examine the biologic agents currently licensed for use in the US and Europe: infliximab, etanercept, adalimumab, rituximab, abatacept, anakinra, alefacept and efalizumab. We also discuss the rationale behind the management of IMIDs using rheumatoid arthritis, Crohn's disease, psoriasis and psoriatic arthritis as examples. For the medical profession, IMID represents a breakthrough in the way pathology is classified. In this burgeoning era of biologic therapy the prospect of complete disease remission is conceivable. PMID:17403952

  1. Phosphorus-containing imide resins - Modification by elastomers

    NASA Technical Reports Server (NTRS)

    Varma, I. K.; Fohlen, G. M.; Parker, J. A.; Varma, D. S.

    1984-01-01

    The syntheses and general features of addition-type maleimide resins based on bis(m-aminophenyl)phosphine oxide and tris(m-aminophenyl)phosphine oxide have been reported previously. These resins have been used to fabricate graphite cloth laminates having excellent flame resistance. These composites did not burn even in pure oxygen. However, these resins were somewhat brittle. This paper reports the modification of these phosphorus-containing resins by an amine-terminated butadiene-acrylonitrile copolymer (ATBN) and a perfluoroalkylene diaromatic amine elastomer (3F). An approximately two-fold increase in short beam shear strength and flexural strength was observed at 7 percent ATBN concentration. The tensile, flexural, and shear strengths were reduced when 18 percent ATBN was used. Anaerobic char yields of the resins at 800 C and the limiting oxygen indexes of the laminates decreased with increasing ATBN concentration. The perfluorodiamine (3F) was used with both imide resins at 6.4 percent concentration. The shear strength was doubled in the case of the bisimide with no loss of flammability characteristics. The modified trisimide laminate also had improved properties over the unmodified one. The dynamic mechanical analysis of a four-ply laminate indicated a glass transition temperature above 300 C. Scanning electron micrographs of the ATBN modified imide resins were also recorded.

  2. Molecular Structure and Transport Dynamics in Perfluoro Sulfonyl Imide Membranes

    SciTech Connect

    Idupulapati, Nagesh B.; Devanathan, Ramaswami; Dupuis, Michel

    2011-05-25

    We report a detailed and comprehensive analysis of the nanostructure, transport dynamics of water and hydronium and water percolation in hydrated perfluoro sulfonyl imides (PFSI), a polymer considered for proton transport in PEM fuel cells, using classical molecular dynamics simulations. The dynamical changes are related to the changes in the membrane nanostructure. Water network percolation threshold, the level at which a consistent spanning water network starts to develop in the membrane, lies between hydration level (λ) 6 and 7. The higher acidity of the sulfonyl imide acid group of PFSI compared to Nafion reported in our earlier ab initio study, translates into more free hydronium ions at low hydration levels. Nevertheless, the calculated diffusion coefficients of the H3O+ ions and H2O molecules as a function the hydration level were observed to be almost the same as that of Nafion, indicating similar conductivity and consistent with the experimental observations. This research was performed in part using the Molecular Science Computing Facility in the William R. Wiley Environmental Molecular Sciences Laboratory, a U.S. Department of Energy (DOE) national scientific user facility located at the Pacific Northwest National Laboratory (PNNL). This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  3. Molecular structure and transport dynamics in perfluoro sulfonyl imide membranes.

    PubMed

    Idupulapati, Nagesh; Devanathan, Ram; Dupuis, Michel

    2011-06-15

    We report a detailed and comprehensive analysis from classical molecular dynamics simulations of the nanostructure of a model of hydrated perfluoro sulfonyl imide (PFSI) membrane, a polymeric system of interest as a proton conductor in polymer electrolyte membrane fuel cells. We also report on the transport dynamics of water and hydronium ions, and water network percolation in this system. We find that the water network percolation threshold for PFSI, i.e. the threshold at which a consistent spanning water network starts to develop in the membrane, is found to occur between hydration levels (λ) 6 and 7. The higher acidity of the sulfonyl imide acid group of PFSI compared to the sulfonic acid group in Nafion, as computationally characterized in our earlier ab initio study (Idupulapati et al 2010 J. Phys. Chem. A 114 6904-12), results in a larger fraction of 'free' hydronium ions at low hydration levels in PFSI compared to Nafion. However, the calculated diffusion coefficients of the H(3)O(+) ions and H(2)O molecules as a function the hydration level are observed to be almost the same as that of Nafion, indicating similar conductivity and consistent with experimental data.

  4. Designing Surface-Confined Coordination Oligomers

    SciTech Connect

    Altman, M.; Rachamim, M; Ichiki, T; Iron, M; Evmenenko, G; Dutta, P; van der Boom, M

    2010-01-01

    HOMO-LUMO engineering of coordination-based oligomers covalently bound to silicon or glass has been achieved by the use of a partially fluorinated chromophore (see graphic). The experimental and computationally derived physical chemical properties of these assemblies are compared to their non-fluorinated analogues.

  5. Glucosamine oligomers: 1. Preparation and characterization.

    PubMed

    Domard, A; Cartier, N

    1989-10-01

    Hydrolysis of chitosan in hot concentrated HCl led to chito-oligosaccharides [beta-(1----4) linked 2-amino-2-deoxy-D-glucose]. The time dependence of the distribution was studied. A convenient choice of the conditions for steric exclusion chromatography of these hydrolysates allowed the separation of the first 15 oligomers and of fractions up to DP = 40.

  6. Effect of the endcapping of reversed-phase high-performance liquid chromatography adsorbents on the adsorption isotherm

    SciTech Connect

    Gritti, Fabrice; Guiochon, Georges A

    2005-09-01

    The retention mechanisms of n-propylbenzoate, 4-t ert-butylphenol, and caffeine on the endcapped Symmetry-C{sub 18} and the non-endcapped Resolve-C{sub 18} are compared. The adsorption isotherms were measured by frontal analysis (FA), using as the mobile phase mixtures of methanol or acetonitrile and water of various compositions. The isotherm data were modeled and the adsorption energy distributions calculated. The surface heterogeneity increases faster with decreasing methanol concentration on the non-endcapped than on the endcapped adsorbent. For instance, for methanol concentrations exceeding 30% (v/v), the adsorption of caffeine is accounted for by assuming three and two different types of adsorption sites on Resolve-C{sub 18} and Symmetry-C{sub 18}, respectively. This is explained by the effect of the mobile phase composition on the structure of the C{sub 18}-bonded layer. The bare surface of bonded silica appears more accessible to solute molecules at high water contents in the mobile phase. On the other hand, replacing methanol by a stronger organic modifier like acetonitrile dampens the differences between non-endcapped and endcapped stationary phase and decreases the degree of surface heterogeneity of the adsorbent. For instance, at acetonitrile concentrations exceeding 20%, the surface appears nearly homogeneous for the adsorption of caffeine.

  7. Synthesis and evaluation of new spacers for use as dsDNA endcaps

    PubMed Central

    Ng, Pei-Sze; Laing, Brian M.; Balasundarum, Ganesan; Pingle, Maneesh; Friedman, Alan; Bergstrom, Donald E.

    2010-01-01

    A series of aliphatic and aromatic spacer molecules designed to cap the ends of DNA duplexes have been synthesized. The spacers were converted into dimethoxytrityl protected phosphoramidites as synthons for oligonucleotides synthesis. The effect of the spacers on the stability of short DNA duplexes was assessed by melting temperature studies. Endcaps containing amide groups were found to be less stabilizing than the hexaethylene glycol spacer. Endcaps containing either a terthiophene or a naphthalene tetracarboxylic acid dimide were found to be significantly more stabilizing. The former showed a preference for stacking above an A•T base pair. Spacers containing only methylene (-CH2-) and amide (-CONH-) groups interact weakly with DNA and consequently may be optimal for applications that require minimal influence on DNA structure but require a way to hold the ends of double-stranded DNA together. PMID:20715857

  8. Synthesis and evaluation of new spacers for use as dsDNA end-caps.

    PubMed

    Ng, Pei-Sze; Laing, Brian M; Balasundarum, Ganesan; Pingle, Maneesh; Friedman, Alan; Bergstrom, Donald E

    2010-08-18

    A series of aliphatic and aromatic spacer molecules designed to cap the ends of DNA duplexes have been synthesized. The spacers were converted into dimethoxytrityl-protected phosphoramidites as synthons for oligonucleotides synthesis. The effect of the spacers on the stability of short DNA duplexes was assessed by melting temperature studies. End-caps containing amide groups were found to be less stabilizing than the hexaethylene glycol spacer. End-caps containing either a terthiophene or a naphthalene tetracarboxylic acid diimide were found to be significantly more stabilizing. The former showed a preference for stacking above an A*T base pair. Spacers containing only methylene (-CH(2)-) and amide (-CONH-) groups interact weakly with DNA and consequently may be optimal for applications that require minimal influence on DNA structure but require a way to hold the ends of double-stranded DNA together.

  9. Wholly Aromatic Ether-Imides as n-Type Semiconductors

    NASA Technical Reports Server (NTRS)

    Weiser, Erik; St. Clair, Terry L.; Dingemans, Theo J.; Samulski, Edward T.; Irene, Gene

    2006-01-01

    Some wholly aromatic ether-imides consisting of rod-shaped, relatively-low-mass molecules that can form liquid crystals have been investigated for potential utility as electron-donor-type (ntype) organic semiconductors. It is envisioned that after further research to improve understanding of their physical and chemical properties, compounds of this type would be used to make thin film semiconductor devices (e.g., photovoltaic cells and field-effect transistors) on flexible electronic-circuit substrates. This investigation was inspired by several prior developments: Poly(ether-imides) [PEIs] are a class of engineering plastics that have been used extensively in the form of films in a variety of electronic applications, including insulating layers, circuit boards, and low-permittivity coatings. Wholly aromatic PEIs containing naphthalene and perylene moieties have been shown to be useful as electrochromic polymers. More recently, low-molecular-weight imides comprising naphthalene-based molecules with terminal fluorinated tails were shown to be useful as n-type organic semiconductors in such devices as field-effect transistors and Schottky diodes. Poly(etherimide)s as structural resins have been extensively investigated at NASA Langley Research Center for over 30 years. More recently, the need for multi-functional materials has become increasingly important. This n-type semiconductor illustrates the scope of current work towards new families of PEIs that not only can be used as structural resins for carbon-fiber reinforced composites, but also can function as sensors. Such a multi-functional material would permit so-called in-situ health monitoring of composite structures during service. The work presented here demonstrates that parts of the PEI backbone can be used as an n-type semiconductor with such materials being sensitive to damage, temperature, stress, and pressure. In the near future, multi-functional or "smart" composite structures are envisioned to be able

  10. Capping of Aβ42 Oligomers by Small Molecule Inhibitors

    PubMed Central

    2015-01-01

    Aβ42 peptides associate into soluble oligomers and protofibrils in the process of forming the amyloid fibrils associated with Alzheimer’s disease. The oligomers have been reported to be more toxic to neurons than fibrils, and have been targeted by a wide range of small molecule and peptide inhibitors. With single touch atomic force microscopy (AFM), we show that monomeric Aβ42 forms two distinct types of oligomers, low molecular weight (MW) oligomers with heights of 1–2 nm and high MW oligomers with heights of 3–5 nm. In both cases, the oligomers are disc-shaped with diameters of ∼10–15 nm. The similar diameters suggest that the low MW species stack to form the high MW oligomers. The ability of Aβ42 inhibitors to interact with these oligomers is probed using atomic force microscopy and NMR spectroscopy. We show that curcumin and resveratrol bind to the N-terminus (residues 5–20) of Aβ42 monomers and cap the height of the oligomers that are formed at 1–2 nm. A second class of inhibitors, which includes sulindac sulfide and indomethacin, exhibit very weak interactions across the Aβ42 sequence and do not block the formation of the high MW oligomers. The correlation between N-terminal interactions and capping of the height of the Aβ oligomers provides insights into the mechanism of inhibition and the pathway of Aβ aggregation. PMID:25422864

  11. Performance of the ATLAS electromagnetic calorimeter end-cap module 0

    NASA Astrophysics Data System (ADS)

    Aubert, B.; Ballansat, J.; Bazan, A.; Beaugiraud, B.; Boniface, J.; Chollet, F.; Colas, J.; Delebecque, P.; Di Ciaccio, L.; Dumont-Dayot, N.; El Kacimi, M.; Gaumer, O.; Ghez, P.; Girard, C.; Gouanère, M.; Kambara, H.; Jérémie, A.; Jézéquel, S.; Lafaye, R.; Leflour, T.; Le Maner, C.; Lesueur, J.; Massol, N.; Moynot, M.; Neukermans, L.; Perrodo, P.; Perrot, G.; Poggioli, L.; Prast, J.; Przysiezniak, H.; Riccadona, X.; Sauvage, G.; Thion, J.; Wingerter-Seez, I.; Zitoun, R.; Zolnierowski, Y.; Chen, H.; Citterio, M.; Farrell, J.; Gordon, H.; Hackenburg, B.; Hoffman, A.; Kierstead, J.; Lanni, F.; Leite, M.; Lissauer, D.; Ma, H.; Makowiecki, D.; Radeka, V.; Rahm, D.; Rajagopalan, S.; Rescia, S.; Stumer, I.; Takai, H.; Yip, K.; Benchekroun, D.; Driouichi, C.; Hoummada, A.; Hakimi, M.; Stroynowski, R.; Ye, J.; Beck Hansen, J.; Belymam, A.; Bremer, J.; Chevalley, J. L.; Fassnacht, P.; Gianotti, F.; Hervas, L.; Marin, C. P.; Pailler, P.; Schilly, P.; Seidl, W.; Vossebeld, J.; Vuillemin, V.; Clark, A.; Efthymiopoulos, I.; Moneta, L.; Belhorma, B.; Collot, J.; Ferrari, A.; Gallin-Martel, M. L.; Hostachy, J. Y.; Martin, P.; Ohlsson-Malek, F.; Saboumazrag, S.; Ban, J.; Cartiglia, N.; Cunitz, H.; Dodd, J.; Gara, A.; Leltchouk, M.; Negroni, S.; Parsons, J. A.; Seman, M.; Simion, S.; Sippach, W.; Willis, W.; Barreiro, F.; Garcia, G.; Labarga, L.; Rodier, S.; del Peso, J.; Alexa, C.; Barrillon, P.; Benchouk, C.; Chekhtman, A.; Dinkespiler, B.; Djama, F.; Duval, P. Y.; Henry-Couannier, F.; Hinz, L.; Jevaud, M.; Karst, P.; Le Van Suu, A.; Martin, L.; Martin, O.; Mirea, A.; Monnier, E.; Nagy, E.; Nicod, D.; Olivier, C.; Pralavorio, P.; Repetti, B.; Raymond, M.; Sauvage, D.; Tisserant, S.; Toth, J.; Wielers, M.; Battistoni, G.; Carminati, L.; Costa, G.; Delmastro, M.; Fanti, M.; Mandelli, L.; Mazzanti, M.; Tartarelli, G. F.; Aulchenko, V.; Kazanin, V.; Kolachev, G.; Malyshev, V.; Maslennikov, A.; Pospelov, G.; Snopkov, R.; Shousharo, A.; Talyshev, A.; Tikhonov, Yu; Augé, E.; Bourdarios, C.; Breton, D.; Bonivento, W.; Cros, P.; de La Taille, C.; Falleau, I.; Fournier, D.; Guilhem, G.; Hassani, S.; Jacquier, Y.; Kordas, K.; Macé, G.; Merkel, B.; Noppe, J. M.; Parrour, G.; Pétroff, P.; Puzo, P.; Richer, J. P.; Rousseau, D.; Seguin-Moreau, N.; Serin, L.; Tocut, V.; Veillet, J. J.; Zerwas, D.; Astesan, F.; Bertoli, W.; Camard, A.; Canton, B.; Fichet, S.; Hubaut, F.; Imbault, D.; Lacour, D.; Laforge, B.; Le Dortz, O.; Martin, D.; Nikolic-Audit, I.; Orsini, F.; Rossel, F.; Schwemling, P.; Cleland, W.; McDonald, J.; Abouelouafa, E. M.; Ben Mansour, A.; Cherkaoui, R.; El Mouahhidi, Y.; Ghazlane, H.; Idrissi, A.; Belorgey, J.; Bernard, R.; Chalifour, M.; Le Coroller, A.; Ernwein, J.; Mansoulié, B.; Renardy, J. F.; Schwindling, J.; Taguet, J.-P.; Teiger, J.; Clément, C.; Lund-Jensen, B.; Lundqvist, J.; Megner, L.; Pearce, M.; Rydstrom, S.; Egdemir, J.; Engelmann, R.; Hoffman, J.; McCarthy, R.; Rijssenbeek, M.; Steffens, J.; This paper is dedicated to the memory of our colleague Dominique Sauvage, actively involved in the detector construction; beam test activities, who died accidentaly on March 16, 2002.

    2003-03-01

    The construction and beam test results of the ATLAS electromagnetic end-cap calorimeter pre-production module 0 are presented. The stochastic term of the energy resolution is between 10% and 12.5% GeV1/2 over the full pseudorapidity range. Position and angular resolutions are found to be in agreement with simulation. A global constant term of 0.6% is obtained in the pseudorapidity range 2.5< η<3.2 (inner wheel).

  12. Hadronic Shower Validation Experience for the ATLAS End-Cap Calorimeter

    SciTech Connect

    Kiryunin, A. E.; Salihagic, D.

    2007-03-19

    Validation of GEANT4 hadronic physics models is carried out by comparing experimental data from beam tests of modules of the ATLAS end-cap calorimeters with GEANT4 based simulations. Two physics lists (LHEP and QGSP) for the simulation of hadronic showers are evaluated. Calorimeter performance parameters like the energy resolution and response for charged pions and shapes of showers are studied. Comparison with GEANT3 predictions is done as well.

  13. Sensors for the End-cap prototype of the Inner Tracker in the ATLAS Detector Upgrade

    NASA Astrophysics Data System (ADS)

    Benítez, V.; Ullán, M.; Quirion, D.; Pellegrini, G.; Fleta, C.; Lozano, M.; Sperlich, D.; Hauser, M.; Wonsak, S.; Parzefall, U.; Mahboubi, K.; Kuehn, S.; Mori, R.; Jakobs, K.; Bernabeu, J.; García, C.; Lacasta, C.; Marco, R.; Rodriguez, D.; Santoyo, D.; Solaz, C.; Soldevila, U.; Ariza, D.; Bloch, I.; Diez, S.; Gregor, I. M.; Keller, J.; Lohwasser, K.; Peschke, R.; Poley, L.; Brenner, R.; Affolder, A.

    2016-10-01

    The new silicon microstrip sensors of the End-cap part of the HL-LHC ATLAS Inner Tracker (ITk) present a number of challenges due to their complex design features such as the multiple different sensor shapes, the varying strip pitch, or the built-in stereo angle. In order to investigate these specific problems, the "petalet" prototype was defined as a small End-cap prototype. The sensors for the petalet prototype include several new layout and technological solutions to investigate the issues, they have been tested in detail by the collaboration. The sensor description and detailed test results are presented in this paper. New software tools have been developed for the automatic layout generation of the complex designs. The sensors have been fabricated, characterized and delivered to the institutes in the collaboration for their assembly on petalet prototypes. This paper describes the lessons learnt from the design and tests of the new solutions implemented on these sensors, which are being used for the full petal sensor development. This has resulted in the ITk strip community acquiring the necessary expertise to develop the full End-cap structure, the petal.

  14. Rodent repellents: Preparation and properties of thiouronium compounds and cyclic imides

    USGS Publications Warehouse

    Bellack, E.; DeWitt, J.B.

    1954-01-01

    Syntheses and bioassays of cyclic imides and thiouronium compounds were carried out as part of a search for materials capable of preventing rodent damage to packaged commodities. Previous studies had shown that repellent activity was associated with functional groups containing nitrogen and sulfur, and was enhanced by the presence of ionic linkages. Twenty-seven thiouronium compounds and 40 imides, including 1 0 compounds not described previously, were prepared for these tests. Ten imides and 26 thiouronium compounds were repellent under the conditions of test. Information obtained in these studies will be utilized in the development and selection of more effective materials for prevention of rodent damage to foods and other commodities.

  15. Monte Carlo Simulation of Endlinking Oligomers

    NASA Technical Reports Server (NTRS)

    Hinkley, Jeffrey A.; Young, Jennifer A.

    1998-01-01

    This report describes initial efforts to model the endlinking reaction of phenylethynyl-terminated oligomers. Several different molecular weights were simulated using the Bond Fluctuation Monte Carlo technique on a 20 x 20 x 20 unit lattice with periodic boundary conditions. After a monodisperse "melt" was equilibrated, chain ends were linked whenever they came within the allowed bond distance. Ends remained reactive throughout, so that multiple links were permitted. Even under these very liberal crosslinking assumptions, geometrical factors limited the degree of crosslinking. Average crosslink functionalities were 2.3 to 2.6; surprisingly, they did not depend strongly on the chain length. These results agreed well with the degrees of crosslinking inferred from experiment in a cured phenylethynyl-terminated polyimide oligomer.

  16. Oligomer functionalized nanotubes and composites formed therewith

    DOEpatents

    Zettl, Alexander K; Sainsbury, Toby; Frechet, Jean M.J.

    2014-03-18

    Disclosed herein is a sequential functionalization methodology for the covalent modification of nanotubes with between one and four repeat units of a polymer. Covalent attachment of oligomer units to the surface of nanotubes results in oligomer units forming an organic sheath around the nanotubes, polymer-functionalized-nanotubes (P-NTs). P-NTs possess chemical functionality identical to that of the functionalizing polymer, and thus provide nanoscale scaffolds which may be readily dispersed within a monomer solution and participate in the polymerization reaction to form a polymer-nanotube/polymer composite. Formation of polymer in the presence of P-NTs leads to a uniform dispersion of nanotubes within the polymer matrix, in contrast to aggregated masses of nanotubes in the case of pristine-NTs. The covalent attachment of oligomeric units to the surface of nanotubes represents the formation of a functional nanoscale building block which can be readily dispersed and integrated within the polymer to form a novel composite material.

  17. Interaction of arginine oligomer with model membrane

    SciTech Connect

    Yi, Dandan . E-mail: yi_dandan@yahoo.com.cn; Guoming, Li; Gao, Li; Wei, Liang

    2007-08-10

    Short oligomers of arginine (R8) have been shown to cross readily a variety of biological barriers. A hypothesis was put forward that inverted micelles form in biological membranes in the presence of arginine oligomer peptides, facilitating their transfer through the membranes. In order to define the role of peptide-lipid interaction in this mechanism, we prepared liposomes as the model membrane to study the ability of R8 inducing calcein release from liposomes, the fusion of liposomes, R8 binding to liposomes and membrane disturbing activity of the bound R8. The results show that R8 binding to liposome membrane depends on lipid compositions, negative surface charge density and interior water phase pH values of liposomes. R8 has no activity to induce the leakage of calcein from liposomes or improve liposome fusion. R8 does not permeabilize through the membrane spontaneously. These peptides delivering drugs through membranes may depend on receptors and energy.

  18. Ethynyl terminated ester oligomers and polymers therefrom

    NASA Technical Reports Server (NTRS)

    Hergenrother, Paul M. (Inventor); hesives and composite matrices. (Inventor)

    1987-01-01

    A new class of ethynyl-terminated oligomers and the process for preparing same are disclosed. Upon the application of heat, with or without a catalyst, the ethynyl groups react to provide crosslinking and chain extension to increase the polymer use temperature and improve the polymer solvent resistance. These improved polyesters are potentially useful in packaging, magnetic tapes, capacitors, industrial belting, protective coatings, structural adhesives and composite matrices.

  19. New Acetylene-Terminated Quinoxaline Oligomers

    DTIC Science & Technology

    1982-03-01

    diketone . In this work, we tried other bases, but potassium t-butoxide and lithium t- butoxide gave unsatisfactory results. Synthesis of acetone adduct...the most expensive ingredient. We have previously been able to improve the synthesis of the bisglyoxals needed for these adhesives,2 and are now...general method of synthesis which have been developed is to first condense the quinoxallne oligomer with glyoxal end groups. 2 r ),-CO--CO-Ar--CO--C&O--j

  20. Structural studies on HCN oligomers. [catalysts for prebiotic processes

    NASA Technical Reports Server (NTRS)

    Ferris, J. P.; Edelson, E. H.; Auyeung, J. M.; Joshi, P. C.

    1981-01-01

    NMR spectral studies on the HCN oligomers suggest the presence of carboxamide and urea groupings. The release of CO2, H2O, HCN, CH3CN, HCONH2 and pyridine on pyrolysis is consistent with the presence of these groupings as well as carboxylic acid groups. No basic primary amine groupings could be detected with fluorescamine. Hydrazinolysis of the HCN oligomers releases 10% of the amino acids normally released by acid hydrolysis. The oligomers give a positive biuret test but this is not due to the presence of peptide bonds. There is no conclusive evidence for the presence of peptide bonds in the HCN oligomers. No diglycine was detected on partial hydrolysis of the HCN oligomers at pH 8.5 suggesting that HCN oligomers were not a source of prebiotic peptides.

  1. DNA sequence similarity recognition by hybridization to short oligomers

    DOEpatents

    Milosavljevic, Aleksandar

    1999-01-01

    Methods are disclosed for the comparison of nucleic acid sequences. Data is generated by hybridizing sets of oligomers with target nucleic acids. The data thus generated is manipulated simultaneously with respect to both (i) matching between oligomers and (ii) matching between oligomers and putative reference sequences available in databases. Using data compression methods to manipulate this mutual information, sequences for the target can be constructed.

  2. Copper-Catalyzed Intermolecular Amidation and Imidation of Unactivated Alkanes

    PubMed Central

    2015-01-01

    We report a set of rare copper-catalyzed reactions of alkanes with simple amides, sulfonamides, and imides (i.e., benzamides, tosylamides, carbamates, and phthalimide) to form the corresponding N-alkyl products. The reactions lead to functionalization at secondary C–H bonds over tertiary C–H bonds and even occur at primary C–H bonds. [(phen)Cu(phth)] (1-phth) and [(phen)Cu(phth)2] (1-phth2), which are potential intermediates in the reaction, have been isolated and fully characterized. The stoichiometric reactions of 1-phth and 1-phth2 with alkanes, alkyl radicals, and radical probes were investigated to elucidate the mechanism of the amidation. The catalytic and stoichiometric reactions require both copper and tBuOOtBu for the generation of N-alkyl product. Neither 1-phth nor 1-phth2 reacted with excess cyclohexane at 100 °C without tBuOOtBu. However, the reactions of 1-phth and 1-phth2 with tBuOOtBu afforded N-cyclohexylphthalimide (Cy-phth), N-methylphthalimide, and tert-butoxycyclohexane (Cy-OtBu) in approximate ratios of 70:20:30, respectively. Reactions with radical traps support the intermediacy of a tert-butoxy radical, which forms an alkyl radical intermediate. The intermediacy of an alkyl radical was evidenced by the catalytic reaction of cyclohexane with benzamide in the presence of CBr4, which formed exclusively bromocyclohexane. Furthermore, stoichiometric reactions of [(phen)Cu(phth)2] with tBuOOtBu and (Ph(Me)2CO)2 at 100 °C without cyclohexane afforded N-methylphthalimide (Me-phth) from β-Me scission of the alkoxy radicals to form a methyl radical. Separate reactions of cyclohexane and d12-cyclohexane with benzamide showed that the turnover-limiting step in the catalytic reaction is the C–H cleavage of cyclohexane by a tert-butoxy radical. These mechanistic data imply that the tert-butoxy radical reacts with the C–H bonds of alkanes, and the subsequent alkyl radical combines with 1-phth2 to form the corresponding N-alkyl imide product

  3. Amyloid β-protein oligomers and Alzheimer’s disease

    PubMed Central

    2013-01-01

    The oligomer cascade hypothesis, which states that oligomers are the initiating pathologic agents in Alzheimer’s disease, has all but supplanted the amyloid cascade hypothesis, which suggested that fibers were the key etiologic agents in Alzheimer’s disease. We review here the results of in vivo, in vitro and in silico studies of amyloid β-protein oligomers, and discuss important caveats that should be considered in the evaluation of these results. This article is divided into four sections that mirror the main approaches used in the field to better understand oligomers: (1) attempts to locate and examine oligomers in vivo in situ; that is, without removing these species from their environment; (2) studies involving oligomers extracted from human or animal tissues and the subsequent characterization of their properties ex vivo; (3) studies of oligomers that have been produced synthetically and studied using a reductionist approach in relatively simple in vitro biophysical systems; and (4) computational studies of oligomers in silico. These multiple orthogonal approaches have revealed much about the molecular and cell biology of amyloid β-protein. However, as informative as these approaches have been, the amyloid β-protein oligomer system remains enigmatic. PMID:24289820

  4. Polyetherurethane oligomers with aldehyde groups as additives for lubricating oils

    SciTech Connect

    Nikolaev, V.N.; Abramov, E.G.; Tenyushev, A.I.

    1995-01-01

    Polyetherurethane oligomers with aldehyde groups, which we synthesized from polyoxypropylene diols (molecular weight 500, 1000, 1500, 2000, or 3000) with toluene diisocyanate and salicylaldehyde, are of interest as additives for lubricating oils. The effects of these oligomers on the service properties and physicochemical characteristics of lubricating oils were investigated by methods prreviously described. As the lube base stocks we used castor oil, a polyoxypropylene diol and a polyethoxysiloxane. The oligomers are readily soluble in organic solvents and in the lube base stocks, and their solutions are stable during storage and use. We found that the optimal concentration of oligomers is 5%, providing the best lubricating properties, in particular the best antiwear properties.

  5. Phenylethynyl Terminated Imide (PETI) Composites Made by High Temperature VARTM

    NASA Technical Reports Server (NTRS)

    Chose, Sayata; Cano, Roberto J.; Britton, Sean M.; Watson, Kent A.; Jensen, Brian J.; Connell, John W.

    2010-01-01

    Fabrication of composite structures using vacuum assisted resin transfer molding (VARTM) is generally more affordable than conventional autoclave techniques. Recent efforts have focused on adapting VARTM for the fabrication of high temperature composites. Due to their low melt viscosity and long melt stability, certain phenylethynyl terminated imides (PETI) can be processed into composites using high temperature VARTM (HT-VARTM). However, one of the disadvantages of the current HT-VARTM resin systems has been the high porosity of the resultant composites. For aerospace applications, a void fraction of <2% is desired. In the current study, two PETI resins, LARC. PETI-330 and LARC. PETI-8 have been used to fabricate test specimens using HT-VARTM. The resins were infused into carbon fiber preforms at 260 C and cured between 316 and 371 C. Photomicrographs of the panels were taken and void contents were determined by acid digestion. Modifications to the thermal cycle used in the laminate fabrication have reduced the void content significantly; typically .3% for carbon fiber biaxially woven fabric and less than 2% for carbon fiber uniaxial fabric. Mechanical properties (short beam shear and flexure) of the panels were determined at both room and elevated temperatures. The results of this work are presented herein. This paper is declared a work of the U.S. Government and is not subject to copyright protection in the United States.

  6. High Temperature VARTM of Phenylethynyl Terminated Imides (PETI) Resins

    NASA Technical Reports Server (NTRS)

    Ghose, Sayata; Cano, Roberto J.; Britton, Sean M.; Watson, Kent A.; Jensen, Brian J.; Connell, John W.

    2010-01-01

    Fabrication of composite structures using vacuum assisted resin transfer molding (VARTM) is generally more affordable than conventional autoclave techniques. Recent efforts have focused on adapting VARTM for the fabrication of high temperature composites. Due to their low melt viscosity and long melt stability, certain phenylethynyl terminated imides (PETI) can be processed into composites using high temperature VARTM (HT-VARTM). However, one of the disadvantages of the current HT-VARTM resin systems has been the high porosity of the resultant composites. For aerospace applications a void fraction of less than 2% is desired. In the current study, two PETI resins, LARCTM PETI-330 and LARCTM PETI-8 have been used to fabricate test specimens using HT-VARTM. The resins were infused into carbon fiber preforms at 260 C and cured between 316 C and 371 C. Modifications to the thermal cycle used in the laminate fabrication have reduced the void content significantly (typically < 3%) for carbon fiber biaxially woven fabric. Photomicrographs of the panels were taken and void contents were determined by acid digestion. For carbon fiber uniaxial fabric, void contents of less than 2% have been obtained using both PETI-8 and PETI-330. Mechanical properties of the panels were determined at both room and elevated temperatures. These include short beam shear and flexure tests. The results of this work are presented herein.

  7. Synthesis, Radiolabeling, and Bioevaluation of Bis(Trifluoromethanesulfonyl) Imide.

    PubMed

    Ersöz, Onur Alp; Soylu, Hale Melis; Er, Ozge; Ocakoglu, Kasim; Lambrecht, Fatma Yurt; Yilmaz, Osman

    2015-11-01

    Imidazolium salts have antitumor potential and toxicological effects on various microorganisms. The authors' aim is to synthesize a new imidazolium salt and to assess its pharmacokinetic and antitumor potentials by in vitro and in vivo studies. In this study, bis(trifluoromethanesulfonyl) imide (ITFSI) was synthesized and labeled with (131)I using the iodogen method. The efficiency of radiolabeling was determined with high yield (95.5% ± 3.7%). Pharmacokinetic properties of the compound were investigated in albino Wistar rats using radiolabeled compound. The radiolabeled compound ((131)I-ITFSI) has been stable during a period of 3 hours in human serum. The uptake of (131)I-ITFSI reached maximum in the spleen, liver, and blood at 60 minutes, large intestine and heart at 30 minutes, and ovary at 120 minutes. It is observed that intracellular uptake of the radiolabeled compound is higher in the CaCo-2 (colon adenocarcinoma tumor) cell line than HEK-293 (human epithelial kidney) cell line. In further study, antitumor potential of ITFSI on a colon adenocarcinoma tumor-bearing animal model may be investigated.

  8. Synthesis and photocatalytic activity of poly(triazine imide).

    PubMed

    Ham, Yeilin; Maeda, Kazuhiko; Cha, Dongkyu; Takanabe, Kazuhiro; Domen, Kazunari

    2013-01-01

    Poly(triazine imide) was synthesized with incorporation of Li(+) and Cl(-) ions (PTI/Li(+)Cl(-)) to form a carbon nitride derivative. The synthesis of this material by the temperature-induced condensation of dicyandiamide was examined both in a eutectic mixture of LiCl-KCl and without KCl. On the basis of X-ray diffraction measurements of the synthesized materials, we suggest that a stoichiometric amount of LiCl is necessary to obtain the PTI/Li(+)Cl(-) phase without requiring the presence of KCl at 873 K. PTI/Li(+)Cl(-) with modification by either Pt or CoO(x) as cocatalyst photocatalytically produced H(2) or O(2), respectively, from water. The production of H(2) or O(2) from water indicates that the valence and conduction bands of PTI/Li(+)Cl(-) were properly located to achieve overall water splitting. The treatment of PTI/Li(+)Cl(-) with [Pt(NH(3))(4)](2+) cations enabled the deposition of Pt through ion exchange, demonstrating photocatalytic activity for H(2) evolution, while treatment with [PtCl(6)](2-) anions resulted in no Pt deposition. This was most likely because of the preferential exchange between Li(+) ions and [Pt(NH(3))(4)](2+) cations.

  9. Langley Research Center - Soluble Imide (LaRC-SI)

    NASA Technical Reports Server (NTRS)

    Stang, David

    1995-01-01

    This report is about experimenting and developing uses for the new thermal plastic developed by Dr. Robert Bryant called the 'Langley Research Center - Soluble Imide' (LaRC-SI). The three developments are: the use of the LaRC-SI as a dielectric for thin film sensors, as an adhesive to place diamonds on surfaces to increase thermal conductivity, and as an intermediate layer to allow the placement of metal on aluminum nitride. The LaRC-SI was developed by Dr. Robert G. Bryant, a chemical engineer at NASA Langley Research Center. The unique properties of this material is that it is an amorphous thermoplastic. This means that it can be reformed at elevated temperature and pressures. It can be applied in the form of a spray, spin, dip coating, paint, or spread with a doctors blade. The LaRC-SI has excellent adhesive and dielectric properties. It can also be recycled. Potential applications for this material are resin for mechanical parts such as gears, bearings and valves, advanced composites like carbon fiber, high strength adhesives, thin film circuits, and as a dielectric film for placing electrical components on conductive materials.

  10. Macrocyclic 2,7-Anthrylene Oligomers.

    PubMed

    Yamamoto, Yuta; Wakamatsu, Kan; Iwanaga, Tetsuo; Sato, Hiroyasu; Toyota, Shinji

    2016-05-06

    A macrocyclic compound consisting of six 2,7-anthrylene units was successfully synthesized by Ni-mediated coupling of the corresponding dibromo precursor as a novel π-conjugated compound. This compound was sufficiently stable and soluble in organic solvents due to the presence of mesityl groups. X-ray analysis showed that the molecule had a nonplanar and hexagonal wheel-shaped framework of approximately S6 symmetry. The dynamic process between two S6 structures was observed by using the dynamic NMR technique, the barrier being 58 kJ mol(-1) . The spectroscopic properties of the hexamer were compared with those of analogous linear oligomers.

  11. Anharmonic Vibrational Dynamics of DNA Oligomers

    NASA Astrophysics Data System (ADS)

    Kühn, O.; Došlić, N.; Krishnan, G. M.; Fidder, H.; Heyne, K.

    Combining two-color infared pump-probe spectroscopy and anharmonic force field calculations we characterize the anharmonic coupling patterns between fingerprint modes and the hydrogen-bonded symmetric vNH2 stretching vibration in adenine-thymine dA20-dT20 DNA oligomers. Specifically, it is shown that the anharmonic coupling between the δNH2 bending and the vC4=O4 stretching vibration, both absorbing around 1665 cm-1, can be used to assign the vNH2 fundamental transition at 3215 cm-1 despite the broad background absorption of water.

  12. Cooperative Switching in Nanofibers of Azobenzene Oligomers

    NASA Astrophysics Data System (ADS)

    Weber, Christopher; Liebig, Tobias; Gensler, Manuel; Zykov, Anton; Pithan, Linus; Rabe, Jürgen P.; Hecht, Stefan; Bléger, David; Kowarik, Stefan

    2016-05-01

    Next-generation molecular devices and machines demand the integration of molecular switches into hierarchical assemblies to amplify the response of the system from the molecular level to the meso- or macro-scale. Here, we demonstrate that multi-azobenzene oligomers can assemble to form robust supramolecular nanofibers in which they can be switched repeatedly between the E- and Z-configuration. While in isolated oligomers the azobenzene units undergo reversible photoisomerization independently, in the nanofibers they are coupled via intermolecular interactions and switch cooperatively as evidenced by unusual thermal and kinetic behavior. We find that the photoisomerization rate from the Z-isomer to the E-isomer depends on the fraction of Z-azobenzene in the nanofibers, and is increased by more than a factor of 4 in Z-rich fibers when compared to E-rich fibers. This demonstrates the great potential of coupling individual photochromic units for increasing their quantum efficiency in the solid state with potential relevance for actuation and sensing.

  13. Computing highly specific and mismatch tolerant oligomers efficiently.

    PubMed

    Yamada, Tomoyuki; Morishita, Shinichi

    2003-01-01

    The sequencing of the genomes of a variety of species and the growing databases containing expressed sequence tags (ESTs) and complementary DNAs (cDNAs) facilitate the design of highly specific oligomers for use as genomic markers, PCR primers, or DNA oligo microarrays. The first step in evaluating the specificity of short oligomers of about twenty units in length is to determine the frequencies at which the oligomers occur. However, for oligomers longer than about fifty units this is not efficient, as they usually have a frequency of only 1. A more suitable procedure is to consider the mismatch tolerance of an oligomer, that is, the minimum number of mismatches that allows a given oligomer to match a sub-sequence other than the target sequence anywhere in the genome or the EST database. However, calculating the exact value of mismatch tolerance is computationally costly and impractical. Therefore, we studied the problem of checking whether an oligomer meets the constraint that its mismatch tolerance is no less than a given threshold. Here, we present an efficient dynamic programming algorithm solution that utilizes suffix and height arrays. We demonstrated the effectiveness of this algorithm by efficiently computing a dense list of oligo-markers applicable to the human genome. Experimental results show that the algorithm runs faster than well-known Abrahamson's algorithm by orders of magnitude and is able to enumerate 63% to approximately 79% of qualified oligomers.

  14. Computing highly specific and noise-tolerant oligomers efficiently.

    PubMed

    Yamada, Tomoyuki; Morishita, Shinichi

    2004-03-01

    The sequencing of the genomes of a variety of species and the growing databases containing expressed sequence tags (ESTs) and complementary DNAs (cDNAs) facilitate the design of highly specific oligomers for use as genomic markers, PCR primers, or DNA oligo microarrays. The first step in evaluating the specificity of short oligomers of about 20 units in length is to determine the frequencies at which the oligomers occur. However, for oligomers longer than about fifty units this is not efficient, as they usually have a frequency of only 1. A more suitable procedure is to consider the mismatch tolerance of an oligomer, that is, the minimum number of mismatches that allows a given oligomer to match a substring other than the target sequence anywhere in the genome or the EST database. However, calculating the exact value of mismatch tolerance is computationally costly and impractical. Therefore, we studied the problem of checking whether an oligomer meets the constraint that its mismatch tolerance is no less than a given threshold. Here, we present an efficient dynamic programming algorithm solution that utilizes suffix and height arrays. We demonstrated the effectiveness of this algorithm by efficiently computing a dense list of numerous oligo-markers applicable to the human genome. Experimental results show that the algorithm runs faster than well-known Abrahamson's algorithm by orders of magnitude and is able to enumerate 65% approximately 76% of qualified oligomers.

  15. Design studies of the PWO Forward End-cap calorimeter for P¯ANDA

    NASA Astrophysics Data System (ADS)

    Moeini, H.; Al-Turany, M.; Babai, M.; Biegun, A.; Bondarenko, O.; Götzen, K.; Kavatsyuk, M.; Lindemulder, M. F.; Löhner, H.; Melnychuk, D.; Messchendorp, J. G.; Smit, H. A. J.; Spataro, S.; Veenstra, R.

    2013-11-01

    The P¯ANDA detection system at FAIR, Germany, is designed to study antiproton-proton annihilations, in order to investigate, among others, the realm of charm-meson states and glueballs, which has still much to reveal. The yet unknown properties of this field are to be unraveled through studying QCD phenomena in the non-perturbative regime. The multipurpose P¯ANDA detector will be capable of tracking, calorimetry, and particle identification, and is planned to run at high luminosities providing average reaction rates up to 2 · 107 interactions/s. The envisaged physics program requires measurements of photons and charged particles with excellent energy, position, and time resolutions. The electromagnetic calorimeter (EMC) will serve as one of the basic components of the detector setup and comprises cooled lead-tungstate (PbWO4) crystals. This paper presents the mechanical design of the Forward End-cap calorimeter and analyzes the response of the Forward End-cap calorimeter in conjunction with the full EMC and the complete P¯ANDA detector. The simulation studies are focused on the performance of the planned EMC with respect to the energy and spatial resolution of the reconstructed photons. Results of the Monte Carlo simulations, excluding very low-energy photons, have been validated by data obtained from a prototype calorimeter and shown to fulfil the requirements imposed by the P¯ANDA physics program.

  16. Effects of implant diameter, drug loading and end-capping on praziquantel release from PCL implants.

    PubMed

    Li, Changyan; Cheng, Liang; Zhang, Yaqiong; Guo, Shengrong; Wu, Weiping

    2010-02-15

    Praziquantel (PZQ)-loaded poly(epsilon-caprolactone) (PCL) cylindrical implants were fabricated and characterized. Implant diameter (3, 4 and 8mm), drug loading (25% and 50%), and the end-capping were investigated to evaluate their effects on drug release. The evolution of implants with release time was conducted in terms of implant microstructure, crystallinity, drug content and molecular weight of PCL. The results showed that drug release was fastest for the implant with a diameter of 3mm and slowest for the implant with a diameter of 8mm; drug release from the implant with a drug content of 50% was faster than that from the implant with a drug content of 25%; the release of PZQ from the end-capped implants was slightly slower than that from the corresponding end-uncapped implants. The effect of drug loadings on PZQ release was related with diameter of the implants and the effect was weakened as diameter of the implants increased. The drug release data for all the implants were best fitted with Ritger-Peppas model, therefore Fickian diffusion was the predominant release mechanism. The evolution of implants with release time verified that PZQ was gradually released from the exterior to the interior of the implants.

  17. R&D Studies on Radiation Hard Wavelength Shifting Fiber for CMS Hadronic Endcap Calorimeter Upgrade

    NASA Astrophysics Data System (ADS)

    Neuhaus, John

    2009-11-01

    The Hadronic Endcap (HE) calorimeters of the CMS experiment cover the pseudorapidity range of 1.4 to 3 on both sides of the CMS detector, contributing to superior jet and missing transverse energy resolutions. As the integrated luminosity of the LHC increases, the scintillator tiles used in the CMS Hadronic Endcap calorimeter will lose their efficiency. Here, we propose to replace the scintillator tiles in high radiation area with ``radiation hard'' quartz plates. To increase the light collection efficiency, the generated Cerenkov photons are collected by UV absorbing wavelength shifting (WLS) fibers. Our previous study has shown that quartz plates and plastic wavelength shifting fibers can be used as an effective calorimeter. However there is no radiation hard WLS fiber commercially available. Here we summarize the R&D studies on constructing a radiation hard WLS fiber prototype in University of Iowa CMS Laboratories. The results from the tests performed on quartz fibers treated with p-Terphenyl, as well as the Geant4 simulations of this prototype are presented.

  18. The Common Cryogenic Test Facility for the ATLAS Barrel and End-Cap Toroid Magnets

    SciTech Connect

    Delruelle, N.; Haug, F.; Junker, S.; Passardi, G.; Pengo, R.; Pirotte, O.

    2004-06-23

    The large ATLAS toroidal superconducting magnet made of the Barrel and two End-Caps needs extensive testing at the surface of the individual components prior to their final assembly into the underground cavern of LHC. A cryogenic test facility specifically designed for cooling sequentially the eight coils making the Barrel Toroid (BT) has been fully commissioned and is now ready for final acceptance of these magnets. This facility, originally designed for testing individually the 46 tons BT coils, will be upgraded to allow the acceptance tests of the two End-Caps, each of them having a 160 tons cold mass. The integrated system mainly comprises a 1.2 kW at 4.5 K refrigerator, a 10 kW liquid-nitrogen precooler, two cryostats housing liquid helium centrifugal pumps of respectively 80 g/s and 600 g/s nominal flow and specific instrumentation to measure the thermal performances of the magnets. This paper describes the overall facility with particular emphasis to the cryogenic features adopted to match the specific requirements of the magnets in the various operating scenarios.

  19. Double-chain phospholipid end-capped polyurethanes: Synthesis, characterization and platelet adhesion study

    NASA Astrophysics Data System (ADS)

    Tan, Dongsheng; Zhang, Xiaoqing; Li, Jiehua; Tan, Hong; Fu, Qiang

    2012-01-01

    A novel phospholipid containing double chains and phosphotidylcholine polar head groups, 2-(10-(2-aminoethylamino)-10-oxodecanamido)-3-(decyloxy)-3-oxopropyl phosphorylcholine (ADDPC), was synthesized and characterized. Two kinds of double-chain phospholipid end-capped polyurethanes with different soft segments were prepared. The structure of prepared polyurethanes was characterized by X-ray photoelectron spectroscopic (XPS), attenuated total reflection Fourier transform infrared (ATR-FTIR) spectrometry and atomic force microscope (AFM), which indicated that the double-chain phospholipids enriched onto the top surface of the prepared polyurethane films. The preliminary evaluation of blood compatibility showed that these novel phospholipid end-capped polyurethanes could suppress platelet adhesion and activation effectively. This property did not depend on the chemical structure of polyurethanes. In addition, according to tensile test results, the phospholipid polyurethanes kept good mechanical properties in comparison with original polyurethanes. It is suggested that double-chain phospholipid end-caption has good potential for achieving both hemocompatibility and good mechanical properties simultaneously for polyurethanes.

  20. Addition polyimide adhesives containing various end groups

    NASA Technical Reports Server (NTRS)

    Saint Clair, A. K.; Saint Clair, T. L.

    1982-01-01

    Addition polyimode oligomers have been synthesized from 3,3 prime, 4,4 prime-benzophenone tetracarboxylic acid dianhydride and 3,3 prime-methylenedianiline using a variety of latent crosslinking groups as end-caps. The nominal 1300 molecular weight imide prepolymers were isolated and characterized for solubility in amide, chlorinated and ether solvents, melt-flow and cure properties, glass transition temperature, and thermal stability on heating in an air atmosphere. Adhesive strengths of the polyimides were obtained both at ambient and elevated temperatures before and after aging at 232 C. Properties of the novel addition polyimides were compared to a known nadic end-capped adhesive, LARC-13.

  1. Origin and diversification of a metabolic cycle in oligomer world.

    PubMed

    Nishio, Tomoaki; Narikiyo, Osamu

    2013-02-01

    Based on the oligomer-world hypothesis we propose an abstract model where the molecular recognition among oligomers is described in the shape space. The origin of life in the oligomer world is regarded as the establishment of a metabolic cycle in a primitive cell. The cycle is sustained by the molecular recognition. If an original cell acquires the ability of the replication of oligomers, the relationship among oligomers changes due to the poor fidelity of the replication. This change leads to the diversification of metabolic cycles. The selection among diverse cycles is the basis of the evolution. The evolvability is one of the essential characters of life. We demonstrate the origin and diversification of the metabolic cycle by the computer simulation of our model. Such a simulation is expected to be the simplified demonstration of what actually occurred in the primordial soup. Our model describes an analog era preceding the digital era based on the genetic code.

  2. Non-aqueous dispersion coatings based on crystalline oligomers

    SciTech Connect

    Jones, F.N.

    1993-12-31

    Amorphous oligomers and polymers are generally used in coatings; crystalline ones are avoided because of the difficulty of achieving homogeneous, defect-free films. However, dispersions of crystalline oligomers offer potential advantages of stability, useful application rheology, and excellent film properties. The authors describe non-aqueous dispersions of mixtures of crystalline and amorphous oligomers. An example is a dispersion of mixtures of crystalline (at ambient temperature) hydroxyl-functional oligomer of terephthalic acid and 1,6-hexanediol mixed with an amorphous hydroxyl-functional oligomer of terephthalic acid and glycidyl neodecanote. Microscopy, WAXD and DSC indicate that the dispersion particles are crystalline and have a diameter of 5 to 20 {mu}m. The dispersions are stable and are thixotropic. Coatings formulated with melamine and polyisocyanate resin crosslinkers form glossy, transparent film with excellent mechanical properties.

  3. Atomic View of a Toxic Amyloid Small Oligomer

    SciTech Connect

    Laganowsky, Arthur; Liu, Cong; Sawaya, Michael R.; Whitelegge, Julian P.; Park, Jiyong; Zhao, Minglei; Pensalfini, Anna; Soriaga, Angela B.; Landau, Meytal; Teng, Poh K.; Cascio, Duilio; Glabe, Charles; Eisenberg, David

    2012-04-30

    Amyloid diseases, including Alzheimer's, Parkinson's, and the prion conditions, are each associated with a particular protein in fibrillar form. These amyloid fibrils were long suspected to be the disease agents, but evidence suggests that smaller, often transient and polymorphic oligomers are the toxic entities. Here, we identify a segment of the amyloid-forming protein {alpha}{beta} crystallin, which forms an oligomeric complex exhibiting properties of other amyloid oligomers: {beta}-sheet-rich structure, cytotoxicity, and recognition by an oligomer-specific antibody. The x-ray-derived atomic structure of the oligomer reveals a cylindrical barrel, formed from six antiparallel protein strands, that we term a cylindrin. The cylindrin structure is compatible with a sequence segment from the {beta}-amyloid protein of Alzheimer's disease. Cylindrins offer models for the hitherto elusive structures of amyloid oligomers.

  4. Glucosamine oligomers: 4. Solid state-crystallization and sustained dissolution.

    PubMed

    Domard, A; Cartier, N

    1992-04-01

    When glucosamine oligomers are stored in the solid state they undergo a process of crystallization. The extent to which this occurs depends on whether the samples are isolated in the -NH3+ or -NH2 form, on the storage time, and on the degree of polymerization of the isolated oligomer. The allomorph obtained by this process seems to correspond to the so-called 'tendon-chitosan'. Dissolution of such aged oligomer samples gives rise to a process of dissociation of the associated chains in the crystal, leading to the establishment of a pseudo-equilibrium between single and associated oligomer chains and hence the simultaneous presence of the 'monomeric', 'dimeric', 'trimeric', etc., forms of the oligomer. The phenomenon cannot be attributed to a process of aggregation in solution. The effects of various parameters on this behaviour have been investigated.

  5. Exploration of an imide capture/N,N-acyl shift sequence for asparagine native peptide bond formation.

    PubMed

    Mhidia, Reda; Boll, Emmanuelle; Fécourt, Fabien; Ermolenko, Mikhail; Ollivier, Nathalie; Sasaki, Kaname; Crich, David; Delpech, Bernard; Melnyk, Oleg

    2013-06-15

    Imide capture of a C-terminal peptidylazide with a side-chain thioacid derivative of an N-terminally protected aspartyl peptide leads to the formation of an imide bond bringing the two peptide ends into close proximity. Unmasking of the N(α) protecting group and intramolecular acyl migration results in the formation of a native peptide bond to asparagine.

  6. High performance asymmetrical push-pull small molecules end-capped with cyanophenyl for solution-processed solar cells.

    PubMed

    Gao, Hang; Li, Yanqin; Wang, Lihui; Ji, Changyan; Wang, Yue; Tian, Wenjing; Yang, Xichuan; Yin, Lunxiang

    2014-09-14

    Two novel asymmetrical push-pull small molecules have been synthesized successfully, consisting of triphenylamine and diketopyrrolopyrrole as a fundamental dipolar D-π-A structure with ethynylbenzene as the π-bridge. TPATDPPCN end-capped with cyanophenyl exhibits a low optical band gap of 1.65 eV, and an impressive PCE of 5.94% has been achieved.

  7. Soluble Aβ oligomer production and toxicity

    PubMed Central

    Larson, Megan E.; Lesné, Sylvain E.

    2011-01-01

    For nearly 100 years following the first description of this neurological disorder by Dr. Alois Alzheimer, amyloid plaques and neurofibrillary tangles have been hypothesized to cause neuronal loss. With evidence that the extent of insoluble, deposited amyloid poorly correlated with cognitive impairment, research efforts focused on soluble forms of Aβ, also referred as Aβ oligomers. Following a decade of studies, soluble oligomeric forms of Aβ are now believed to induce the deleterious cascade(s) involved in the pathophysiology of Alzheimer’s disease. In this review, we will discuss our current understanding about endogenous oligomeric Aβ production, their relative toxicity in vivo and in vitro, and explore the potential future directions needed for the field. PMID:22121920

  8. Complementary inverter using high mobility air-stable perylene di-imide derivatives

    NASA Astrophysics Data System (ADS)

    Ling, Mang-mang; Bao, Zhenan; Erk, Peter; Koenemann, Martin; Gomez, Marcos

    2007-02-01

    The authors report the fabrication and electrical characterization of organic complementary inverters using pentacene as p-type material and our previously reported air-stable perylene di-imide derivatives tetrachloro-perylene-tetracarboxyldi-imide (TC-PTCDI) and N ,N'-bis(2-phenylethyl)perylene-3,4:9:10-bis-(dicarboximide) (BPE-PTCDI) as n-type materials. Both p- and n-type thin film transistors were integrated onto the same substrate using a top contact configuration. The corresponding inverters show good performance with gains about 12 and 10 for TC-PTCDI and BPE-PTCDI inverters, respectively.

  9. Structural and functional properties of prefibrillar α-synuclein oligomers.

    PubMed

    Pieri, Laura; Madiona, Karine; Melki, Ronald

    2016-04-14

    The deposition of fibrillar alpha-synuclein (α-syn) within inclusions (Lewy bodies and Lewy neurites) in neurons and glial cells is a hallmark of synucleinopathies. α-syn populates a variety of assemblies ranging from prefibrillar oligomeric species to fibrils whose specific contribution to neurodegeneration is still unclear. Here, we compare the specific structural and biological properties of distinct soluble prefibrillar α-syn oligomers formed either spontaneously or in the presence of dopamine and glutaraldehyde. We show that both on-fibrillar assembly pathway and distinct dopamine-mediated and glutaraldehyde-cross-linked α-syn oligomers are only slightly effective in perturbing cell membrane integrity and inducing cytotoxicity, while mature fibrils exhibit the highest toxicity. In contrast to low-molecular weight and unstable oligomers, large stable α-syn oligomers seed the aggregation of soluble α-syn within reporter cells although to a lesser extent than mature α-syn fibrils. These oligomers appear elongated in shape. Our findings suggest that α-syn oligomers represent a continuum of species ranging from unstable low molecular weight particles to mature fibrils via stable elongated oligomers composed of more than 15 α-syn monomers that possess seeding capacity.

  10. Toxic species in amyloid disorders: Oligomers or mature fibrils

    PubMed Central

    Verma, Meenakshi; Vats, Abhishek; Taneja, Vibha

    2015-01-01

    Protein aggregation is the hallmark of several neurodegenerative disorders. These protein aggregation (fibrillization) disorders are also known as amyloid disorders. The mechanism of protein aggregation involves conformation switch of the native protein, oligomer formation leading to protofibrils and finally mature fibrils. Mature fibrils have long been considered as the cause of disease pathogenesis; however, recent evidences suggest oligomeric intermediates formed during fibrillization to be toxic. In this review, we have tried to address the ongoing debate for these toxic amyloid species. We did an extensive literature search and collated information from Pubmed (http://www.ncbi.nlm.nih.gov) and Google search using various permutations and combinations of the following keywords: Neurodegeneration, amyloid disorders, protein aggregation, fibrils, oligomers, toxicity, Alzheimer's Disease, Parkinson's Disease. We describe different instances showing the toxicity of mature fibrils as well as oligomers in Alzheimer's Disease and Parkinson's Disease. Distinct structural framework and morphology of amyloid oligomers suggests difference in toxic effect between oligomers and fibrils. We highlight the difference in structure and proposed toxicity pathways for fibrils and oligomers. We also highlight the evidences indicating that intermediary oligomeric species can act as potential diagnostic biomarker. Since the formation of these toxic species follow a common structural switch among various amyloid disorders, the protein aggregation events can be targeted for developing broad-range therapeutics. The therapeutic trials based on the understanding of different protein conformers (monomers, oligomers, protofibrils and fibrils) in amyloid cascade are also described. PMID:26019408

  11. A Generic Method for Design of Oligomer-Specific Antibodies

    PubMed Central

    Brännström, Kristoffer; Lindhagen-Persson, Malin; Gharibyan, Anna L.; Iakovleva, Irina; Vestling, Monika; Sellin, Mikael E.; Brännström, Thomas; Morozova-Roche, Ludmilla; Forsgren, Lars; Olofsson, Anders

    2014-01-01

    Antibodies that preferentially and specifically target pathological oligomeric protein and peptide assemblies, as opposed to their monomeric and amyloid counterparts, provide therapeutic and diagnostic opportunities for protein misfolding diseases. Unfortunately, the molecular properties associated with oligomer-specific antibodies are not well understood, and this limits targeted design and development. We present here a generic method that enables the design and optimisation of oligomer-specific antibodies. The method takes a two-step approach where discrimination between oligomers and fibrils is first accomplished through identification of cryptic epitopes exclusively buried within the structure of the fibrillar form. The second step discriminates between monomers and oligomers based on differences in avidity. We show here that a simple divalent mode of interaction, as within e.g. the IgG isotype, can increase the binding strength of the antibody up to 1500 times compared to its monovalent counterpart. We expose how the ability to bind oligomers is affected by the monovalent affinity and the turnover rate of the binding and, importantly, also how oligomer specificity is only valid within a specific concentration range. We provide an example of the method by creating and characterising a spectrum of different monoclonal antibodies against both the Aβ peptide and α-synuclein that are associated with Alzheimer's and Parkinson's diseases, respectively. The approach is however generic, does not require identification of oligomer-specific architectures, and is, in essence, applicable to all polypeptides that form oligomeric and fibrillar assemblies. PMID:24618582

  12. Structural and functional properties of prefibrillar α-synuclein oligomers

    PubMed Central

    Pieri, Laura; Madiona, Karine; Melki, Ronald

    2016-01-01

    The deposition of fibrillar alpha-synuclein (α-syn) within inclusions (Lewy bodies and Lewy neurites) in neurons and glial cells is a hallmark of synucleinopathies. α-syn populates a variety of assemblies ranging from prefibrillar oligomeric species to fibrils whose specific contribution to neurodegeneration is still unclear. Here, we compare the specific structural and biological properties of distinct soluble prefibrillar α-syn oligomers formed either spontaneously or in the presence of dopamine and glutaraldehyde. We show that both on-fibrillar assembly pathway and distinct dopamine-mediated and glutaraldehyde-cross-linked α-syn oligomers are only slightly effective in perturbing cell membrane integrity and inducing cytotoxicity, while mature fibrils exhibit the highest toxicity. In contrast to low-molecular weight and unstable oligomers, large stable α-syn oligomers seed the aggregation of soluble α-syn within reporter cells although to a lesser extent than mature α-syn fibrils. These oligomers appear elongated in shape. Our findings suggest that α-syn oligomers represent a continuum of species ranging from unstable low molecular weight particles to mature fibrils via stable elongated oligomers composed of more than 15 α-syn monomers that possess seeding capacity. PMID:27075649

  13. Elucidating molecular mass and shape of a neurotoxic Aβ oligomer.

    PubMed

    Sebollela, Adriano; Mustata, Gina-Mirela; Luo, Kevin; Velasco, Pauline T; Viola, Kirsten L; Cline, Erika N; Shekhawat, Gajendra S; Wilcox, Kyle C; Dravid, Vinayak P; Klein, William L

    2014-12-17

    Alzheimer's disease (AD), the most prevalent type of dementia, has been associated with the accumulation of amyloid β oligomers (AβOs) in the central nervous system. AβOs vary widely in size, ranging from dimers to larger than 100 kDa. Evidence indicates that not all oligomers are toxic, and there is yet no consensus on the size of the actual toxic oligomer. Here we used NU4, a conformation-dependent anti-AβO monoclonal antibody, to investigate size and shape of a toxic AβO assembly. By using size-exclusion chromatography and immuno-based detection, we isolated an AβO-NU4 complex amenable for biochemical and morphological studies. The apparent molecular mass of the NU4-targeted oligomer was 80 kDa. Atomic force microscopy imaging of the AβO-NU4 complex showed a size distribution centered at 5.37 nm, an increment of 1.5 nm compared to the size of AβOs (3.85 nm). This increment was compatible with the size of NU4 (1.3 nm), suggesting a 1:1 oligomer to NU4 ratio. NU4-reactive oligomers extracted from AD human brain concentrated in a molecular mass range similar to that found for in vitro prepared oligomers, supporting the relevance of the species herein studied. These results represent an important step toward understanding the connection between AβO size and toxicity.

  14. Direct Electrodeposition of UO2 from Uranyl Bis(trifluoromethanesulfonyl)imide Dissolved in 1-Ethyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)imide Room Temperature Ionic Liquid System

    DOE PAGES

    Freiderich, John W.; Wanigasekara, Eranda P.; Sun, Xiao-Guang; ...

    2013-11-11

    Our study demonstrates a direct electrodeposition of UO2 at a Pt cathode from a solution of uranyl bis(trifluoromethanesulfonyl)imide [UO2(NTf2)2)] in a bulk room-temperature ionic liquid (RTIL), 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMIM+NTf2–). Cyclic voltammetry (CV) studies revealed two reduction waves corresponding to the conversion of uranium(VI) to uranium(IV), and a mechanism for the overall electroreduction is proposed. A controlled-potential experiment was performed, holding the reduction potential at–1.0 V for 24 h to obtain a brown-black deposit of UO2 on the Pt cathode. The Faradaic efficiency of the reduction process was determined to be >80%. The UO2deposit was characterized by powder X-ray diffraction (XRD)more » and X-ray photoelectron spectroscopy (XPS).« less

  15. Pramipexole prevents neurotoxicity induced by oligomers of beta-amyloid.

    PubMed

    Uberti, Daniela; Bianchi, Irene; Olivari, Luca; Ferrari-Toninelli, Giulia; Canonico, PierLuigi; Memo, Maurizio

    2007-08-27

    Here we demonstrate that pramipexole, an antiparkinsonian dopamine receptor agonist drug, exerts neuroprotective effects against beta-amyloid neurotoxicity. Using a specific protocol to test individually oligomers, fibrils, or unaggregated amyloid beta-peptide, we found pramipexole able to protect cells against oligomers and fibrils. Unaggregated amyloid beta-peptide was found unable to cause cell death. Fibrils and oligomers were also found to produce elevated amount of free radicals, and this effect was prevented by pramipexole. We propose pramipexole may become in the future a coadjuvant in the treatment of neuropathologies, besides Parkinson's disease, where amyloid beta-peptide-mediated oxidative injury exerts a relevant role.

  16. Performance of the Prototype Readout System for the CMS Endcap Hadron Calorimeter Upgrade

    NASA Astrophysics Data System (ADS)

    Chaverin, Nate; Dittmann, Jay; Hatakeyama, Kenichi; Pastika, Nathaniel; CMS Collaboration

    2016-03-01

    The Compact Muon Solenoid (CMS) experiment at the CERN Large Hadron Collider (LHC) will upgrade the photodetectors and readout systems of the endcap hadron calorimeter during the technical stop scheduled for late 2016 and early 2017. A major milestone for this project was a highly successful testbeam run at CERN in August 2015. The testbeam run served as a full integration test of the electronics, allowing a study of the response of the preproduction electronics to the true detector light profile, as well as a test of the light yield of various new plastic scintillator materials. We present implications for the performance of the hadron calorimeter front-end electronics based on testbeam data, and we report on the production status of various components of the system in preparation for the upgrade.

  17. Stability of the Gains of the STAR Endcap Calorimeter from 2006 to 2011

    NASA Astrophysics Data System (ADS)

    Kutz, Kayla

    2012-10-01

    The Solenoid Tracker at RHIC (STAR) experiment, based at Brookhaven National Laboratory's Relativistic Heavy Ion Collider (RHIC), uses polarized-proton collisions to investigate sea quark and gluon contributions to the known proton spin. The STAR detector's Endcap Electromagnetic Calorimeter (EEMC) measures the energy of particles produced by those collisions using a lead-scintillator sampling calorimeter, consisting of several layers that include pre-shower, shower maximum, tower, and post-shower detectors. In these detectors, the energy gains, which convert a measured pulse into an energy deposition, have been determined using data taken from the years, 2006, 2009 and 2011. Changes in the gains over time may result from known high voltage changes or deterioration of the detector, such as from radiation damage. A comparison of the gains from the three years will be presented.

  18. Inclusive 0̂ Production in Polarized pp Collisions using the STAR Endcap Calorimeter

    NASA Astrophysics Data System (ADS)

    Webb, Jason

    2007-10-01

    The two-spin helicity asymmetry for inclusive 0̂ production in polarized pp collisions can provide constraints on the gluon contribution to the spin of the proton with sensitivity comparable to that attainable with full jet reconstruction [1]. In 2006, the STAR experiment accumulated 6 pb-1 of data with beams longitudinally polarized (P 60%) at the Relativistic Heavy Ion Collider. Measurements of ALL(0̂) in the range 1 < η< 2 provide information about a different mix of partonic subprocesses and are subject to different experimental uncertainties than mid-rapidity jet measurements, providing an important cross check. Status of the analysis of ALL(0̂) measured using the STAR Endcap Calorimeter [2] is discussed. [1] B. Jager, M. Stratmann and W. Vogelsang, Phys. Rev. D 70, 034010 (2004) [arXiv:hep-ph/0404057]. [2] K. H. Ackermann et al. [STAR Collaboration], Nucl. Instrum. Meth. A 499, 624 (2003).

  19. ATLAS Liquid Argon Endcap Calorimeter R&D for sLHC

    NASA Astrophysics Data System (ADS)

    Schacht, P.

    2010-04-01

    The performance of the ATLAS liquid argon endcap has been studied for luminosities as expected for the operation at sLHC. The increase of integrated luminosity by a factor of ten has serious consequences for the signal reconstruction, radiation hardness requirements and operations of the forward liquid argon calorimeters. The response has been studied with small modules of the type as built for ATLAS in a very high intensity beam at IHEP/Protvino. The highest intensity obtained was well above the level of energy impact expected for ATLAS at sLHC. The signal processing of the ATLAS Hadronic Endcap Calorimeter employs the concept of 'active pads' which keep the detector capacities at the input of the amplifiers small and thereby achieves a fast rise time of the signal. This concept is realized using highly integrated amplifier and summing chips in GaAs technology. With an increase of luminosity by a factor of ten the safety factor for the radiation hardness is essentially eliminated. Therefore new, more radiation hard technologies have been studied: SiGe bipolar, Si CMOS FET and GaAs FET transistors have been irradiated with neutrons up to an integrated fluence of 2.2 × 1016n/cm2. All technologies exceed the limit required for the radiation hardness for the operation at sLHC of 2 × 1015n/cm2. The temperature dependence of the gain has been studied as well. Here the bipolar technologies - in contrast to CMOS - need an adjustment of the operation point when going from room temperature to liquid nitrogen temperature.

  20. Oligomer formation in the radiation-induced polymerization of styrene

    NASA Astrophysics Data System (ADS)

    Harayma, Hiroshi; Al-Sheikhly, Mohamad; Silverman, Joseph

    2003-12-01

    Analyses of the oligomers formed in radiation-induced polymerization of purified styrene were performed. The principal dimeric products were cis- and trans-diphenyl-cyclobutane with a relatively small amount of 1-phenyltetralin; the trimeric products were the optical isomers of 1-phenyl-4-[1'-phenylethyl-(1')]-tetralin in gamma-ray and 60 MeV proton irradiation. Oligomer formation increased with increasing dose, but more gradually than the linear formation of high polymer with dose. The yield was 0.25-3.1 μmol/J at low doses and decreased to an asymptotic value of 0.15 at higher doses. It appears that oligomers act as chain transfer agents during the polymerization reaction which would account for the observed decrease in molecular weight of the high polymer with increase in dose. Although the thermal and radiation-induced polymerization of styrene have different initiation steps, the oligomers produced by both reactions are similar in composition.

  1. Biomimetic peptoid oligomers as dual-action antifreeze agents

    PubMed Central

    Huang, Mia L.; Ehre, David; Jiang, Qi; Hu, Chunhua; Kirshenbaum, Kent; Ward, Michael D.

    2012-01-01

    The ability of natural peptides and proteins to influence the formation of inorganic crystalline materials has prompted the design of synthetic compounds for the regulation of crystal growth, including the freezing of water and growth of ice crystals. Despite their versatility and ease of structural modification, peptidomimetic oligomers have not yet been explored extensively as crystallization modulators. This report describes a library of synthetic N-substituted glycine peptoid oligomers that possess “dual-action” antifreeze activity as exemplified by ice crystal growth inhibition concomitant with melting temperature reduction. We investigated the structural features responsible for these phenomena and observed that peptoid antifreeze activities depend both on oligomer backbone structure and side chain chemical composition. These studies reveal the capability of peptoids to act as ice crystallization regulators, enabling the discovery of a unique and diverse family of synthetic oligomers with potential as antifreeze agents in food production and biomedicine. PMID:23169638

  2. Synthesis of 1H-Indazoles from Imidates and Nitrosobenzenes via Synergistic Rhodium/Copper Catalysis.

    PubMed

    Wang, Qiang; Li, Xingwei

    2016-05-06

    Nitrosobenzenes have been used as a convenient aminating reagent for the efficient synthesis of 1H-indazoles via rhodium and copper catalyzed C-H activation and C-N/N-N coupling. The reaction occurred under redox-neutral conditions with high efficiency and functional group tolerance. Moreover, a rhodacyclic imidate complex has been identified as a key intermediate.

  3. Increased effect of IMiDs by addition of cytokine-induced killer cells in multiple myeloma.

    PubMed

    Bullok, Katharina F; Sippel, Christoph; Schmidt-Wolf, Ingo G H

    2016-12-01

    Immunomodulatory drugs (IMiDs), such as thalidomide, lenalidomide and pomalidomide, represent the basic principle of multiple myeloma treatment. However, the development of resistance is a limiting factor. Over the last years, the efficient application of cytokine-induced killer (CIK) cells has been reported as an alternative strategy to treat hematological neoplasms. In this study, we tested for a potential synergistic effect by combining the IMiDs thalidomide, lenalidomide and pomalidomide with CIK cells in different myeloma cell lines in vitro. Myeloma cells tested with CIK cells were significantly reduced. In the combination, myeloma cells were significantly reduced compared with cells only tested with IMiDs but not to the cells tested with CIK cells. Otherwise, the number of CIK cells was significantly reduced when treated with IMiDs. Because IMiDs are active in patients with myeloma, these results lead to the expectation that combination of IMiDs and CIK cells achieve better results in the treatment of multiple myeloma compared with the single use of IMiDs. Therefore, further examinations in an in vivo setting are necessary to have a closer look on the cellular interactions. Copyright © 2015 John Wiley & Sons, Ltd.

  4. Wholly Aromatic Ether-imides. Potential Materials for n-Type Semiconductors

    NASA Technical Reports Server (NTRS)

    Dingemans, Theo J.; St.Clair, Terry L.; Samulski, Edward T.; Bushnell, Dennis M. (Technical Monitor)

    2002-01-01

    We report on the synthesis and characterization of a novel series low-molar-mass ether-imide rod-shaped model compounds. All ether-imides were obtained by terminating the appropriate rigid core dianhydride, i.e. pyromellitic dianhydride (PMDA), 1,4,5,8-naphthalenetetracarboxylic dianhydride (NDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), and 3,3,4,4'-oxydiphthalic dianhydride (ODPA) with three flexible aryl-ether tails of different chain length. The mono-functional aryl-ether amines, i.e. 4-(3-phenoxy-phenoxy)-phenylamine (2) and 4-(3-phenoxy-3-phenoxy-phenoxy)-phenylamine (4), were synthesized using standard fluoro-displacement and Ullmann condensation techniques. The corresponding ether-imide model compounds were obtained in high yields using a one-step solution imidization procedure. Increasing the number of meta-substituted aryl-ether units reduces the melt transition temperatures and at the same time it increases the solubility of the model compounds. Most model compounds are crystalline solids and form isotropic melts upon heating. 2,7-Bis-(-4-phenoxy-phenyl)-benzo[Imn][3,8]phenanthroline1,3,6,8-tetraone (NDA-n0), however, displays a smectic A (SA) when cooled from the isotropic phase, followed by what appears to be either a highly ordered smectic phase or a, columnar phase. This is the first example, known to date, in which a mesophase is detected in a wholly aromatic ether-imide compound. For all compounds we present spectroscopic data and X-ray diffraction data. Cyclic voltammetry was used to determine the redox behavior and pertinent energy levels of the model compounds.

  5. Subdiffusion of proteins and oligomers on membranes

    NASA Astrophysics Data System (ADS)

    Lepzelter, David; Zaman, Muhammad

    2012-11-01

    Diffusion of proteins on lipid membranes plays a central role in cell signaling processes. From a mathematical perspective, most membrane diffusion processes are explained by the Saffman-Delbrück theory. However, recent studies have suggested a major limitation in the theoretical framework, the lack of complexity in the modeled lipid membrane. Lipid domains (sometimes termed membrane rafts) are known to slow protein diffusion, but there have been no quantitative theoretical examinations of how much diffusion is slowed in a general case. We provide an overall theoretical framework for confined-domain ("corralled") diffusion. Further, there have been multiple apparent contradictions of the basic conclusions of Saffman and Delbrück, each involving cases in which a single protein or an oligomer has multiple transmembrane regions passing through a lipid phase barrier. We present a set of corrections to the Saffman-Delbrück theory to account for these experimental observations. Our corrections are able to provide a quantitative explanation of numerous cellular signaling processes that have been considered beyond the scope of the Saffman-Delbrück theory, and may be extendable to other forms of subdiffusion.

  6. Functional Diversity of Isoamylase Oligomers: The ISA1 Homo-Oligomer Is Essential for Amylopectin Biosynthesis in Rice Endosperm1[W][OA

    PubMed Central

    Utsumi, Yoshinori; Utsumi, Chikako; Sawada, Takayuki; Fujita, Naoko; Nakamura, Yasunori

    2011-01-01

    Rice (Oryza sativa) endosperm has two isoamylase (ISA) oligomers, ISA1 homo-oligomer and ISA1-ISA2 hetero-oligomer. To examine their contribution to starch synthesis, expression of the ISA1 or ISA2 gene was differently regulated in various transgenic plants. Although suppression of ISA2 gene expression caused the endosperm to have only the homo-oligomer, no significant effects were detected on the starch phenotypes. In contrast, ISA2 overexpression led to endosperm having only the hetero-oligomer, and starch synthesis in the endosperm was drastically impaired, both quantitatively and qualitatively, because the starch was devoid of typical starch features, such as thermal and x-ray diffraction properties, and water-soluble highly branched maltodextrins were accumulated. In the ISA2 overexpressed line, about 60% to 70% of the ISA1-ISA2 hetero-oligomer was bound to starch, while the ISA homo- and hetero-oligomers from the wild type were mostly present in the soluble form at the early milking stage of the endosperm. Detailed analysis of the relative amounts of homo- and hetero-oligomers in various lines also led us to the conclusion that the ISA1 homo-oligomer is essential, but not the ISA1-ISA2 oligomer, for starch production in rice endosperm. The relative amounts of ISA1 and ISA2 proteins were shown to determine the ratio of both oligomers and the stoichiometry of both ISAs in the hetero-oligomer. It was noted when compared with the homo-oligomer that all the hetero-oligomers from rice endosperm and leaf and potato (Solanum tuberosum) tuber were much more stable at 40°C. This study provides substantial data on the structural and functional diversity of ISA oligomers between plant tissues and species. PMID:21436381

  7. Column selectivity in reversed-phase liquid chromatography. VI. Columns with embedded or end-capping polar groups.

    PubMed

    Wilson, N S; Gilroy, J; Dolan, J W; Snyder, L R

    2004-02-13

    A previous model of column selectivity for reversed-phase liquid chromatography (RP-LC) has been applied to an additional 21 columns with embedded or end-capping polar groups (EPGs). Embedded-polar-group columns exhibit a significantly different selectivity vs. non-EPG, type-B columns, generally showing preferential retention of hydrogen-bond donors, as well as decreased retention for hydrogen-bond acceptors or ionized bases. EPG-columns are also generally less hydrophobic (more polar) than are non-EPG-columns. Interestingly, columns with polar end-capping tend to more closely resemble non-EPG columns, suggesting that the polar group has less effect on column selectivity when used to end-cap the column versus the case of an embedded polar group. Column selectivity data reported here for EPG-columns can be combined with previously reported values for non-EPG columns to provide a database of 154 different columns. This enables a comparison of any two of these columns in terms of selectivity. However, comparisons that involve EPG columns are more approximate.

  8. DC Potentials Applied to an End-cap Electrode of a 3-D Ion Trap for Enhanced MSn Functionality

    PubMed Central

    Prentice, Boone M.; Xu, Wei; Ouyang, Zheng; McLuckey, Scott A.

    2010-01-01

    The effects of the application of various DC magnitudes and polarities to an end-cap of a 3-D quadrupole ion trap throughout a mass spectrometry experiment were investigated. Application of a monopolar DC field was achieved by applying a DC potential to the exit end-cap electrode, while maintaining the entrance end-cap electrode at ground potential. Control over the monopolar DC magnitude and polarity during time periods associated with ion accumulation, mass analysis, ion isolation, ion/ion reaction, and ion activation can have various desirable effects. Included amongst these are increased ion capture efficiency, increased ion ejection efficiency during mass analysis, effective isolation of ions using lower AC resonance ejection amplitudes, improved temporal control of the overlap of oppositely charged ion populations, and the performance of “broad-band” collision induced dissociation (CID). These results suggest general means to improve the performance of the 3-D ion trap in a variety of mass spectrometry and tandem mass spectrometry experiments. PMID:21927573

  9. Key Role of End-Capping Groups in Optoelectronic Properties of Poly-p-phenylene Cation Radicals

    PubMed Central

    2015-01-01

    Poly-p-phenylenes (PPs) are prototype systems for understanding the charge transport in π-conjugated polymers. In a combined computational and experimental study, we demonstrate that the smooth evolution of redox and optoelectronic properties of PP cation radicals toward the polymeric limit can be significantly altered by electron-donating iso-alkyl and iso-alkoxy end-capping groups. A multiparabolic model (MPM) developed and validated here rationalizes this unexpected effect by interplay of the two modes of hole stabilization: due to the framework of equivalent p-phenylene units and due to the electron-donating end-capping groups. A symmetric, bell-shaped hole in unsubstituted PPs becomes either slightly skewed and shifted toward an end of the molecule in iso-alkyl-capped PPs or highly deformed and concentrated on a terminal unit in PPs with strongly electron-donating iso-alkoxy capping groups. The MPM shows that the observed linear 1/n evolution of the PP cation radical properties toward the polymer limit originates from the hole stabilization due to the growing chain of p-phenylene units, while shifting of the hole toward electron-donating end-capping groups leads to early breakdown of these 1/n dependencies. These insights, along with the readily applicable and flexible multistate parabolic model, can guide studies of complex donor–spacer–acceptor systems and doped molecular wires to aid the design of the next generation materials for long-range charge transport and photovoltaic applications. PMID:25264475

  10. Conductivity and spectroscopic investigation of bis(trifluoromethanesulfonyl)imide solution in ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide.

    PubMed

    Yu, Lei; Pizio, Benjamin S; Vaden, Timothy D

    2012-06-07

    Protic ionic liquids (PILs) are promising alternatives to water for swelling Nafion as a fuel cell proton exchange membrane (PEM). PILs can significantly improve the high-temperature performance of a PEM. The proton dissociation and solvation mechanisms in a PIL, which are keys to understanding the proton transportation and conductivity, have not been fully explored. In this paper, we used FTIR, Raman, and electronic spectroscopy with computational simulation techniques to explore the spectroscopic properties of bis(trifluoromethanesulfonyl)imide (HTFSI) solutions in 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMITFSI) ionic liquid at concentrations from ∼0.1 to as high as ∼1.0 M. Solution conductivities were measured at room temperature and elevated temperatures up to ∼65 °C. The solution structure and properties depend on the concentration of HTFSI. At lower concentration, around 0.1 M, the HTFSI solution has higher conductivity than pure BMITFSI. However, the conductivity decreases when the concentration increases from 0.1 to 1.0 M. Temperature-dependent conductivities followed the Vogel-Fulcher-Tamman equation at all concentrations. Conductivity and spectroscopy results elucidate the complicated ionization and solvation mechanism of HTFSI in BMITFSI solutions. Raman spectroscopy and density functional theory (DFT) calculations are consistent with the complete ionization of HTFSI to generate solvated H(+) at low concentrations. FTIR, Raman, and electronic spectroscopic results as well as DFT computational simulation indicated that when the concentration is as high as 1.0 M, a significant amount of TFSI(-) is protonated, most likely at the imide nitrogen.

  11. ortho-Phenylene oligomers with terminal push-pull substitution.

    PubMed

    He, Jian; Mathew, Sanyo M; Cornett, Sarah D; Grundy, Stephan C; Hartley, C Scott

    2012-05-07

    ortho-Phenylenes are an emerging class of helical oligomers and polymers. We have synthesized a series of push-pull-substituted o-phenylene oligomers (dimethylamino/nitro) up to the octamer. Conformational analysis of the hexamer using a combination of low-temperature NMR spectroscopy and ab initio predictions of (1)H NMR chemical shifts indicates that, like other o-phenylenes, they exist as compact helices in solution. However, the substituents are found to have a significant effect on their conformational behavior: the nitro-functionalized terminus is 3-fold more likely to twist out of the helix. Protonation of the dimethylamino group favors the helical conformer. UV/vis spectroscopy indicates that the direct charge-transfer interaction between the push-pull substituents attenuates quickly compared to other conjugated systems, with no significant charge-transfer band for oligomers longer than the trimer. On protonation of the dimethylamino group, significant bathochromic shifts with increasing oligomer length are observed: the effective conjugation length is 9 repeat units, more than twice that of the parent oligomer. This behavior may be rationalized through examination of the frontier molecular orbitals of these compounds, which exhibit greater delocalization after protonation, as shown by DFT calculations.

  12. Stability of the Tower Gains of the STAR Endcap Calorimeter in 2012 Data

    NASA Astrophysics Data System (ADS)

    Amarasinghe, Chamindu; STAR Collaboration

    2016-09-01

    The Solenoid Tracker at RHIC (STAR) experiment, based at Brookhaven National Laboratory's Relativistic Heavy Ion Collider (RHIC), uses polarized-proton collisions to investigate sea quark and gluon contributions to the proton spin. The STAR detector's Endcap Electromagnetic Calorimeter (EEMC) is of particular interest in this experiment because it covers a kinematic region that is sensitive to gluons carrying a low fraction of the proton momentum, where the gluon's contribution to the spin of the proton is poorly constrained. The EEMC is located in the intermediate pseudorapidity range, 1 < η <2, and as a lead-scintillator sampling calorimeter, measures the electromagnetic energy of particles produced in the polarized-proton collisions. The calorimeter consists of several layers that include pre-shower, shower maximum, tower, and post-shower detectors. In these detectors, the energy gains, which convert a measured signal into an energy deposition, have been determined using data taken from the year 2012. The sensitivities of the tower energy gains to beam intensity and running time were studied. The results from these sensitivity studies will be reported. Funded by the US Department of Energy.

  13. Adsorption of hydrophobically end-capped poly(ethylene glycol) on cellulose.

    PubMed

    Holappa, Susanna; Kontturi, Katri S; Salminen, Arto; Seppälä, Jukka; Laine, Janne

    2013-11-12

    Adsorption of poly(ethylene glycol), hydrophobically end-capped with octadecenylsuccinic anhydride (OSA-PEG-OSA), on an ultrathin film of cellulose has been studied by quartz crystal microbalance with dissipation monitoring (QCM-D) and atomic force microscopy (AFM). Normally, PEG does not adsorb on cellulosic surfaces, but the use of the telechelic hydrophobic modification was found to promote adsorption. The influence of the conformation of the polymer in solution prior to adsorption and the subsequent properties of the adsorbed layer were investigated. The adsorption experiments were done at concentrations below and above the critical association concentration. The adsorption of OSA-PEG-OSA on cellulose was observed to occur in four distinct stages. Because of the amphiphilic nature of cellulose, further adsorption experiments were performed on hydrophobic (polystyrene) and hydrophilic (silica) model substrates to illuminate the contribution of hydrophobic and hydrophilic factors in the adsorption phenomenon. As expected, the kinetics and the mechanism of adsorption were strongly dependent on the chemical composition of the substrate.

  14. Surface reconstruction and hemocompatibility improvement of a phosphorylcholine end-capped poly(butylene succinate) coating.

    PubMed

    Hao, Ni; Wang, Yan-Bing; Zhang, Shi-Ping; Shi, Su-Qing; Nakashima, Kenichi; Gong, Yong-Kuan

    2014-09-01

    Control over cell-material surface interactions is the key to many new and improved biomedical devices. In this study, we present a simple yet effective surface modification method that allows for the surface reconstruction and formation of cell outer membrane mimetic structure on coatings that have significantly increased hemocompatibility. To achieve this, a phosphorylcholine end-capped poly(butylene succinate) (PBS-PC) was synthesized and dip-coated on coverslips. The surface structure of the amphiphilic PBS-PC film was reconstructed by heating in a vacuum oven to obtain the less hydrophilic surface and by immersing in hot water to obtain the more hydrophilic surface. Significant changes in the surface element concentration were observed by X-ray photoelectron spectroscopy analysis and changes in surface wettability were measured by sensitive dynamic contact angle technique. Scanning electron microscope images showed different morphologies of the reconstructed surfaces. Interestingly, the reconstruction between the less hydrophilic and more hydrophilic surfaces is reversible. More importantly, both the reconstructed surfaces are stable in room condition for more than 6 months, and both the surfaces show significant improvement in hemocompatibility as revealed by protein adsorption and platelet adhesion measurements. This reversible surface reconstruction strategy and the interesting results may be significant for fabricating stable and hemocompatible surfaces on differently shaped biomedical devices.

  15. N-15 NMR Spectroscopy as a Method for Comparing the Rates of Imidization of Several Diamines

    NASA Technical Reports Server (NTRS)

    Johnson, J. Christopher; Kuczmarski, Maria A.

    2006-01-01

    The relative rates of the conversion of amide-acid to imide was measured for a series or aromatic diamines that have been identified as potential replacements for 4,4'-methylene dianiline (MDA) in high-temperature polyimides and polymer composites. These rates were compared with the N-15 NMR resonances of the unreacted amines. The initial rates of imidization track with the difference in chemical shift between the amine nitrogens in MDA and those in the subject diamines. This comparison demonstrated that N-15 NMR spectroscopy is appropriate for the rapid screening of candidate diamines to determine their reactivity relative to MDA, and can serve to provide guidance to the process of creating the time-temperature profiles used in processing these materials into polymer matrix composites.

  16. Tetracene dicarboxylic imide and its disulfide: synthesis of ambipolar organic semiconductors for organic photovoltaic cells.

    PubMed

    Okamoto, Toshihiro; Suzuki, Tsuyoshi; Tanaka, Hideyuki; Hashizume, Daisuke; Matsuo, Yutaka

    2012-01-02

    We have designed and synthesized a new donor/acceptor-type tetracene derivative by the introduction of dicarboxylic imide and disulfide groups as electron-withdrawing and -donating units, respectively. The prepared compounds, tetracene dicarboxylic imide (TI) and its disulfide (TIDS) have high chemical and electrochemical stability as well as long-wavelength absorptions of up to 886 nm in the thin films. The crystal packing structure of TIDS molecules features face-to-face π-stacking, derived from dipole-dipole interactions. Notably, TIDS exhibited ambipolar properties of both electron-donating and -accepting natures in p-n and p-i-n heterojunction organic thin-film photovoltaic devices. Accordingly, TI and TIDS are expected to be promising compounds for designing new organic semiconductors.

  17. Demonstrating hydrogen production from ammonia using lithium imide - Powering a small proton exchange membrane fuel cell

    NASA Astrophysics Data System (ADS)

    Hunter, Hazel M. A.; Makepeace, Joshua W.; Wood, Thomas J.; Mylius, O. Simon; Kibble, Mark G.; Nutter, Jamie B.; Jones, Martin O.; David, William I. F.

    2016-10-01

    Accessing the intrinsic hydrogen content within ammonia, NH3, has the potential to play a very significant role in the future of a CO2-free sustainable energy supply. Inexpensive light metal imides and amides are effective at decomposing ammonia to hydrogen and nitrogen (2NH3 → 3H2 + N2), at modest temperatures, and thus represent a low-cost approach to on-demand hydrogen production. Building upon this discovery, this paper describes the integration of an ammonia cracking unit with a post-reactor gas purification system and a small-scale PEM fuel cell to create a first bench-top demonstrator for the production of hydrogen using light metal imides.

  18. Lithium bis(fluorosulfonyl)imide-PYR 14TFSI ionic liquid electrolyte compatible with graphite

    NASA Astrophysics Data System (ADS)

    Nádherná, Martina; Reiter, Jakub; Moškon, Jože; Dominko, Robert

    Lithium bis(fluorosulfonyl)imide (LiFSI) in 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR 14TFSI) was successfully tested as an electrolyte for graphite composite anodes at elevated temperature of 55 °C. The graphite anode showed a good cyclability during the galvanostatic testing at C/10 rate and 55 °C with the capacity close to theoretical. The formation of SEI in different electrolytes was the subject of study using impedance spectroscopy on symmetrical cells containing two lithium electrodes. The 0.7 m LiFSI in PYR 14TFSI exhibits a good ionic conductivity (5.9 mS cm -1 at 55 °C) along with high electrochemical stability and high thermal stability. These properties allow their potential application in large-scale lithium ion batteries with improved safety.

  19. Single Particle Characterization of Aβ Oligomers in Solution

    PubMed Central

    Yusko, Erik C.; Prangkio, Panchika; Sept, David; Rollings, Ryan C.; Li, Jiali; Mayer, Michael

    2012-01-01

    Determining the pathological role of amyloids in amyloid-associated diseases will require a method for determining the dynamic distributions in size and shape of amyloid oligomers with high resolution. Here, we explored the potential of resistive-pulse sensing through lipid bilayer-coated nanopores to measure the size of individual amyloid-β oligomers directly in solution and without chemical modification. This method classified individual amyloid-β aggregates as spherical oligomers, protofibrils, or mature fibers and made it possible to account for the large heterogeneity of amyloid-β aggregate sizes. The approach revealed the distribution of protofibrillar lengths as well as the average cross-sectional area of protofibrils and fibers. PMID:22686709

  20. Proportion effect in diblock co-oligomer molecular diodes

    NASA Astrophysics Data System (ADS)

    Hu, G. C.; Zhang, G. P.; Li, Y.; Ren, J. F.; Wang, C. K.

    2014-10-01

    Based on ab-initio theory and nonequilibrium Green's function method, the effect of proportion on the rectification in pyrimidinyl-phenyl diblock co-oligomer diodes is investigated in two regimes. For a short co-oligomer diode, it is found that the 1:1 proportion of the two moieties favors the largest rectification ratio. For a long co-oligomer diode, an interesting proportion-dependent variation of the rectifying direction is observed. Furthermore, the optimal proportion for the largest rectification ratio is not 1:1 any longer. A deep understanding can be achieved by analyzing the bias-dependent transmission spectra combined with the evolution of the molecular orbitals.

  1. Aggregation of inorganic nanoparticles mediated by biomimetic oligomers.

    PubMed

    Tigger-Zaborov, Hagar; Maayan, Galia

    2015-09-14

    Assemblies of nanoparticles (NPs) have been broadly used for the construction of materials with unique spectroscopic and chiral properties for applications in various scientific disciplines such as sensing, bio-nanotechnology and medicine. Mediating the aggregation of NPs by synthetic biomimetic oligomers, namely, DNA, PNA, peptides and peptide mimics, rather than by small organic molecules has been shown to produce interesting supramolecular structures and enable the combination of the biocompatibility of the mediators and the spectroscopic properties of the NPs. Yet, the key to using this powerful approach for designing new functional materials is to understand the NPs aggregation patterns induced by biopolymers and biomimetic oligomers. Herein we describe the important developments in this field, from early studies to recent work with an emphasis on synthetic methods and tools for controlled assembly of metal NPs by biomimetic polymers and oligomers.

  2. Phenylethynyl Phthalic Anhydride

    NASA Technical Reports Server (NTRS)

    Hergenrother, Paul M. (Inventor); Smith, Joseph G., Jr. (Inventor)

    1997-01-01

    Controlled molecular weight PhenylEthynyl Terminated Imide oligomers (PETIs) have been prepared by the cyclodehydration of precursor phenylethynyl terminated amic acid oligomers. Amino terminated amic acid oligomers are prepared from the reaction of dianhydride(s) with an excess of diamine(s) and subsequently endcapped with PhenylEthynyl Phthalic Anhydride(s) (PEPA). The polymerizations are carried out in polar aprotic solvents such as N-methyl-2pyrrolidinone or N N-dimethylacetamide under nitrogen at room temperature. The amic acid oligomers are subsequently cyclodehydrated either thermally or chemically to the corresponding imide oligomers. Direct preparation of PETIs from the reaction of dianhydride(s) with an excess of diamine(s) and endcapped with phenylethynyl phthalic anhydride(s) has been performed in m-cresol. Phenylethynyl phthalic anhydrides are synthesized by the palladium catalyzed reaction of phenylacetylene with bromo substituted phthalic anhydrides in triethylamine. These new materials exhibit excellent properties and are potentially useful as adhesives, coatings, films, moldings and composite matrices.

  3. Direct Electrodeposition of UO2 from Uranyl Bis(trifluoromethanesulfonyl)imide Dissolved in 1-Ethyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)imide Room Temperature Ionic Liquid System

    SciTech Connect

    Freiderich, John W.; Wanigasekara, Eranda P.; Sun, Xiao-Guang; Meisner, Roberta Ann; Meyer, III, Harry M.; Luo, Huimin; Delmau, Laetitia Helene; Dai, Sheng; Moyer, Bruce A

    2013-11-11

    Our study demonstrates a direct electrodeposition of UO2 at a Pt cathode from a solution of uranyl bis(trifluoromethanesulfonyl)imide [UO2(NTf2)2)] in a bulk room-temperature ionic liquid (RTIL), 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMIM+NTf2). Cyclic voltammetry (CV) studies revealed two reduction waves corresponding to the conversion of uranium(VI) to uranium(IV), and a mechanism for the overall electroreduction is proposed. A controlled-potential experiment was performed, holding the reduction potential at–1.0 V for 24 h to obtain a brown-black deposit of UO2 on the Pt cathode. The Faradaic efficiency of the reduction process was determined to be >80%. The UO2deposit was characterized by powder X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS).

  4. Direct detection of alpha synuclein oligomers in vivo

    PubMed Central

    2013-01-01

    Background Rat models of Parkinson’s disease are widely used to elucidate the mechanisms underlying disease etiology or to investigate therapeutic approaches. Models were developed using toxins such as MPTP or 6-OHDA to specifically target dopaminergic neurons resulting in acute neuronal loss in the substantia nigra or by using viral vectors to induce the specific and gradual expression of alpha synuclein in the substantia nigra. The detection of alpha- synuclein oligomers, the presumed toxic species, in these models and others has been possible using only indirect biochemical approaches to date. Here we coinjected AAVs encoding alpha-synuclein fused to the N- or C-terminal half of VenusYFP in rat substantia nigra pars compacta and describe for the first time a novel viral vector rodent model with the unique ability to directly detect and track alpha synuclein oligomers ex vivo and in vivo. Results Viral coinjection resulted in widespread VenusYFP signal within the nigrostriatal pathway, including cell bodies in the substantia nigra and synaptic accumulation in striatal terminals, suggestive of in vivo alpha-synuclein oligomers formation. Transduced rats showed alpha-synuclein induced dopaminergic neuron loss in the substantia nigra, the appearance of dystrophic neurites, and gliosis in the striatum. Moreover, we have applied in vivo imaging techniques in the living mouse to directly image alpha-synuclein oligomers in the cortex. Conclusion We have developed a unique animal model that provides a tool for the Parkinson’s disease research community with which to directly detect alpha- synuclein oligomers in vivo and screen therapeutic approaches targeting alpha-synuclein oligomers. PMID:24252244

  5. Memantine rescues transient cognitive impairment caused by high-molecular-weight aβ oligomers but not the persistent impairment induced by low-molecular-weight oligomers.

    PubMed

    Figueiredo, Cláudia P; Clarke, Julia R; Ledo, José Henrique; Ribeiro, Felipe C; Costa, Carine V; Melo, Helen M; Mota-Sales, Axa P; Saraiva, Leonardo M; Klein, William L; Sebollela, Adriano; De Felice, Fernanda G; Ferreira, Sergio T

    2013-06-05

    Brain accumulation of soluble amyloid-β oligomers (AβOs) has been implicated in synapse failure and cognitive impairment in Alzheimer's disease (AD). However, whether and how oligomers of different sizes induce synapse dysfunction is a matter of controversy. Here, we report that low-molecular-weight (LMW) and high-molecular-weight (HMW) Aβ oligomers differentially impact synapses and memory. A single intracerebroventricular injection of LMW AβOs (10 pmol) induced rapid and persistent cognitive impairment in mice. On the other hand, memory deficit induced by HMW AβOs (10 pmol) was found to be reversible. While memory impairment in LMW oligomer-injected mice was associated with decreased hippocampal synaptophysin and GluN2B immunoreactivities, synaptic pathology was not detected in the hippocampi of HMW oligomer-injected mice. On the other hand, HMW oligomers, but not LMW oligomers, induced oxidative stress in hippocampal neurons. Memantine rescued both neuronal oxidative stress and the transient memory impairment caused by HMW oligomers, but did not prevent the persistent cognitive deficit induced by LMW oligomers. Results establish that different Aβ oligomer assemblies act in an orchestrated manner, inducing different pathologies and leading to synapse dysfunction. Furthermore, results suggest a mechanistic explanation for the limited efficacy of memantine in preventing memory loss in AD.

  6. Oligomer Molecules for Efficient Organic Photovoltaics.

    PubMed

    Lin, Yuze; Zhan, Xiaowei

    2016-02-16

    Solar cells, a renewable, clean energy technology that efficiently converts sunlight into electricity, are a promising long-term solution for energy and environmental problems caused by a mass of production and the use of fossil fuels. Solution-processed organic solar cells (OSCs) have attracted much attention in the past few years because of several advantages, including easy fabrication, low cost, lightweight, and flexibility. Now, OSCs exhibit power conversion efficiencies (PCEs) of over 10%. In the early stage of OSCs, vapor-deposited organic dye materials were first used in bilayer heterojunction devices in the 1980s, and then, solution-processed polymers were introduced in bulk heterojunction (BHJ) devices. Relative to polymers, vapor-deposited small molecules offer potential advantages, such as a defined molecular structure, definite molecular weight, easy purification, mass-scale production, and good batch-to-batch reproducibility. However, the limited solubility and high crystallinity of vapor-deposited small molecules are unfavorable for use in solution-processed BHJ OSCs. Conversely, polymers have good solution-processing and film-forming properties and are easily processed into flexible devices, whereas their polydispersity of molecular weights and difficulty in purification results in batch to batch variation, which may hamper performance reproducibility and commercialization. Oligomer molecules (OMs) are monodisperse big molecules with intermediate molecular weights (generally in the thousands), and their sizes are between those of small molecules (generally with molecular weights <1000) and polymers (generally with molecular weights >10000). OMs not only overcome shortcomings of both vapor-deposited small molecules and solution-processed polymers, but also combine their advantages, such as defined molecular structure, definite molecular weight, easy purification, mass-scale production, good batch-to-batch reproducibility, good solution processability

  7. Electronic coherence dynamics in trans-polyacetylene oligomers.

    PubMed

    Franco, Ignacio; Brumer, Paul

    2012-04-14

    Electronic coherence dynamics in trans-polyacetylene oligomers are considered by explicitly computing the time dependent molecular polarization from the coupled dynamics of electronic and vibrational degrees of freedom in a mean-field mixed quantum-classical approximation. The oligomers are described by the Su-Schrieffer-Heeger Hamiltonian and the effect of decoherence is incorporated by propagating an ensemble of quantum-classical trajectories with initial conditions obtained by sampling the Wigner distribution of the nuclear degrees of freedom. The electronic coherence of superpositions between the ground and excited and between pairs of excited states is examined for chains of different length, and the dynamics is discussed in terms of the nuclear overlap function that appears in the off-diagonal elements of the electronic reduced density matrix. For long oligomers the loss of coherence occurs in tens of femtoseconds. This time scale is determined by the decay of population into other electronic states through vibronic interactions, and is relatively insensitive to the type and class of superposition considered. By contrast, for smaller oligomers the decoherence time scale depends strongly on the initially selected superposition, with superpositions that can decay as fast as 50 fs and as slow as 250 fs. The long-lived superpositions are such that little population is transferred to other electronic states and for which the vibronic dynamics is relatively harmonic.

  8. Unique Properties of the Rabbit Prion Protein Oligomer

    PubMed Central

    Yu, Ziyao; Huang, Pei; Yu, Yuanhui; Zheng, Zhen; Huang, Zicheng; Guo, Chenyun; Lin, Donghai

    2016-01-01

    Prion diseases, also known as transmissible spongiform encephalopathies (TSEs), are a group of fatal neurodegenerative disorders infecting both humans and animals. Recent works have demonstrated that the soluble prion protein oligomer (PrPO), the intermediate of the conformational transformation from the host-derived cellular form (PrPC) to the disease-associated Scrapie form (PrPSc), exerts the major neurotoxicity in vitro and in vivo. Rabbits show strong resistance to TSEs, the underlying mechanism is unclear to date. It is expected that the relative TSEs-resistance of rabbits is closely associated with the unique properties of rabbit prion protein oligomer which remain to be addressed in detail. In the present work, we prepared rabbit prion protein oligomer (recRaPrPO) and human prion protein oligomer (recHuPrPO) under varied conditions, analyzed the effects of pH, NaCl concentration and incubation temperature on the oligomerization, and compared the properties of recRaPrPO and recHuPrPO. We found that several factors facilitated the formation of prion protein oligomers, including low pH, high NaCl concentration, high incubation temperature and low conformational stability of monomeric prion protein. RecRaPrPO was formed more slowly than recHuPrPO at physiological-like conditions (< 57°C, < 150 mM NaCl). Furthermore, recRaPrPO possessed higher susceptibility to proteinase K and lower cytotoxicity in vitro than recHuPrPO. These unique properties of recRaPrPO might substantially contribute to the TSEs-resistance of rabbits. Our work sheds light on the oligomerization of prion proteins and is of benefit to mechanistic understanding of TSEs-resistance of rabbits. PMID:27529173

  9. Novel Poly(imide dioxime) Sorbents: Development and testing for enhanced extraction of uranium from natural seawater

    SciTech Connect

    Das, Sadananda; Brown, Suree S.; Mayes, Richard T.; Janke, Christopher J.; Tsouris, Costas; Kuo, Li-Jung; Gill, Gary A.; Dai, Sheng

    2016-04-09

    A new series of amidoxime-based polymer adsorbents were synthesized at the Oak Ridge National Laboratory (ORNL) by electron beam induced grafting of acrylonitrile and itaconic acid onto polyethylene fiber. Hydroxylamine derivatives of poly(acrylonitrile) (PAN) moiety are demonstrated to possess two kinds of functional groups: open-chain amidoxime and cyclic imide dioxime. The open-chain amidoxime is shown to convert to imide dioxime on heat treatment in the presence of an aprotic solvent, like dimethylsulfoxide (DMSO). The formation of amidoxime and imide dioxime was confirmed by 13-C CPMAS spectra. The adsorbents were evaluated for uranium adsorption efficiency at ORNL with simulated seawater spiked with 8 ppm uranium and 5 gallon seawater in a batch reactor, and in flow-through columns with natural seawater at the Marine Science Laboratory (MSL) of Pacific Northwest National Laboratory (PNNL) at Sequim Bay, WA. The DMSO-heat-treated sorbents adsorbed uranium as high as 4.48 g-U/kg-ads. from seawater. Experimental evidence is presented that the poly(imide dioxime) is primarily responsible for enhanced uranium adsorption capacity from natural seawater. The conjugated system in the imide dioxime ligand possesses increased electron donation ability, which is believed to significantly enhance the uranyl coordination in seawater

  10. Sulphonated imidized graphene oxide (SIGO) based polymer electrolyte membrane for improved water retention, stability and proton conductivity

    NASA Astrophysics Data System (ADS)

    Pandey, Ravi P.; Shahi, Vinod K.

    2015-12-01

    Sulphonated imidized graphene oxide (SIGO) (graphene oxide (GO) tethered sulphonated polyimide) has been successfully synthesized by polycondensation reaction using dianhydride and sulphonated diamine. Polymer electrolyte membranes (PEMs) are prepared by using SIGO (different wt%) and sulphonated poly(imide) (SPI). Resultant SPI/SIGO composite PEMs exhibit improved stabilities (thermal, mechanical and oxidative) and good water-retention properties (high bound water content responsible for proton conduction at high temperature by internal self-humidification). Incorporation of covalent bonded SIGO into SPI matrix results hydrophobic-hydrophilic phase separation and facile architecture of proton conducting path. Well optimized sulphonated poly(imide)/sulphonated imidized graphene oxide (15 wt%) (SPI/SIGO-15) composite membrane shows 2.24 meq g-1 ion-exchange capacity (IEC); 11.38 × 10-2 S cm-1 proton conductivity; 5.12% bound water content; and 10.52 × 10-7 cm2 s-1 methanol permeability. Maximum power density for pristine SPI membrane (57.12 mW cm-2) improves to 78.53 mW cm-2 for SPI/SIGO-15 membrane, in single-cell direct methanol fuel cell (DMFC) test at 70 °C using 2 M methanol fuel. Under similar experimental conditions, Nafion 117 membrane exhibits 62.40 mW cm-2 maximum power density. Reported strategy for the preparation of PEMs, offers a useful protocol for grafting of functionalized inorganic materials with in organic polymer chain by imidization.

  11. Low Melt Viscosity Resins for Resin Transfer Molding

    NASA Technical Reports Server (NTRS)

    Harris, Frank W.

    2002-01-01

    In recent years, resin transfer molding (RTM) has become one of the methods of choice for high performance composites. Its cost effectiveness and ease of fabrication are major advantages of RTM. RTM process usually requires resins with very low melt viscosity (less than 10 Poise). The optimum RTM resins also need to display high thennal-oxidative stability, high glass transition temperature (T(sub g)), and good toughness. The traditional PMR-type polyimides (e.g. PMR-15) do not fit this requirement, because the viscosities are too high and the nadic endcap cures too fast. High T(sub g), low-melt viscosity resins are highly desirable for aerospace applications and NASA s Reusable Launch Vehicle (RLV) program. The objective of this work is to prepare low-melt viscosity polyimide resins for RTM or resin film infusion (RFI) processes. The approach involves the synthesis of phenylethynyl-terminated imide oligomers. These materials have been designed to minimize their melt viscosity so that they can be readily processed. During the cure, the oligomers undergo both chain extension and crosslinking via the thermal polymerization of the phenylethynyl groups. The Phenylethynyl endcap is preferred over the nadic group due to its high curing temperature, which provides broader processing windows. This work involved the synthesis and polymerization of oligomers containing zig-zag backbones and twisted biphenyl structures. Some A-B type precursors which possessed both nitro and anhydride functionality, or both nitro and amine functionality, were also synthesized in order to obtain the well defined oligomers. The resulting zig-zag structured oligomers were then end-capped with 4-phenylethynylphthalic anhydride (PEPA) for further cure. The properties of these novel imide oligomers are evaluated.

  12. Aryne [3 + 2] cycloaddition with N-sulfonylpyridinium imides and in situ generated N-sulfonylisoquinolinium imides: a potential route to pyrido[1,2-b]indazoles and indazolo[3,2-a]isoquinolines.

    PubMed

    Zhao, Jingjing; Li, Pan; Wu, Chunrui; Chen, Hongli; Ai, Wenying; Sun, Renhong; Ren, Hailong; Larock, Richard C; Shi, Feng

    2012-03-07

    The aryne [3 + 2] cycloaddition process with pyridinium imides breaks the aromaticity of the pyridine ring. By equipping the imide nitrogen with a sulfonyl group, the intermediate readily eliminates a sulfinate anion to restore the aromaticity, leading to the formation of pyrido[1,2-b]indazoles. The scope and limitation of this reaction are discussed. As an extension of this chemistry, N-tosylisoquinolinium imides, generated in situ from N'-(2-alkynylbenzylidene)-tosylhydrazides via an AgOTf-catalyzed 6-endo-dig electrophilic cyclization, readily undergo aryne [3 + 2] cycloaddition to afford indazolo[3,2-a]-isoquinolines in the same pot, offering a highly efficient route to these potential anticancer agents.

  13. Capping of aβ42 oligomers by small molecule inhibitors.

    PubMed

    Fu, Ziao; Aucoin, Darryl; Ahmed, Mahiuddin; Ziliox, Martine; Van Nostrand, William E; Smith, Steven O

    2014-12-23

    Aβ42 peptides associate into soluble oligomers and protofibrils in the process of forming the amyloid fibrils associated with Alzheimer's disease. The oligomers have been reported to be more toxic to neurons than fibrils, and have been targeted by a wide range of small molecule and peptide inhibitors. With single touch atomic force microscopy (AFM), we show that monomeric Aβ42 forms two distinct types of oligomers, low molecular weight (MW) oligomers with heights of 1-2 nm and high MW oligomers with heights of 3-5 nm. In both cases, the oligomers are disc-shaped with diameters of ~10-15 nm. The similar diameters suggest that the low MW species stack to form the high MW oligomers. The ability of Aβ42 inhibitors to interact with these oligomers is probed using atomic force microscopy and NMR spectroscopy. We show that curcumin and resveratrol bind to the N-terminus (residues 5-20) of Aβ42 monomers and cap the height of the oligomers that are formed at 1-2 nm. A second class of inhibitors, which includes sulindac sulfide and indomethacin, exhibit very weak interactions across the Aβ42 sequence and do not block the formation of the high MW oligomers. The correlation between N-terminal interactions and capping of the height of the Aβ oligomers provides insights into the mechanism of inhibition and the pathway of Aβ aggregation.

  14. Poly(arylsulfone imide) as E-beam resist: synthesis and radiolysis. Technical report

    SciTech Connect

    Chien, J.C.; Cheng, Z.S.

    1989-01-01

    Aromatic diamines containing -SO/sub 2/-and-S- moieties were used to prepare soluble polyimides with ditrifluoromethyl methane bis(phthalic anhydride) (F-series polyimides) and polyamic acid with pyromellitic dianhydride (P-series). Gamma radiolysis gave G(S) values for scission between 1 to 2 with no crosslinking. Significant weight loss occurred with radiolysis is attributable to efficient -SO/sub 2/-bond scission for the R-series polyimides, as well as imidization in the cases of P-series polyamic acids.

  15. Copper Complexes of Anionic Nitrogen Ligands in the Amidation and Imidation of Aryl Halides

    PubMed Central

    Tye, Jesse W.; Weng, Zhiqiang; Johns, Adam M.; Incarvito, Christopher D.; Hartwig, John F.

    2010-01-01

    Copper(I) imidate and amidate complexes of chelating N,N-donor ligands, which are proposed intermediates in copper-catalyzed amidations of aryl halides, have been synthesized and characterized by X-ray diffraction and detailed solution-phase methods. In some cases, the complexes adopt neutral, three-coordinate trigonal planar structures in the solid state, but in other cases they adopt an ionic form consisting of an L2Cu+ cation and a CuX2− anion. A tetraalkylammonium salt of the CuX2− anion in which X = phthalimidate was also isolated. Conductivity measurements and 1H NMR spectra of mixtures of two complexes all indicate that the complexes exist predominantly in the ionic form in DMSO and DMF solutions. One complex was sufficiently soluble for conductance measurements in less polar solvents and was shown to adopt some degree of the ionic form in THF and predominantly the neutral form in benzene. The complexes containing dative nitrogen ligands reacted with iodoarenes and bromoarenes to form products from C–N coupling, but the ammonium salt of [Cu(phth)2]− did not. Similar selectivities for stoichiometric and catalytic reactions with two different iodoarenes and faster rates for the stoichiometric reactions implied that the isolated amidate and imidate complexes are intermediates in the reactions of amides and imides with haloarenes catalyzed by copper complexes containing dative N,N ligands. These amidates and imidates reacted much more slowly with chloroarenes, including chloroarenes that possess more favorable reduction potentials than some bromoarenes and that are known to undergo fast dissociation of chloride from the chloroarene radical anion. The reaction of o-(allyloxy)iodobenzene with [(phen)2Cu][Cu(pyrr)2] results in formation of the C-N coupled product in high yield and no detectable amount of the 3-methyl-2,3-dihydrobenzofuran or 3-methylene-2,3-dihydrobenzofuran products that would be expected from a reaction that generated free radicals. These

  16. Poly(imide)/Organically-Modified Montmorillonite Nanocomposite as a Potential Membrane for Alkaline Fuel Cells

    PubMed Central

    Battirola, Liliane C.; Gasparotto, Luiz H. S.; Rodrigues-Filho, Ubirajara P.; Tremiliosi-Filho, Germano

    2012-01-01

    In this work we evaluated the potentiality of a poly(imide) (PI)/organically-modified montmorillonite (O-MMT) nanocomposite membrane for the use in alkaline fuel cells. Both X-ray diffraction and scanning electron microscopy revealed a good dispersion of O-MMT into the PI matrix and preservation of the O-MMT layered structure. When compared to the pure PI, the addition of O-MMT improved thermal stability and markedly increased the capability of absorbing electrolyte and ionic conductivity of the composite. The results show that the PI/O-MMT nanocomposite is a promising candidate for alkaline fuel cell applications. PMID:24958290

  17. Stabilization of different conformers of bis(trifluoromethanesulfonyl)imide anion in ammonium-based ionic liquids at low temperatures.

    PubMed

    Vitucci, F M; Trequattrini, F; Palumbo, O; Brubach, J-B; Roy, P; Navarra, M A; Panero, S; Paolone, A

    2014-09-25

    The infrared absorption spectra of two ionic liquids with bis(trifluoromethanesulfonyl)imide (TFSI) as an anion and ammonium with different alkyl chains as cations are reported as a function of temperature. Using the comparison with ab initio calculations of the infrared-active intramolecular vibrations, the experimental lines were ascribed to the various ions composing the ionic liquids. In the liquid state of the samples, both conformers of the TFSI ion are present. In the solid state, however, the two conformers survive in N-trimethyl-N-propylammonium bis(trifluoromethanesulfonyl)imide (TMPA-TFSI), while only cis-TFSI is retained in N-trimethyl-N-hexylammonium bis(trifluoromethanesulfonyl)imide (TMHA-TFSI). We suggest that the longer alkyl chains of the former compound stabilize the less stable conformer of TFSI by means of stronger interactions between anions and cations.

  18. Alzheimer's therapeutics targeting amyloid beta 1-42 oligomers II: Sigma-2/PGRMC1 receptors mediate Abeta 42 oligomer binding and synaptotoxicity.

    PubMed

    Izzo, Nicholas J; Xu, Jinbin; Zeng, Chenbo; Kirk, Molly J; Mozzoni, Kelsie; Silky, Colleen; Rehak, Courtney; Yurko, Raymond; Look, Gary; Rishton, Gilbert; Safferstein, Hank; Cruchaga, Carlos; Goate, Alison; Cahill, Michael A; Arancio, Ottavio; Mach, Robert H; Craven, Rolf; Head, Elizabeth; LeVine, Harry; Spires-Jones, Tara L; Catalano, Susan M

    2014-01-01

    Amyloid beta (Abeta) 1-42 oligomers accumulate in brains of patients with Mild Cognitive Impairment (MCI) and disrupt synaptic plasticity processes that underlie memory formation. Synaptic binding of Abeta oligomers to several putative receptor proteins is reported to inhibit long-term potentiation, affect membrane trafficking and induce reversible spine loss in neurons, leading to impaired cognitive performance and ultimately to anterograde amnesia in the early stages of Alzheimer's disease (AD). We have identified a receptor not previously associated with AD that mediates the binding of Abeta oligomers to neurons, and describe novel therapeutic antagonists of this receptor capable of blocking Abeta toxic effects on synapses in vitro and cognitive deficits in vivo. Knockdown of sigma-2/PGRMC1 (progesterone receptor membrane component 1) protein expression in vitro using siRNA results in a highly correlated reduction in binding of exogenous Abeta oligomers to neurons of more than 90%. Expression of sigma-2/PGRMC1 is upregulated in vitro by treatment with Abeta oligomers, and is dysregulated in Alzheimer's disease patients' brain compared to age-matched, normal individuals. Specific, high affinity small molecule receptor antagonists and antibodies raised against specific regions on this receptor can displace synthetic Abeta oligomer binding to synaptic puncta in vitro and displace endogenous human AD patient oligomers from brain tissue sections in a dose-dependent manner. These receptor antagonists prevent and reverse the effects of Abeta oligomers on membrane trafficking and synapse loss in vitro and cognitive deficits in AD mouse models. These findings suggest sigma-2/PGRMC1 receptors mediate saturable oligomer binding to synaptic puncta on neurons and that brain penetrant, small molecules can displace endogenous and synthetic oligomers and improve cognitive deficits in AD models. We propose that sigma-2/PGRMC1 is a key mediator of the pathological effects of

  19. A Comparative Ab Initio Study of the Primary Hydration and Proton Dissociation of Various Imide and Sulfonic Acid Ionomers

    SciTech Connect

    Clark II, Jeffrey K.; Paddison, Stephen J.; Eikerling, Michael; Dupuis, Michel; Zawodzinski, Jr., Thomas A.

    2012-03-29

    We compare the role of neighboring group substitutions on proton dissociation of hydrated acidic moieties suitable for proton exchange membranes through electronic structure calculations. Three pairs of ionomers containing similar electron withdrawing groups within the pair were chosen for the study: two fully fluorinated sulfonyl imides (CF3SO2NHSO2CF3 and CF3CF2SO2NHSO2CF3), two partially fluorinated sulfonyl imides (CH3SO2NHSO2CF3 and C6H5SO2NHSO2CF2CF3), and two aromatic sulfonic acid based material s (CH3C6H4SO3H and CH3 OC6 - H3OCH3C6H4SO3H). Fully optimized counterpoise (CP) corrected geometries were obtained for each ionomer fragment with the inclusion of water molecules at the B3LYP/6-311G** level of density functional theory. Spontaneous proton dissociation was observed upon addition of three water molecules in each system, and the transition to a solvent-separated ion pair occurred when four water molecules were introduced. No considerable quantitative or qualitative differences in proton dissociation, hydrogen bond networks formed, or water binding energies were found between systems containing similar electron withdrawing groups. Each of the sulfonyl imide ionomers exhibited qualitatively similar results regarding proton dissociation and separation. The fully fluorinated sulfonyl imides, however, showed a greater propensity to exist in dissociated and ion-pair separated states at low degrees of hydration than the partially fluorinated sulfonyl imides. This effect is due to the additional electron withdrawing groups providing charge stabilization as the dissociated proton migrates away from the imide anion.

  20. Porous Cross-Linked Polyimide Networks

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B. (Inventor); Guo, Haiquan (Inventor)

    2015-01-01

    Porous cross-linked polyimide networks are provided. The networks comprise an anhydride end-capped polyamic acid oligomer. The oligomer (i) comprises a repeating unit of a dianhydride and a diamine and terminal anhydride groups, (ii) has an average degree of polymerization of 10 to 50, (iii) has been cross-linked via a cross-linking agent, comprising three or more amine groups, at a balanced stoichiometry of the amine groups to the terminal anhydride groups, and (iv) has been chemically imidized to yield the porous cross-linked polyimide network. Also provided are porous cross-linked polyimide aerogels comprising a cross-linked and imidized anhydride end-capped polyamic acid oligomer, wherein the oligomer comprises a repeating unit of a dianhydride and a diamine, and the aerogel has a density of 0.10 to 0.333 g/cm.sup.3 and a Young's modulus of 1.7 to 102 MPa. Also provided are thin films comprising aerogels, and methods of making porous cross-linked polyimide networks.

  1. Anticoagulant flavonoid oligomers from the rhizomes of Alpinia platychilus.

    PubMed

    Shen, Chuan-Pu; Luo, Jian-Guang; Yang, Ming-Hua; Kong, Ling-Yi

    2015-10-01

    Two pairs of enantiomers of flavonoid oligomers (1a and 1b, 2a and 2b) along with one known chalcone (3) were isolated from the rhizomes of Alpinia platychilus. Their structures were elucidated on the basis of spectroscopic data (MS and 1D/2D NMR). The absolute configurations of the flavonoid oligomers were established by their ECD spectra. Separation of the enantiomeric mixtures (1a and 1b, 2a and 2b) was achieved on a chiral column using hexane:isopropyl alcohol:ethanol (7:2:1) as eluents. The anticoagulant assay showed that 2a, 2b and 3 exhibited potent activities to prolong the prothrombin times (PT) and the thrombin times (TT).

  2. Phase transition in conjugated oligomers suspended in chloroform

    NASA Astrophysics Data System (ADS)

    Dwivedi, Shikha; Kumar, Anupam; Yadav, S. N. S.; Mishra, Pankaj

    2015-08-01

    Density functional theory (DFT) has been used to investigate the isotropic-nematic (I-N) phase transition in a system of high aspect ratio conjugated oligomers suspended in chloroform. The interaction between the oligomers is modeled using Gay-Berne potential in which effect of solvent is implicit. Percus-Yevick integral equation theory has been used to evaluate the pair correlation functions of the fluid phase at several temperatures and densities. These pair correlation function has been used in the DFT to evaluate the I-N freezing parameters. Highly oriented nematic is found to stabilize at low density. The results obtained are in qualitative agreement with the simulation and are verifiable.

  3. Synthesis of long prebiotic oligomers on mineral surfaces.

    PubMed

    Ferris, J P; Hill, A R; Liu, R; Orgel, L E

    1996-05-02

    Most theories of the origin of biological organization assume that polymers with lengths in the range of 30-60 monomers are needed to make a genetic system viable. But it has not proved possible to synthesize plausibly prebiotic polymers this long by condensation in aqueous solution, because hydrolysis competes with polymerization. The potential of mineral surfaces to facilitate prebiotic polymerization was pointed out long ago. Here we describe a system that models prebiotic polymerization by the oligomerization of activated monomers--both nucleotides and amino acids. We find that whereas the reactions in solution produce only short oligomers (the longest typically being a 10-mer), the presence of mineral surfaces (montmorillonite for nucleotides, illite and hydroxylapatite for amino acids) induces the formation of oligomers up to 55 monomers long. These are formed by successive 'feedings' with the monomers; polymerization takes place on the mineral surfaces in a manner akin to solid-phase synthesis of biopolymers.

  4. Synthesis of long Prebiotic Oligomers on Mineral Surfaces

    NASA Technical Reports Server (NTRS)

    Ferris, James P.; Hill, Aubrey R., Jr.; Liu, Rihe; Orgel, Leslie E.

    1996-01-01

    Most theories of the origin of biological organization assume that polymers with lengths in the range of 30-60 monomers are needed to make a genetic system viable. But it has not proved possible to synthesize plausibly prebiotic polymers this long by condensation in aqueous solution, because hydrolysis competes with polymerization. The potential of mineral surfaces to facilitate prebiotic polymerization was pointed out long ago. Here we describe a system that models prebiotic polymerization by the oligomerization of activated monomers -both nucleotides and amino acids. We find that whereas the reactions in solution produce only short oligomers (the longest typically being a 10-mer), the presence of mineral surfaces (montmorillonite for nucleotides, illite and hydroxylapatite for amino adds) induces the formation of oligomers up to 55 monomers long. These are formed by successive "feedings" with the monomers; polymerization takes place on the mineral surfaces in a manner akin to solid-phase synthesis of biopolymers.

  5. Phase behavior of a lattice hydrophobic oligomer in explicit water.

    PubMed

    Romero-Vargas Castrillón, Santiago; Matysiak, Silvina; Stillinger, Frank H; Rossky, Peter J; Debenedetti, Pablo G

    2012-08-09

    We investigate the thermodynamics of hydrophobic oligomer collapse using a water-explicit, three-dimensional lattice model. The model captures several aspects of protein thermodynamics, including the emergence of cold- and thermal-unfolding, as well as unfolding at high solvent density (a phenomenon akin to pressure-induced denaturation). We show that over a range of conditions spanning a ≈14% increase in solvent density, the oligomer transforms into a compact, strongly water-penetrated conformation at low temperature. This contrasts with thermal unfolding at high temperature, where the system "denatures" into an extended random coil conformation. We report a phase diagram for hydrophobic collapse that correctly captures qualitative aspects of cold and thermal unfolding at low to intermediate solvent densities.

  6. Production of random DNA oligomers for scalable DNA computing.

    PubMed

    Wang, Sixue S L; Johnson, John J X; Hughes, Bradley S T; Karabay, Dundar A O; Bader, Karson D W; Austin, Allen; Austin, Alan; Habib, Aisha; Hatef, Husnia; Joshi, Megha; Nguyen, Lawrence; Mills, Allen P

    2009-01-01

    While remarkably complex networks of connected DNA molecules can form from a relatively small number of distinct oligomer strands, a large computational space created by DNA reactions would ultimately require the use of many distinct DNA strands. The automatic synthesis of this many distinct strands is economically prohibitive. We present here a new approach to producing distinct DNA oligomers based on the polymerase chain reaction (PCR) amplification of a few random template sequences. As an example, we designed a DNA template sequence consisting of a 50-mer random DNA segment flanked by two 20-mer invariant primer sequences. Amplification of a dilute sample containing about 30 different template molecules allows us to obtain around 10(11) copies of these molecules and their complements. We demonstrate the use of these amplicons to implement some of the vector operations that will be required in a DNA implementation of an analog neural network.

  7. Changes of adiponectin oligomer composition by moderate weight reduction.

    PubMed

    Bobbert, Thomas; Rochlitz, Helmut; Wegewitz, Uta; Akpulat, Suzan; Mai, Knut; Weickert, Martin O; Möhlig, Matthias; Pfeiffer, Andreas F H; Spranger, Joachim

    2005-09-01

    Adiponectin affects lipid metabolism and insulin sensitivity. However, adiponectin circulates in three different oligomers that may also have distinct biological functions. We aimed to analyze the role of these oligomers in obesity and lipid metabolism after weight reduction. A total of 17 obese volunteers (15 women and 2 men) participated in a weight reduction program. Individuals were characterized before and after 6 months of a balanced diet. Adiponectin was determined by enzyme-linked immunosorbent assay, and oligomers were detected by nondenaturating Western blot. BMI decreased (35.1 +/- 1.2 to 32.8 +/- 1.1 kg/m(2), P < 0.001), which was associated with an improved metabolite profile. Total adiponectin increased from 5.3 +/- 0.5 to 6.1 +/- 0.6 microg/ml (P = 0.076). High (HMW) and medium molecular weight (MMW) adiponectin oligomers significantly increased during weight reduction (HMW: 0.37 +/- 0.07 to 0.4 +/- 0.08 microg/ml, P = 0.042; MMW: 2.3 +/- 0.2 to 2.9 +/- 0.3 microg/ml, P = 0.007), while low molecular weight (LMW) did not significantly change. Body weight inversely correlated with HMW (r = -0.695, P = 0.002) and positively with LMW (r = 0.579, P = 0.015). Interestingly, HDL cholesterol and HMW were strongly correlated (r = 0.665, P = 0.007). Indeed, HMW and free fatty acids before weight reduction predicted approximately 60% of HDL changes during intervention. In conclusion, weight reduction results in a relative increase of HMW/MMW adiponectin and a reduction of LMW adiponectin. Total adiponectin and especially HMW adiponectin are related to circulating HDL cholesterol.

  8. Ethynyl-terminated ester oligomers and polymers therefrom

    NASA Technical Reports Server (NTRS)

    Hergenrother, Paul M. (Inventor); Havens, Stephen J. (Inventor)

    1986-01-01

    A class of ethynyl terminated oligomers and the process for preparing the same are disclosed. Upon the application of heat, with or without a catalyst, the ethynyl groups react to provide crosslinking and chain extension to increase the polymer use temperature and improve the polymer solvent resistance. These polyesters are potentially useful in packaging, magnetic tapes, capacitors, industrial belting, protective coatings, structural adhesives and composite matrices.

  9. Using hyperbranched oligomer functionalized glass fillers to reduce shrinkage stress

    PubMed Central

    Ye, Sheng; Azarnoush, Setareh; Smith, Ian R.; Cramer, Neil B.; Stansbury, Jeffrey W.; Bowman, Christopher N

    2012-01-01

    Objective Fillers are widely utilized to enhance the mechanical properties of polymer resins. However, polymerization stress has the potential to increase due to the higher elastic modulus achieved upon filler addition. Here, we demonstrate a hyperbranched oligomer functionalized glass filler UV curable resin composite which is able to reduce the shrinkage stress without sacrificing mechanical properties. Methods A 16-functional alkene-terminated hyperbranched oligomer is synthesized by thiol-acrylate and thiol-yne reactions and the product structure is analyzed by 1H-NMR, mass spectroscopy, and gel permeation chromatography. Surface functionalization of the glass filler is measured by thermogravimetric analysis. Reaction kinetics, mechanical properties and shrinkage stress are studied via Fourier transform infrared spectroscopy, dynamic mechanical analysis and a tensometer, respectively. Results Silica nanoparticles are functionalized with a flexible 16-functional alkene-terminated hyperbranched oligomer which is synthesized by multistage thiol-ene/yne reactions. 93% of the particle surface was covered by this oligomer and an interfacial layer ranging from 0.7 – 4.5 nm thickness is generated. A composite system with these functionalized silica nanoparticles incorporated into the thiol-yne-methacrylate resin demonstrates 30% reduction of shrinkage stress (from 0.9 MPa to 0.6 MPa) without sacrificing the modulus (3100 ± 300 MPa) or glass transition temperature (62 ± 3 °C). Moreover, the shrinkage stress of the composite system builds up at much later stages of the polymerization as compared to the control system. Significance Due to the capability of reducing shrinkage stress without sacrificing mechanical properties, this composite system will be a great candidate for dental composite applications. PMID:22717296

  10. Characterization of reducible peptide oligomers as carriers for gene delivery.

    PubMed

    Kiselev, Anton; Egorova, Anna; Laukkanen, Antti; Baranov, Vladislav; Urtti, Arto

    2013-01-30

    The stability of DNA-polyplexes and intracellular DNA release are important features of gene delivery systems. To study these features, we have evaluated reducible cysteine-flanked linear lysine and arginine-rich peptides, modified with histidine residues. The reducible disulfide bonds in cysteine flanked peptides and histidine residues should augment DNA release from the peptide-DNA complexes upon disintegration of the reducible bonds. Template polymerization and oxidative polycondensation were applied to obtain peptide oligomers used for DNA-polyplex preparation. The peptides and DNA-peptide complexes were investigated with physical, chemical and transfection measurements. Physicochemical and transfection properties of DNA-polyplexes depended on the amino acid sequence of the peptidic polymers and type of the polymerization. MALDI-TOF analysis of oxidatively polycondensed products revealed several forms of peptide oligomers corresponding to 5-8 amino acid monomers. DNA-peptide particles based on template-polymerized complexes were more resistant to relaxation by negatively charged heparan sulfate than polyplexes formed with oxidatively condensed peptides. Complexes of DNA with the polycations prepared by oxidative polycondensation exhibited a 100-1000-fold higher level of gene expression compared to DNA/template-polymerized peptide complexes. The most efficient transgene expression was shown with arginine-rich polyplexes. Transfection efficacy of the arginine-rich polyplexes was even 10-fold better than that of DNA/PEI complexes. On average, polyplexes based on cysteine-flanked peptide oligomers showed lower cytotoxicity than non-reducible high molecular weight polylysine/DNA particles. We conclude that reducible peptide oligomers provide efficient DNA transfection and have the potential as vehicles for gene delivery.

  11. Synthesis of soybean oil-based thiol oligomers.

    PubMed

    Wu, Jennifer F; Fernando, Shashi; Weerasinghe, Dimuthu; Chen, Zhigang; Webster, Dean C

    2011-08-22

    Industrial grade soybean oil (SBO) and thiols were reacted to generate thiol-functionalized oligomers via a thermal, free radical initiated thiol-ene reaction between the SBO double bond moieties and the thiol functional groups. The effect of the reaction conditions, including thiol concentration, catalyst loading level, reaction time, and atmosphere, on the molecular weight and the conversion to the resultant soy-thiols were examined in a combinatorial high-throughput fashion using parallel synthesis, combinatorial FTIR, and rapid gel permeation chromatography (GPC). High thiol functionality and concentration, high thermal free radical catalyst concentration, long reaction time, and the use of a nitrogen reaction atmosphere were found to favor fast consumption of the SBO, and produced high molecular weight products. The thiol conversion during the reaction was inversely affected by a high thiol concentration, but was favored by a long reaction time and an air reaction atmosphere. These experimental observations were explained by the initial low affinity of the SBO and thiol, and the improved affinity between the generated soy-thiol oligomers and unreacted SBO during the reaction. The synthesized soy-thiol oligomers can be used for renewable thiol-ene UV curable materials and high molecular solids and thiourethane thermal cure materials.

  12. Molecular modeling of crystalline alkylthiophene oligomers and polymers.

    PubMed

    Moreno, Margherita; Casalegno, Mosè; Raos, Guido; Meille, Stefano V; Po, Riccardo

    2010-02-04

    We present the results of a thorough molecular modeling study of several alkylthiophene-based oligomers and polymers. In particular, we consider two polymers whose limit-ordered crystal structures have been recently reported by our group, on the basis of powder X-ray data analysis: poly(3-(S)-2-methylbutylthiophene) (P3MBT) and form I' of poly(3-butylthiophene) (P3BT). We first describe the development of a series general purpose force fields for the simulation of these and related systems. The force fields incorporate the results of ab initio calculations of the bond torsion energies of selected oligomers and differ in the set of atomic charges used to represent the electrostatic interactions. We then present the results of an extensive validation of these force fields, by means of molecular mechanics (MM) energy minimizations and molecular dynamics (MD) simulations of the crystal structures of these oligomers and polymers. While our "best" force field does not outperform the others on each of the investigated systems, it provides a balanced description of their overall structure and energetics. Finally, our MM minimizations and MD simulations confirm that the reported crystal structures of P3MBT and P3BT are stable and correspond to well-defined energetic minima. The room-temperature MD simulations reveal a certain degree of side-chain disorder, even in our virtually defect-free polymer crystal models.

  13. Deuteration-induced scission of C{sub 58} oligomers

    SciTech Connect

    Loeffler, Daniel; Jester, Stefan-S.; Weis, Patrick; Boettcher, Artur; Kappes, Manfred M.

    2006-12-14

    The reaction of solid C{sub 58} films with atomic deuterium to yield deuterofullerenes, C{sub 58}D{sub x}, has been investigated by thermal desorption spectroscopy coupled with mass spectrometric detection, ultraviolet photoionization spectroscopy (21.2 eV), and atomic force microscopy (AFM). The average composition of the deuterofullerenes created depends on deuterium dose, beam flux, and surface temperature. Low deuterium exposures at room temperature yield predominantly C{sub 58}D{sub 6-8} cages. Saturation exposures at room temperature yield mass spectra peaked at C{sub 58}D{sub 26}. After saturation exposures at elevated surface temperatures ({approx}500 K), the (subsequently) desorbed material reveals a comparatively narrow mass spectral distribution centered at C{sub 58}D{sub 30}. Deuteration is associated with cleavage of covalent cage-cage bonds in the starting C{sub 58} oligomer material, as evidenced by a considerable lowering of the sublimation energies of C{sub 58}D{sub x} compared to desorption of C{sub 58} desorbed from pure oligomer films. Correspondingly, AFM images reveal a D-induced, thermally activated transition from dendritic C{sub 58} oligomer islands into smooth-rimmed islands composed of deuterated cages. Deuterated films exhibit a significantly lower work function than bare C{sub 58} films. Progressing deuteration also gradually raises the surface ionization potential.

  14. α-Synuclein oligomers and clinical implications for Parkinson disease.

    PubMed

    Kalia, Lorraine V; Kalia, Suneil K; McLean, Pamela J; Lozano, Andres M; Lang, Anthony E

    2013-02-01

    Protein aggregation within the central nervous system has been recognized as a defining feature of neurodegenerative diseases since the early 20th century. Since that time, there has been a growing list of neurodegenerative disorders, including Parkinson disease, which are characterized by inclusions of specific pathogenic proteins. This has led to the long-held dogma that these characteristic protein inclusions, which are composed of large insoluble fibrillar protein aggregates and visible by light microscopy, are responsible for cell death in these diseases. However, the correlation between protein inclusion formation and cytotoxicity is inconsistent, suggesting that another form of the pathogenic proteins may be contributing to neurodegeneration. There is emerging evidence implicating soluble oligomers, smaller protein aggregates not detectable by conventional microscopy, as potential culprits in the pathogenesis of neurodegenerative diseases. The protein α-synuclein is well recognized to contribute to the pathogenesis of Parkinson disease and is the major component of Lewy bodies and Lewy neurites. However, α-synuclein also forms oligomeric species, with certain conformations being toxic to cells. The mechanisms by which these α-synuclein oligomers cause cell death are being actively investigated, as they may provide new strategies for diagnosis and treatment of Parkinson disease and related disorders. Here we review the possible role of α-synuclein oligomers in cell death in Parkinson disease and discuss the potential clinical implications.

  15. Oligomers, organosulfates, and nitroxy organosulfates identified in rainwater

    NASA Astrophysics Data System (ADS)

    Altieri, K. E.; Turpin, B. J.; Seitzinger, S. P.

    2008-12-01

    Wet deposition is an important removal mechanism for atmospheric organic matter, and a potentially important input for receiving ecosystems, yet less than 50 percent of rainwater organic matter is considered chemically characterized. Precipitation samples collected in New Jersey, USA, were analyzed by negative ion ultra-high resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). We document the presence of 552 unique compounds in the rainwater over a mass range of 50-500 Da, in four compound classes (i.e., CHO, CHOS, CHON, and CHONS). The presence of oligomers, organosulfates, nitroxy organosulfates, organic acids, and linear alkylbenzene sulfonates is reported. Some compounds detected have distinct primary sources; however, the composition of the bulk of this material suggests it is formed in the atmosphere and composed of known contributors to secondary organic aerosol. For example, eight oligomer series known to form through aqueous photooxidation of methylglyoxal and organosulfate compounds known to form from 4 precursors in smog chamber experiments were identified in the rainwater samples. The oligomers, organosulfates, and nitroxy organosulfates detected in the rainwater could all contribute to the HULIS fraction of atmospheric organic matter.

  16. Size-dependent neurotoxicity of β-amyloid oligomers

    PubMed Central

    Cizas, Paulius; Budvytyte, Rima; Morkuniene, Ramune; Moldovan, Radu; Broccio, Matteo; Lösche, Mathias; Niaura, Gediminas; Valincius, Gintaras; Borutaite, Vilmante

    2010-01-01

    The link between the size of soluble amyloid β (Aβ) oligomers and their toxicity to rat cerebellar granule cells (CGC) was investigated. Variation in conditions during in vitro oligomerization of Aβ1-42 resulted in peptide assemblies with different particle size as measured by atomic force microscopy and confirmed by the dynamic light scattering and fluorescence correlation spectroscopy. Small oligomers of Aβ1-42 with a mean particle z-height of 1-2 nm exhibited propensity to bind to the phospholipid vesicles and they were the most toxic species that induced rapid neuronal necrosis at submicromolar concentrations whereas the bigger aggregates (z-height above 4-5 nm) did not bind vesicles and did not cause detectable neuronal death. Similar neurotoxic pattern was also observed in primary cultures of cortex neurons whereas Aβ1–42 oligomers, monomers and fibrils were non-toxic to glial cells in CGC cultures or macrophage J774 cells. However, both oligomeric forms of Aβ1-42 induced reduction of neuronal cell densities in the CGC cultures. PMID:20153288

  17. Size-dependent neurotoxicity of beta-amyloid oligomers.

    PubMed

    Cizas, Paulius; Budvytyte, Rima; Morkuniene, Ramune; Moldovan, Radu; Broccio, Matteo; Lösche, Mathias; Niaura, Gediminas; Valincius, Gintaras; Borutaite, Vilmante

    2010-04-15

    The link between the size of soluble amyloid beta (Abeta) oligomers and their toxicity to rat cerebellar granule cells (CGC) was investigated. Variation in conditions during in vitro oligomerization of Abeta(1-42) resulted in peptide assemblies with different particle size as measured by atomic force microscopy and confirmed by dynamic light scattering and fluorescence correlation spectroscopy. Small oligomers of Abeta(1-42) with a mean particle z-height of 1-2 nm exhibited propensity to bind to phospholipid vesicles and they were the most toxic species that induced rapid neuronal necrosis at submicromolar concentrations whereas the bigger aggregates (z-height above 4-5 nm) did not bind vesicles and did not cause detectable neuronal death. A similar neurotoxic pattern was also observed in primary cultures of cortex neurons whereas Abeta(1-42) oligomers, monomers and fibrils were non-toxic to glial cells in CGC cultures or macrophage J774 cells. However, both oligomeric forms of Abeta(1-42) induced reduction of neuronal cell densities in the CGC cultures.

  18. The Viscoelastic Behavior of Polymer/Oligomer Blends

    NASA Astrophysics Data System (ADS)

    Zheng, Wei; McKenna, Gregory; Simon, Sindee

    2009-03-01

    The dynamics in athermal blends of poly(α-methyl styrene) (PaMS) and its short chain oligomer are investigated using rheometry and differential scanning calorimetry (DSC). Master curves for the dynamic shear responses, G' and G", are successfully constructed for both the pure materials and the blends, indicating the validity of the time-temperature superposition principle. The temperature dependence of the shift factor follows the WLF (Williams-Landel-Ferry) behavior over the temperature range studied, and for the blends, the dependence is dominated by the high mobility oligomer. The discrete relaxation spectra of the materials are calculated and are found to be broader for the blends than for the pure materials. A similar domination of the dynamics by the oligomer is observed in DSC enthalpy recovery studies and in the broadened glass transition from DSC. The ability to predict the dynamic responses of the blends from the responses of the neat materials is examined, and whether this prediction needs to incorporate the self-concentration idea as described in Colmenero's model will be discussed.

  19. Calcium-activated gene transfection from DNA/poly(amic acid-co-imide) complexes.

    PubMed

    Wu, Szu-Yuan; Chang, Li-Ting; Peng, Sydeny; Tsai, Hsieh-Chih

    2015-01-01

    In this study, we synthesized a water-soluble poly(amic acid-co-imide) (PA-I) from ethylenediaminetetraacetic dianhydride (EDTA) and 2,2'-(ethylenedioxy)bis(ethylamine) that possesses comparable transfection efficiency to that of polyethylenimine (PEI), when prepared in combination with divalent calcium cations. The polycondensation of monomers afforded poly(amic acid) (PA) precursors, and subsequent thermal imidization resulted in the formation of PA-I. At a polymer/DNA ratio (indicated by the molar ratio of nitrogen in the polymer to phosphate in DNA) of 40, complete retardation of the DNA band was observed by gel electrophoresis, indicating the strong association of DNA with PA-I. A zeta potential of -22 mV was recorded for the PA-I polymer solution, and no apparent cytotoxicity was observed at concentrations up to 500 μg·mL(-1). In the presence of divalent Ca(2+), the transfection efficiency of PA-I was higher than that of PA, due to the formation of a copolymer/Ca(2+)/DNA polyplex and the reduction in negative charge due to thermal cyclization. Interestingly, a synergistic effect of Ca(2+) and the synthesized copolymer on DNA transfection was observed. The use of Ca(2+) or copolymer alone resulted in unsatisfactory delivery, whereas the formation of three-component polyplexes synergistically increased DNA transfection. Our findings demonstrated that a PA-I/Ca(2+)/DNA polyplex could serve as a promising candidate for gene delivery.

  20. Combinations of fluorinated solvents with imide salts or methide salts for electrolytes

    DOEpatents

    Tikhonov, Konstantin; Yip, Ka Ki; Lin, Tzu-Yuan; Lei, Norman; Guerrero-Zavala, Guillermo; Kwong, Kristie W

    2015-11-10

    Provided are electrochemical cells and electrolytes used to build such cells. The electrolytes include imide salts and/or methide salts as well as fluorinated solvents capable of maintaining single phase solutions at between about -30.degree. C. to about 80.degree. C. The fluorinated solvents, such as fluorinated carbonates, fluorinated esters, and fluorinated esters, are less flammable than their non-fluorinated counterparts and improve safety characteristics of cells containing these solvents. The amount of fluorinated solvents in electrolytes may be between about 30% and 80% by weight not accounting weight of the salts. Linear and cyclic imide salts, such as LiN(SO.sub.2CF.sub.2CF.sub.3).sub.2, and LiN(SO.sub.2CF.sub.3).sub.2, as well as methide salts, such as LiC(SO.sub.2CF.sub.3).sub.3 and LiC(SO.sub.2CF.sub.2CF.sub.3).sub.3, may be used in these electrolytes. Fluorinated alkyl groups enhance solubility of these salts in the fluorinated solvents. In some embodiments, the electrolyte may also include a flame retardant, such as a phosphazene, and/or one or more ionic liquids.

  1. Homoleptic alkaline earth metal bis(trifluoromethanesulfonyl)imide complex compounds obtained from an ionic liquid.

    PubMed

    Babai, Arash; Mudring, Anja-Verena

    2006-04-17

    The first homoleptic alkaline earth bis(trifluoromethanesulfonyl)imide (Tf2N) complexes [mppyr]2[Ca(Tf2N)4], [mppyr]2[Sr(Tf2N)4], and [mppyr][Ba(Tf2N)3] were crystallized from a solution of the respective alkaline earth bis(trifluoromethanesulfonyl)imide and the ionic liquid [mppyr][Tf2N] (mppyr = 1,1-N-methyl-N-propylpyrrolidinium). In the calcium and strontium compounds, the alkaline earth metal (AE) is coordinated by four bidentately chelating Tf2N ligands to form isolated (distorted) square antiprismatic [AE(Tf2N)4]2- complexes which are separated by N-methyl-N-propylpyrrolidinium cations. In contrast, the barium compound, [mppyr][Ba(Tf2N)3], forms an extended structure. Here the alkaline earth cation is surrounded by six oxygen atoms belonging to three Tf2N- anions which coordinate in a bidentate chelating fashion. Three further oxygen atoms of the same ligands are linking the Ba2+ cations to infinite (infinity)(1)[Ba(Tf2N)3] chains.

  2. Optimized Ultrasonic Irradiation Finds Out Ultrastable Aβ1-40 Oligomers.

    PubMed

    Nakajima, Kichitaro; So, Masatomo; Takahashi, Kazuma; Tagawa, Yoh-Ichi; Hirao, Masahiko; Goto, Yuji; Ogi, Hirotsugu

    2017-03-16

    Oligomer species of amyloid β (Aβ) peptides are intensively investigated because of their relevance to Alzheimer's disease (AD), and a stable oligomer will be a cause of AD. In this article, we investigate the structural stability of two representative Aβ1-40 oligomers, which are with and without the β-sheet structure, denoted by β and non-β oligomers, respectively, using optimized ultrasonic irradiation (OUI). Recent studies reveal that OUI significantly accelerates the fibril formation in Aβ1-40 monomers; it is capable of transforming any unstable oligomers into fibrils (the dead-end products) in a short time. First, we find that β oligomers can be produced under high-speed stirring agitation; their β-sheet structures are evaluated by the circular-dichroism spectrum measurement, by the immunoassay using the fibril-specific OC antibody, and by the seeding experiment, showing identical characteristics to those formed in previous reports. Second, we form non-β oligomers in a high-concentration NaCl solution and confirm that they include no β-sheet structure, and they are recognized by the oligomer-specific A11 antibody. Furthermore, we confirm the neurotoxicity of the two types of oligomers using the neural tissue derived from mouse embryonic stem cells. We apply the OUI agitation to the β and non-β oligomers. The non-β oligomers are transformed into the fibrils, indicating that they are intermediate species in the fibrillation pathway. However, the β oligomers are surprisingly unaffected by OUI, indicating their high thermodynamic stability. We conclude that the β oligomers should be the independent dead-end products of another pathway, different from the fibrillation pathway.

  3. Synthesis and characterization of mixed oligoheterocycles based on end-capped oligothiophenes suited for LED applications

    NASA Astrophysics Data System (ADS)

    Baeuerle, Peter; Mitschke, Ullrich; Mena-Osteritz, E.; Sokolowski, M.; Mueller, David C.; Gross, Markus S.; Meerholz, Klaus

    1998-12-01

    Homologous series of mixed oligoheterocycles based on end- capped oligothiophenes ECnT 1 were synthesized by introduction of electronegative heteroatoms like oxygen and nitrogen into the conjugated (pi) -system. This led to novel structures 2-11 in which thiophene units of the parent compounds are substituted by other heterocycles with more pronounced acceptor character. Other moieties like phenylsubstituted thiophenes, benzo(c)thiophene, and spiro- bithiophenes have also been implemented resulting in oligothiophenes 12-16. The characterization of the optical and electrochemical properties clearly reveals the influence of the heteroatoms on the electronic properties. Thus e.g., due to the electron withdrawing character of the central heterocycle oxidation of the oligomer is rendered more difficult while reduction is facilitated. In some cases, a hypsochromic shift of the longest wavelength absorption and emission is observed and additionally a significant enhancement of the fluorescence quantum yield in solution and in the solid state. The HOMO/LUMO energy differences determined from the optical measurement correspond qualitatively well with the values obtained from electrochemical data. First experiments on single layer organic light emitting diodes show that these mixed oliogoheterocycles can be used as emitting materials.

  4. A chromatographic estimate of the degree of surface heterogeneity of reversed-phase liquid chromatography packing materials II-Endcapped monomeric C18-bonded stationary phase

    SciTech Connect

    Gritti, Fabrice; Guiochon, Georges A

    2006-01-01

    In a previous report, the heterogeneity of a non-endcapped C{sub 30}-bonded stationary phase was investigated, based on the results of the measurements of the adsorption isotherms of two neutral compounds (phenol and caffeine) and two ionizable compounds (sodium naphthalene sulfonate and propranololium chloride) by frontal analysis (FA). The same method is applied here for the characterization of the surface heterogeneity of two new brands of endcapped C{sub 18}-bonded stationary phases (Gemini and Sunfire). The adsorption isotherms of the same four chemicals were measured by FA and the results confirmed by the independent calculation of the adsorption energy distribution (AED), using the expectation-maximization (EM) method. The effect of the length of the bonded alkyl chain was investigated. Shorter alkyl-bonded-chains (C{sub 18} versus C{sub 30}) and the end-capping of the silica surface contribute to decrease the surface heterogeneity under the same experimental conditions (30% methanol, 25 mM NaCl). The AEDs of phenol and caffeine are bimodal with the C{sub 18}-bonded columns while they are trimodal and quadrimodal, respectively, with a non-endcapped C{sub 30}-bonded column. The 'supersites' (adsorption energy >20 kJ/mol) found on the C{sub 30}-Prontosil column and attributed to a cation exchange mechanism completely disappear on the C{sub 18}-Gemini and C{sub 18}-Sunfire, probably because the end-capping of the silica surface eliminates most if not all the ionic interactions.

  5. Synthesis and Optoelectronic Characterization of Some Star-Shaped Oligomers with Benzene and Triphenylamine Cores

    PubMed Central

    Ivan, Teofilia; Vacareanu, Loredana; Grigoras, Mircea

    2012-01-01

    Six star-shaped oligomers containing triphenylamine (D1–D3) and benzene unit (D4–D6) as cores have been synthesized by Wittig condensation or Heck coupling reaction using aromatic aldehydes and triphenylphosphonium salts or aromatic halogenated compounds with vinyl triphenylamine. All oligomers have well-defined molecular structure and high purity. Characterization of the oligomers was made by FT-IR, 1H-NMR spectroscopy, UV-Vis, and fluorescence spectroscopy. The electrochemical behavior was studied by cyclic voltammetry (CV). The cyclic voltammograms have revealed that oligomers undergo quasireversible or irreversible redox processes. The irreversible process is associated with electrochemical polymerization of oligomers by dimerization of unsubstituted triphenylamine groups. Thermal characterization was accomplished by TGA and DSC methods and evidenced that all oligomers were stable materials until 250°C and have formed stable molecular glasses after first heating scan. PMID:24052859

  6. Radiative decay of excitons in model aggregates of {pi}-conjugated oligomers

    SciTech Connect

    Manas, E.S.; Spano, F.C.

    1998-07-01

    Spontaneous emission from exciton states in an aggregate of {pi}-conjugated oligomers is studied theoretically. Each oligomer is taken as a ring of N carbon atoms and is treated using a PPP Hamiltonian. Coulombic interactions between rings are treated to first order. The radiative decay rate {gamma} from an exciton state in an aggregate of M aligned oligomers is superradiant, being M times faster than the decay rate of an isolated oligomer exciton. Inter-oligomer interactions have little effect on the exciton size and energy when the oligomer size N is large compared to the interoligomer spacing. However, when N is small, both the exciton size and energy are strongly affected by these interactions, leading to a markedly different N dependence for {gamma}.

  7. Organoarsenic compounds with and As=N bond. VII. Reactions of N-aryltriphenylarsine imides with iodoalkanes

    SciTech Connect

    Kokorev, G.I.; Yambushev, F.D.; Badrutdinov, Sh.Kh.

    1987-10-10

    The authors describe the kinetics of the synthesis and the resulting yields of methyltriphenylarsonium triiodide, butyltriphenylarsonium triiodide, and hexyltriphenylarsonoium iodide. N-aryltriphenylarsine imides, unlike their phosphorus analogs, were found to react with the iodoalkanes with breakage of the As=N double bond. Structural and quantitative analyses are performed.

  8. Phase behavior and ionic conductivity in lithium bis(trifluoromethanesulfonyl)imide-doped ionic liquids of the pyrrolidinium cation and Bis(trifluoromethanesulfonyl)imide anion.

    PubMed

    Martinelli, Anna; Matic, Aleksandar; Jacobsson, Per; Börjesson, Lars; Fernicola, Alessandra; Scrosati, Bruno

    2009-08-13

    The phase behavior and the ionic conductivity of ionic liquids (ILs) of the N-alkyl-N-alkylpyrrolidinium (PYR(xy)) cation and the bis(trifluoromethanesulfonyl)imide (TFSI) anion are investigated upon addition of LiTFSI salt. We compare the case of two new ILs of the PYR(2y) cation (where 2 is ethyl and y is butyl or propyl) with that of the PYR(14) (where 1 is methyl and 4 is butyl). We find that the addition of LiTFSI increases the glass transition temperature, decreases the melting temperature and the heat of fusion and, in the ILs of the PYR(2y) family, suppresses crystallization. In the solid state, significant ionic conductivities are found, being as high as 10(-5) S cm(-1), strongly increasing with Li(+) concentration. The opposite trend is found in the liquid state, where the conductivity is on the order of 10(-3)-10(-2) S cm(-1) at room temperature. A T(g)-scaled Arrhenius plot shows that the liquid-state ionic conductivity in these systems is mainly governed by viscosity and that the fragility of the liquids is slightly influenced by the structural modifications on the cation.

  9. Algorithm and implementation of muon trigger and data transmission system for barrel-endcap overlap region of the CMS detector

    NASA Astrophysics Data System (ADS)

    Zabolotny, W. M.; Byszuk, A.

    2016-03-01

    The CMS experiment Level-1 trigger system is undergoing an upgrade. In the barrel-endcap transition region, it is necessary to merge data from 3 types of muon detectors—RPC, DT and CSC. The Overlap Muon Track Finder (OMTF) uses the novel approach to concentrate and process those data in a uniform manner to identify muons and their transversal momentum. The paper presents the algorithm and FPGA firmware implementation of the OMTF and its data transmission system in CMS. It is foreseen that the OMTF will be subject to significant changes resulting from optimization which will be done with the aid of physics simulations. Therefore, a special, high-level, parameterized HDL implementation is necessary.

  10. Neutron and Proton Tests of Different Technologies for the Upgrade of Cold Readout Electronics of the Atlas Hadronic Endcap Calorimeter

    NASA Astrophysics Data System (ADS)

    Nagel, M.

    2012-08-01

    The expected increase of total integrated luminosity by a factor of ten at the HL-LHC compared to the design goals for LHC essentially eliminates the safety factor for radiation hardness realized at the current cold amplifiers of the ATLAS Hadronic Endcap Calorimeter (HEC). New more radiation hard technologies have been studied: SiGe bipolar, Si CMOS FET and GaAs FET transistors have been irradiated with neutrons up to an integrated fluence of 2.2 · 1016 n/cm2 and with 200 MeV protons up to an integrated fluence of 2.6 · 1014 p/cm2. Comparisons of transistor parameters such as the gain for both types of irradiations are presented.

  11. Removal of a femoral nail with osseous overgrowth at the end-cap: A navigated and cannulated minimally invasive technique.

    PubMed

    Marintschev, Ivan; Rausch, Sascha; Fujak, Albert; Klos, Kajetan; Hofmann, Gunther O; Gras, Florian

    2013-01-01

    Intramedullary nail removal can be demanding, especially in cases of implant breakage or bony overgrowth at the end-cap, if the exact insertion depth of the nail is neglected in the index surgery. In the presented case, two challenging nail removals were necessary. The first was performed in a re-nailing procedure due to a pseudarthrosis with implant breakage, and the second was performed during hardware removal after fracture healing in a situation where there was deep intramedullary placement of the exchange nail. For the second implant removal a minimally invasive approach based on instrument placements over a navigated guide-wire was used to reduce the iatrogenic morbidity associated with an extensive open approach to the nail and to decrease the radiation exposure for the patient and the operating team.

  12. Direct Correlation Between Ligand-Induced α-Synuclein Oligomers and Amyloid-like Fibril Growth

    PubMed Central

    Nors Perdersen, Martin; Foderà, Vito; Horvath, Istvan; van Maarschalkerweerd, Andreas; Nørgaard Toft, Katrine; Weise, Christoph; Almqvist, Fredrik; Wolf-Watz, Magnus; Wittung-Stafshede, Pernilla; Vestergaard, Bente

    2015-01-01

    Aggregation of proteins into amyloid deposits is the hallmark of several neurodegenerative diseases such as Alzheimer’s and Parkinson’s disease. The suggestion that intermediate oligomeric species may be cytotoxic has led to intensified investigations of pre-fibrillar oligomers, which are complicated by their transient nature and low population. Here we investigate alpha-synuclein oligomers, enriched by a 2-pyridone molecule (FN075), and the conversion of oligomers into fibrils. As probed by leakage assays, the FN075 induced oligomers potently disrupt vesicles in vitro, suggesting a potential link to disease related degenerative activity. Fibrils formed in the presence and absence of FN075 are indistinguishable on microscopic and macroscopic levels. Using small angle X-ray scattering, we reveal that FN075 induced oligomers are similar, but not identical, to oligomers previously observed during alpha-synuclein fibrillation. Since the levels of FN075 induced oligomers correlate with the amounts of fibrils among different FN075:protein ratios, the oligomers appear to be on-pathway and modeling supports an ‘oligomer stacking model’ for alpha-synuclein fibril elongation. PMID:26020724

  13. Quantitative analysis of co-oligomer formation by amyloid-beta peptide isoforms

    NASA Astrophysics Data System (ADS)

    Iljina, Marija; Garcia, Gonzalo A.; Dear, Alexander J.; Flint, Jennie; Narayan, Priyanka; Michaels, Thomas C. T.; Dobson, Christopher M.; Frenkel, Daan; Knowles, Tuomas P. J.; Klenerman, David

    2016-06-01

    Multiple isoforms of aggregation-prone proteins are present under physiological conditions and have the propensity to assemble into co-oligomers with different properties from self-oligomers, but this process has not been quantitatively studied to date. We have investigated the amyloid-β (Aβ) peptide, associated with Alzheimer’s disease, and the aggregation of its two major isoforms, Aβ40 and Aβ42, using a statistical mechanical modelling approach in combination with in vitro single-molecule fluorescence measurements. We find that at low concentrations of Aβ, corresponding to its physiological abundance, there is little free energy penalty in forming co-oligomers, suggesting that the formation of both self-oligomers and co-oligomers is possible under these conditions. Our model is used to predict the oligomer concentration and size at physiological concentrations of Aβ and suggests the mechanisms by which the ratio of Aβ42 to Aβ40 can affect cell toxicity. An increased ratio of Aβ42 to Aβ40 raises the fraction of oligomers containing Aβ42, which can increase the hydrophobicity of the oligomers and thus promote deleterious binding to the cell membrane and increase neuronal damage. Our results suggest that co-oligomers are a common form of aggregate when Aβ isoforms are present in solution and may potentially play a significant role in Alzheimer’s disease.

  14. Low-resolution structure of a vesicle disrupting α-synuclein oligomer that accumulates during fibrillation

    PubMed Central

    Giehm, Lise; Svergun, Dmitri I.; Otzen, Daniel E.; Vestergaard, Bente

    2011-01-01

    One of the major hallmarks of Parkinson disease is aggregation of the protein α-synuclein (αSN). Aggregate cytotoxicity has been linked to an oligomeric species formed at early stages in the aggregation process. Here we follow the fibrillation process of αSN in solution over time using small angle X-ray scattering and resolve four major coexisting species in the fibrillation process, namely monomer, dimer, fibril and an oligomer. By ab initio modeling to fit the data, we obtain a low-resolution structure of a symmetrical and slender αSN fibril in solution, consisting of a repeating unit with a maximal distance of 900 Å and a diameter of ∼180 Å. The same approach shows the oligomer to be shaped like a wreath, with a central channel and with dimensions corresponding to the width of the fibril. The structure, accumulation and decay of this oligomer is consistent with an on-pathway role for the oligomer in the fibrillation process. We propose an oligomer-driven αSN fibril formation mechanism, where the fibril is built from the oligomers. The wreath-shaped structure of the oligomer highlights its potential cytotoxicity by simple membrane permeabilization. This is confirmed by the ability of the purified oligomer to disrupt liposomes. Our results provide the first structural description in solution of a potentially cytotoxic oligomer, which accumulates during the fibrillation of αSN. PMID:21300904

  15. Self-Assembly of Telechelic Tyrosine End-Capped PEO and Poly(alanine) Polymers in Aqueous Solution.

    PubMed

    Kirkham, Steven; Castelletto, Valeria; Hamley, Ian William; Reza, Mehedi; Ruokolainen, Janne; Hermida-Merino, Daniel; Bilalis, Panayiotis; Iatrou, Hermis

    2016-03-14

    The self-assembly in aqueous solution of three novel telechelic conjugates comprising a central hydrophilic polymer and short (trimeric or pentameric) tyrosine end-caps has been investigated. Two of the conjugates have a central poly(oxyethylene) (polyethylene oxide, PEO) central block with different molar masses. The other conjugate has a central poly(L-alanine) (PAla) sequence in a purely amino-acid based conjugate. All three conjugates self-assemble into β-sheet based fibrillar structures, although the fibrillar morphology revealed by cryogenic-TEM is distinct for the three polymers--in particular the Tyr5-PEO6k-Tyr5 forms a population of short straight fibrils in contrast to the more diffuse fibril aggregates observed for Tyr5-PEO2k-Tyr5 and Tyr3-PAla-Tyr3. Hydrogel formation was not observed for these samples (in contrast to prior work on related systems) up to quite high concentrations, showing that it is possible to prepare solutions of peptide-polymer-peptide conjugates with hydrophobic end-caps without conformational constraints associated with hydrogelation. The Tyr5-PEO6k-Tyr5 shows significant PEO crystallization upon drying in contrast to the Tyr5-PEO2k-Tyr5 conjugate. Our findings point to the remarkable ability of short hydrophobic peptide end groups to modulate the self-assembly properties of polymers in solution in model peptide-capped "associative polymers". Retention of fluidity at high conjugate concentration may be valuable in potential future applications of these conjugates as bioresponsive or biocompatible materials, for example exploiting the enzyme-responsiveness of the tyrosine end-groups.

  16. (Photo)physical Properties of New Molecular Glasses End-Capped with Thiophene Rings Composed of Diimide and Imine Units

    PubMed Central

    2014-01-01

    New symmetrical arylene bisimide derivatives formed by using electron-donating–electron-accepting systems were synthesized. They consist of a phthalic diimide or naphthalenediimide core and imine linkages and are end-capped with thiophene, bithiophene, and (ethylenedioxy)thiophene units. Moreover, polymers were obtained from a new diamine, N,N′-bis(5-aminonaphthalenyl)naphthalene-1,4,5,8-dicarboximide and 2,5-thiophenedicarboxaldehyde or 2,2′-bithiophene-5,5′-dicarboxaldehyde. The prepared azomethine diimides exhibited glass-forming properties. The obtained compounds emitted blue light with the emission maximum at 470 nm. The value of the absorption coefficient was determined as a function of the photon energy using spectroscopic ellipsometry. All compounds are electrochemically active and undergo reversible electrochemical reduction and irreversible oxidation processes as was found in cyclic voltammetry and differential pulse voltammetry (DPV) studies. They exhibited a low electrochemically (DPV) calculated energy band gap (Eg) from 1.14 to 1.70 eV. The highest occupied molecular orbital and lowest unoccupied molecular orbital levels and Eg were additionally calculated theoretically by density functional theory at the B3LYP/6-31G(d,p) level. The photovoltaic properties of two model compounds as the active layer in organic solar cells in the configuration indium tin oxide/poly(3,4-(ethylenedioxy)thiophene):poly(styrenesulfonate)/active layer/Al under an illumination of 1.3 mW/cm2 were studied. The device comprising poly(3-hexylthiophene) with the compound end-capped with bithiophene rings showed the highest value of Voc (above 1 V). The conversion efficiency of the fabricated solar cell was in the range of 0.69–0.90%. PMID:24966893

  17. A chromatographic estimate of the degree of surface heterogeneity of RPLC packing materials. III. Endcapped amido-embedded reversed phase

    SciTech Connect

    Gritti, Fabrice; Guiochon, Georges A

    2006-01-01

    The difference in adsorption behavior between a conventional monomeric endcapped C{sub 18} stationary phase (3.43 {micro}mol/m{sup 2}) and an endcapped polymeric RP-Amide phase (3.31 {micro}mol/m{sup 2}) was investigated. The adsorption isotherms of four compounds (phenol, caffeine, sodium 2-naphthalene sulfonate, and propranololium chloride) were measured by frontal analysis (FA) and the degree of heterogeneity of each phase for each solute was characterized by their adsorption energy distributions (AED), derived using the Expectation-Maximization method. The results show that only certain analytes (phenol and 2-naphthalene sulfonate) are sensitive to the presence of the polar embedded amide groups within the RP phase. Their binding constants on the amide-bonded phase are significantly higher than on conventional RPLC phases. Furthermore, an additional type of adsorption sites was observed for these two compounds. However, these sites having a low density, their presence does not affect much the retention factors of the two analytes. On the other hand, the adsorption behavior of the other two analytes (caffeine and propranololium chloride) is almost unaffected by the presence of the amide group in the bonded layer. Strong selective interactions may explain these observations. For example, hydrogen-bond interactions between an analyte (e.g., phenol or naphthalene sulfonate) and the carbonyl group (acceptor) or the nitrogen (donor) of the amido-embedded group may take place. No such interactions may take place with either caffeine or the cation propranololium chloride. This study confirms the hypothesis that analytes have ready access to locations deep inside the bonded layer, where the amide groups are present.

  18. Versatile and sustainable synthesis of cyclic imides from dicarboxylic acids and amines by Nb2O5 as a base-tolerant heterogeneous Lewis acid catalyst.

    PubMed

    Ali, Md Ayub; Siddiki, S M A Hakim; Kon, Kenichi; Hasegawa, Junya; Shimizu, Ken-Ichi

    2014-10-27

    Catalytic condensation of dicarboxylics acid and amines without excess amount of activating reagents is the most atom-efficient but unprecedented synthetic method of cyclic imides. Here we present the first general catalytic method, proceeding selectively and efficiently in the presence of a commercial Nb2 O5 as a reusable and base-tolerant heterogeneous Lewis acid catalyst. The method is effective for the direct synthesis of pharmaceutically or industrially important cyclic imides, such as phensuximide, N-hydroxyphthalimide (NHPI), and unsubstituted cyclic imides from dicarboxylic acid or anhydrides with amines, hydroxylamine, or ammonia.

  19. Modified Phenylethynyl Containing Imides for Secondary Bonding: Non-Autoclave, Low Temperature Processable Adhesives

    NASA Technical Reports Server (NTRS)

    Dezern, James F. (Technical Monitor); Chang, Alice C.

    1999-01-01

    As part of a program to develop structural adhesives for high performance aerospace applications, research continued on the development of modified phenylethynyl containing imides, LaRC(trademark)MPEIs. In previous reports, the polymer properties were controlled by varying the molecular weight, the amount of branching, and the phenylethynyl content and by blending with low molecular weight materials. This research involves changing the flexibility in the copolyimide backbone of the branched, phenylethynyl terminated adhesives. These adhesives exhibit excellent processability at pressures as low as 15 psi and temperatures as low as 288 C. The Ti/Ti lap shear specimens are processable in an autoclave or a temperature programmable oven under a vacuum bag at 288-300 C without external pressure. The cured polymers exhibit high mechanical properties and excellent solvent resistance. The chemistry and properties of these adhesives are presented.

  20. Challenges in Laser Sintering of Melt-Processable Thermoset Imide Resin

    NASA Technical Reports Server (NTRS)

    Chuang, Kathy C.; Gornet, Timothy; Koerner, Hilmar

    2016-01-01

    Polymer Laser Sintering (LS) is an additive manufacturing technique that builds 3D models layer by layer using a laser to selectively melt cross sections in powdered polymeric materials, following sequential slices of the CAD model. LS generally uses thermoplastic polymeric powders, such as polyamides (i.e. Nylon), and the resultant 3D objects are often weaker in their strength compared to traditionally processed materials, due to the lack of polymer inter-chain connection in the z-direction. The objective of this project is to investigate the possibility of printing a melt-processable RTM370 imide resin powder terminated with reactive phenylethynyl groups by LS, followed by a postcure in order to promote additional crosslinking to achieve higher temperature (250-300 C) capability. A preliminary study to build tensile specimens by LS and the corresponding DSC and rheology study of RTM370 during LS process is presented.

  1. Transparent organic p-dopant in carbon nanotubes: bis(trifluoromethanesulfonyl)imide.

    PubMed

    Kim, Soo Min; Jo, Young Woo; Kim, Ki Kang; Duong, Dinh Loc; Shin, Hyeon-Jin; Han, Jong Hun; Choi, Jae-Young; Kong, Jing; Lee, Young Hee

    2010-11-23

    We propose bis(trifluoromethanesulfonyl)imide [(CF(3)SO(2))(2)N](-) (TFSI) as a transparent strong electron-withdrawing p-type dopant in carbon nanotubes (CNTs). The conventional p-dopant, AuCl(3), has several drawbacks, such as hygroscopic effect, formation of Au clusters, decrease in transmittance, and high cost in spite of the significant increase in conductivity. TFSI is converted from bis(trifluoromethanesulfonyl)amine (TFSA) by accepting electrons from CNTs, subsequently losing a proton as a characteristic of a Brønsted acid, and has an inductive effect from atoms with high electronegativity, such as halogen, oxygen, and nitrogen. TFSI produced a similar improvement in conductivity to AuCl(3), while maintaining high thermal stability, and no appreciable change in transmittance with no cluster formation. The effectiveness of TFSI was compared with that of other derivatives.

  2. Electrorheology of aniline-oligomer suspensions under oscillatory shear

    NASA Astrophysics Data System (ADS)

    Mrlik, M.; Pavlinek, V.; Almajdalawi, S.; Saha, P.; Bober, P.; Stejskal, J.

    2013-02-01

    Preparation of the aniline oligomers by the oxidation of aniline with p-benzoquinone in the solutions of methanesulfonic acid (MSA) and the rheology of their suspensions in silicone oil are presented in this study. This synthesis provides particles of flake-like morphology and various conductivities depending on the molar concentration of MSA. Further, the electrorheological (ER) performance of the particles suspended in the silicone oil was measured as well as dielectric properties of suspensions. Finally, the effect of the temperature on the ER activity was investigated.

  3. High-Performance Nonfullerene Polymer Solar Cells based on Imide-Functionalized Wide-Bandgap Polymers.

    PubMed

    Fan, Baobing; Zhang, Kai; Jiang, Xiao-Fang; Ying, Lei; Huang, Fei; Cao, Yong

    2017-03-23

    High-performance nonfullerene polymer solar cells (PSCs) are developed by integrating the nonfullerene electron-accepting material 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophne) (ITIC) with a wide-bandgap electron-donating polymer PTzBI or PTzBI-DT, which consists of an imide functionalized benzotriazole (TzBI) building block. Detailed investigations reveal that the extension of conjugation can affect the optical and electronic properties, molecular aggregation properties, charge separation in the bulk-heterojunction films, and thus the overall photovoltaic performances. Single-junction PSCs based on PTzBI:ITIC and PTzBI-DT:ITIC exhibit remarkable power conversion efficiencies (PCEs) of 10.24% and 9.43%, respectively. To our knowledge, these PCEs are the highest efficiency values obtained based on electron-donating conjugated polymers consisting of imide-functionalized electron-withdrawing building blocks. Of particular interest is that the resulting device based on PTzBI exhibits remarkable PCE of 7% with the thickness of active layer of 300 nm, which is among the highest values of nonfullerene PSCs utilizing thick photoactive layer. Additionally, the device based on PTzBI:ITIC exhibits prominent stability, for which the PCE remains as 9.34% after thermal annealing at 130 °C for 120 min. These findings demonstrate the great promise of using this series of wide-bandgap conjugated polymers as electron-donating materials for high-performance nonfullerene solar cells toward high-throughput roll-to-roll processing technology.

  4. Calcium-activated gene transfection from DNA/poly(amic acid-co-imide) complexes

    PubMed Central

    Wu, Szu-Yuan; Chang, Li-Ting; Peng, Sydeny; Tsai, Hsieh-Chih

    2015-01-01

    In this study, we synthesized a water-soluble poly(amic acid-co-imide) (PA-I) from ethylenediaminetetraacetic dianhydride (EDTA) and 2,2′-(ethylenedioxy)bis(ethylamine) that possesses comparable transfection efficiency to that of polyethylenimine (PEI), when prepared in combination with divalent calcium cations. The polycondensation of monomers afforded poly(amic acid) (PA) precursors, and subsequent thermal imidization resulted in the formation of PA-I. At a polymer/DNA ratio (indicated by the molar ratio of nitrogen in the polymer to phosphate in DNA) of 40, complete retardation of the DNA band was observed by gel electrophoresis, indicating the strong association of DNA with PA-I. A zeta potential of −22 mV was recorded for the PA-I polymer solution, and no apparent cytotoxicity was observed at concentrations up to 500 μg·mL−1. In the presence of divalent Ca2+, the transfection efficiency of PA-I was higher than that of PA, due to the formation of a copolymer/Ca2+/DNA polyplex and the reduction in negative charge due to thermal cyclization. Interestingly, a synergistic effect of Ca2+ and the synthesized copolymer on DNA transfection was observed. The use of Ca2+ or copolymer alone resulted in unsatisfactory delivery, whereas the formation of three-component polyplexes synergistically increased DNA transfection. Our findings demonstrated that a PA-I/Ca2+/DNA polyplex could serve as a promising candidate for gene delivery. PMID:25767385

  5. Aromatic small molecules remodel toxic soluble oligomers of amyloid beta through three independent pathways.

    PubMed

    Ladiwala, Ali Reza A; Dordick, Jonathan S; Tessier, Peter M

    2011-02-04

    In protein conformational disorders ranging from Alzheimer to Parkinson disease, proteins of unrelated sequence misfold into a similar array of aggregated conformers ranging from small oligomers to large amyloid fibrils. Substantial evidence suggests that small, prefibrillar oligomers are the most toxic species, yet to what extent they can be selectively targeted and remodeled into non-toxic conformers using small molecules is poorly understood. We have evaluated the conformational specificity and remodeling pathways of a diverse panel of aromatic small molecules against mature soluble oligomers of the Aβ42 peptide associated with Alzheimer disease. We find that small molecule antagonists can be grouped into three classes, which we herein define as Class I, II, and III molecules, based on the distinct pathways they utilize to remodel soluble oligomers into multiple conformers with reduced toxicity. Class I molecules remodel soluble oligomers into large, off-pathway aggregates that are non-toxic. Moreover, Class IA molecules also remodel amyloid fibrils into the same off-pathway structures, whereas Class IB molecules fail to remodel fibrils but accelerate aggregation of freshly disaggregated Aβ. In contrast, a Class II molecule converts soluble Aβ oligomers into fibrils, but is inactive against disaggregated and fibrillar Aβ. Class III molecules disassemble soluble oligomers (as well as fibrils) into low molecular weight species that are non-toxic. Strikingly, Aβ non-toxic oligomers (which are morphologically indistinguishable from toxic soluble oligomers) are significantly more resistant to being remodeled than Aβ soluble oligomers or amyloid fibrils. Our findings reveal that relatively subtle differences in small molecule structure encipher surprisingly large differences in the pathways they employ to remodel Aβ soluble oligomers and related aggregated conformers.

  6. Amyloid oligomer structure characterization from simulations: A general method

    SciTech Connect

    Nguyen, Phuong H.; Li, Mai Suan

    2014-03-07

    Amyloid oligomers and plaques are composed of multiple chemically identical proteins. Therefore, one of the first fundamental problems in the characterization of structures from simulations is the treatment of the degeneracy, i.e., the permutation of the molecules. Second, the intramolecular and intermolecular degrees of freedom of the various molecules must be taken into account. Currently, the well-known dihedral principal component analysis method only considers the intramolecular degrees of freedom, and other methods employing collective variables can only describe intermolecular degrees of freedom at the global level. With this in mind, we propose a general method that identifies all the structures accurately. The basis idea is that the intramolecular and intermolecular states are described in terms of combinations of single-molecule and double-molecule states, respectively, and the overall structures of oligomers are the product basis of the intramolecular and intermolecular states. This way, the degeneracy is automatically avoided. The method is illustrated on the conformational ensemble of the tetramer of the Alzheimer's peptide Aβ{sub 9−40}, resulting from two atomistic molecular dynamics simulations in explicit solvent, each of 200 ns, starting from two distinct structures.

  7. Broadband terahertz dynamics of propylene glycol monomer and oligomers

    NASA Astrophysics Data System (ADS)

    Koda, Shota; Mori, Tatsuya; Kojima, Seiji

    2016-12-01

    We investigated the broadband terahertz spectra (0.1-5.0 THz) of glass-forming liquids, propylene glycol (PG), its oligomers poly (propylene glycol)s (PPGs), and poly (propylene glycol) diglycidyl ether (PPG-de) using broadband terahertz time-domain spectroscopy and low-frequency Raman scattering. The numerical value of the dielectric loss at around 1.5 THz, which is the peak position of broad peaks in all samples, decreased as the molecular weight increased. Furthermore, the peak at around 1.5 THz is insensitive to the molecular weight. For PPGs, the side chain effect of the oligomer was observed in the terahertz region. Based on the experimental and calculation results for the PPGs and PPG-de, whose end groups are epoxy groups, the beginnings of the increases in the observed dielectric loss above 3.5 THz of the PPGs are assigned to the OH bending vibration. The higher value of the dielectric loss in the terahertz region for the PPG-de can be the tail of a broad peak located in the MHz region. The difference between the Raman susceptibility and dielectric loss reflects the difference in the observable molecular dynamics between the infrared and Raman spectroscopies.

  8. Amyloid oligomer structure characterization from simulations: A general method

    NASA Astrophysics Data System (ADS)

    Nguyen, Phuong H.; Li, Mai Suan; Derreumaux, Philippe

    2014-03-01

    Amyloid oligomers and plaques are composed of multiple chemically identical proteins. Therefore, one of the first fundamental problems in the characterization of structures from simulations is the treatment of the degeneracy, i.e., the permutation of the molecules. Second, the intramolecular and intermolecular degrees of freedom of the various molecules must be taken into account. Currently, the well-known dihedral principal component analysis method only considers the intramolecular degrees of freedom, and other methods employing collective variables can only describe intermolecular degrees of freedom at the global level. With this in mind, we propose a general method that identifies all the structures accurately. The basis idea is that the intramolecular and intermolecular states are described in terms of combinations of single-molecule and double-molecule states, respectively, and the overall structures of oligomers are the product basis of the intramolecular and intermolecular states. This way, the degeneracy is automatically avoided. The method is illustrated on the conformational ensemble of the tetramer of the Alzheimer's peptide Aβ9-40, resulting from two atomistic molecular dynamics simulations in explicit solvent, each of 200 ns, starting from two distinct structures.

  9. Lipid raft disruption protects mature neurons against amyloid oligomer toxicity.

    PubMed

    Malchiodi-Albedi, Fiorella; Contrusciere, Valentina; Raggi, Carla; Fecchi, Katia; Rainaldi, Gabriella; Paradisi, Silvia; Matteucci, Andrea; Santini, Maria Teresa; Sargiacomo, Massimo; Frank, Claudio; Gaudiano, Maria Cristina; Diociaiuti, Marco

    2010-04-01

    A specific neuronal vulnerability to amyloid protein toxicity may account for brain susceptibility to protein misfolding diseases. To investigate this issue, we compared the effects induced by oligomers from salmon calcitonin (sCTOs), a neurotoxic amyloid protein, on cells of different histogenesis: mature and immature primary hippocampal neurons, primary astrocytes, MG63 osteoblasts and NIH-3T3 fibroblasts. In mature neurons, sCTOs increased apoptosis and induced neuritic and synaptic damages similar to those caused by amyloid beta oligomers. Immature neurons and the other cell types showed no cytotoxicity. sCTOs caused cytosolic Ca(2+) rise in mature, but not in immature neurons and the other cell types. Comparison of plasma membrane lipid composition showed that mature neurons had the highest content in lipid rafts, suggesting a key role for them in neuronal vulnerability to sCTOs. Consistently, depletion in gangliosides protected against sCTO toxicity. We hypothesize that the high content in lipid rafts makes mature neurons especially vulnerable to amyloid proteins, as compared to other cell types; this may help explain why the brain is a target organ for amyloid-related diseases.

  10. Charge transfer interactions in oligomer coated gold nanoclusters

    NASA Astrophysics Data System (ADS)

    Newmai, M. Boazbou; Kumar, Pandian Senthil

    2016-05-01

    Gold nanoclusters were synthesized by a bottom-up synergistic approach of in-situ oligomerization of the monomer, N-vinyl pyrrolidone (NVP) and simultaneous weak reduction of Au-NVP complexes in the absence of any other external energy sources, thereby making these tiny gold clusters as the most elemental building blocks to construct further novel nano/microstructures with application potentials. It is well-known that metal clusters with less than 2 nm size do not show the usual surface plasmon band, because of the presence of a band-gap at the fermi level. Nevertheless, our present oligomer coated gold clusters show a discrete intense band at around 630 nm, which could very well be attributed to the charge transfer between the oligomer chain and the surface Au atoms. Such kind of sacrificial plasmon induced charge transfer interaction, observed for the very first time to the best of our knowledge, were also strongly corroborated through the enhancement / shifting of specific vibrational / rotational peaks as observed from the FTIR and Raman measurements as a function of the metal oxidation states, thus representing a new prototype for an efficient solar energy conversion probe.

  11. Amyloid oligomer structure characterization from simulations: a general method.

    PubMed

    Nguyen, Phuong H; Li, Mai Suan; Derreumaux, Philippe

    2014-03-07

    Amyloid oligomers and plaques are composed of multiple chemically identical proteins. Therefore, one of the first fundamental problems in the characterization of structures from simulations is the treatment of the degeneracy, i.e., the permutation of the molecules. Second, the intramolecular and intermolecular degrees of freedom of the various molecules must be taken into account. Currently, the well-known dihedral principal component analysis method only considers the intramolecular degrees of freedom, and other methods employing collective variables can only describe intermolecular degrees of freedom at the global level. With this in mind, we propose a general method that identifies all the structures accurately. The basis idea is that the intramolecular and intermolecular states are described in terms of combinations of single-molecule and double-molecule states, respectively, and the overall structures of oligomers are the product basis of the intramolecular and intermolecular states. This way, the degeneracy is automatically avoided. The method is illustrated on the conformational ensemble of the tetramer of the Alzheimer's peptide Aβ9-40, resulting from two atomistic molecular dynamics simulations in explicit solvent, each of 200 ns, starting from two distinct structures.

  12. Sedimentation studies on human amylin fail to detect low-molecular-weight oligomers.

    PubMed

    Vaiana, Sara M; Ghirlando, Rodolfo; Yau, Wai-Ming; Eaton, William A; Hofrichter, James

    2008-04-01

    Sedimentation velocity experiments show that only monomers coexist with amyloid fibrils of human islet amyloid-polypeptide. No oligomers containing <100 monomers could be detected, suggesting that the putative toxic oligomers are much larger than those found for the Alzheimer's peptide, Abeta(1-42).

  13. Heat Resistant Characteristics of Major Royal Jelly Protein 1 (MRJP1) Oligomer.

    PubMed

    Moriyama, Takanori; Ito, Aimi; Omote, Sumire; Miura, Yuri; Tsumoto, Hiroki

    2015-01-01

    Soluble royal jelly protein is a candidate factor responsible for mammiferous cell proliferation. Major royal jelly protein 1 (MRJP1), which consists of oligomeric and monomeric forms, is an abundant proliferative protein in royal jelly. We previously reported that MRJP1 oligomer has biochemical heat resistance. Therefore, in the present study, we investigated the effects of several heat treatments (56, 65 and 96°C) on the proliferative activity of MRJP1 oligomer. Heat resistance studies showed that the oligomer molecular forms were slightly maintained until 56℃, but the molecular forms were converted to macromolecular heat-aggregated MRJP1 oligomer at 65℃ and 96℃. But, the growth activity of MRJP1 oligomer treated with 96°C was slightly attenuated when compared to unheated MRJP1 oligomer. On the other hand, the cell proliferation activity was preserved until 96℃ by the cell culture analysis of Jurkat cells. In contrast, those of IEC-6 cells were not preserved even at 56°C. The present observations suggest that the bioactive heat-resistance properties were different by the origin of the cells. The cell proliferation analysis showed that MRJP1 oligomer, but not MRJP2 and MRJP3, significantly increased cell numbers, suggesting that MRJP1 oligomer is the predominant proliferation factor for mammiferous cells.

  14. Seeding induced by alpha-synuclein oligomers provides evidence for spreading of alpha-synuclein pathology.

    PubMed

    Danzer, Karin M; Krebs, Simon K; Wolff, Michael; Birk, Gerald; Hengerer, Bastian

    2009-10-01

    Lewy bodies, alpha-synuclein (alpha-syn) immunopositive intracellular deposits, are the pathological hallmark of Parkinson's disease (PD). Interestingly, Lewybody-like structures have been identified in fetal tissue grafts about one decade after transplantation into the striatum of PD patients. One possible explanation for the accelerated deposition of alpha-syn in the graft is that the aggregation of alpha-syn from the host tissue to the graft is spread by a prion disease-like mechanism. We discuss here an in vitro model which might recapitulate some aspects of disease propagation in PD. We found here that in vitro-generated alpha-syn oligomers induce transmembrane seeding of alpha-syn aggregation in a dose- and time-dependent manner. This effect was observed in primary neuronal cultures as well as in neuronal cell lines. The seeding oligomers were characterized by a distinctive lithium dodecyl sulfate-stable oligomer pattern and could be generated in a dynamic process out of pore-forming oligomers. We propose that alpha-syn oligomers form as a dynamic mixture of oligomer types with different properties and that alpha-syn oligomers can be converted into different types depending on the brain milieu conditions. Our data indicate that extracellular alpha-syn oligomers can induce intracellular alpha-syn aggregation, therefore we hypothesize that a similar mechanism might lead to alpha-syn pathology propagation.

  15. Amyloid-beta oligomers increase the localization of prion protein at the cell surface.

    PubMed

    Caetano, Fabiana A; Beraldo, Flavio H; Hajj, Glaucia N M; Guimaraes, Andre L; Jürgensen, Sofia; Wasilewska-Sampaio, Ana Paula; Hirata, Pedro H F; Souza, Ivana; Machado, Cleiton F; Wong, Daisy Y-L; De Felice, Fernanda G; Ferreira, Sergio T; Prado, Vania F; Rylett, R Jane; Martins, Vilma R; Prado, Marco A M

    2011-05-01

    In Alzheimer's disease, the amyloid-β peptide (Aβ) interacts with distinct proteins at the cell surface to interfere with synaptic communication. Recent data have implicated the prion protein (PrP(C)) as a putative receptor for Aβ. We show here that Aβ oligomers signal in cells in a PrP(C)-dependent manner, as might be expected if Aβ oligomers use PrP(C) as a receptor. Immunofluorescence, flow cytometry and cell surface protein biotinylation experiments indicated that treatment with Aβ oligomers, but not monomers, increased the localization of PrP(C) at the cell surface in cell lines. These results were reproduced in hippocampal neuronal cultures by labeling cell surface PrP(C). In order to understand possible mechanisms involved with this effect of Aβ oligomers, we used live cell confocal and total internal reflection microscopy in cell lines. Aβ oligomers inhibited the constitutive endocytosis of PrP(C), but we also found that after Aβ oligomer-treatment PrP(C) formed more clusters at the cell surface, suggesting the possibility of multiple effects of Aβ oligomers. Our experiments show for the first time that Aβ oligomers signal in a PrP(C)-dependent way and that they can affect PrP(C) trafficking, increasing its localization at the cell surface.

  16. Wnt-5a occludes Aβ oligomer-induced depression of glutamatergic transmission in hippocampal neurons

    PubMed Central

    2010-01-01

    Background Soluble amyloid-β (Aβ;) oligomers have been recognized to be early and key intermediates in Alzheimer's disease (AD)-related synaptic dysfunction. Aβ oligomers block hippocampal long-term potentiation (LTP) and impair rodent spatial memory. Wnt signaling plays an important role in neural development, including synaptic differentiation. Results We report here that the Wnt signaling activation prevents the synaptic damage triggered by Aβ oligomers. Electrophysiological analysis of Schaffer collaterals-CA1 glutamatergic synaptic transmission in hippocampal slices indicates that Wnt-5a increases the amplitude of field excitatory postsynaptic potentials (fEPSP) and both AMPA and NMDA components of the excitatory postsynaptic currents (EPSCs), without modifying the paired pulse facilitation (PPF). Conversely, in the presence of Aβ oligomers the fEPSP and EPSCs amplitude decreased without modification of the PPF, while the postsynaptic scaffold protein (PSD-95) decreased as well. Co-perfusion of hippocampal slices with Wnt-5a and Aβ oligomers occludes against the synaptic depression of EPSCs as well as the reduction of PSD-95 clusters induced by Aβ oligomers in neuronal cultures. Taken together these results indicate that Wnt-5a and Aβ oligomers inversely modulate postsynaptic components. Conclusion These results indicate that post-synaptic damage induced by Aβ oligomers in hippocampal neurons is prevented by non-canonical Wnt pathway activation. PMID:20205789

  17. Theory of microphase separation in homopolymer oligomer mixtures

    NASA Astrophysics Data System (ADS)

    Olemskoi, Alexander; Savelyev, Alexey

    2005-11-01

    This work starts with the review of theoretical methods proposed, during past decades, for description of phase behavior in different polymer systems, involving variety of linear polymers (regular and polydisperse block (co)polymers, random polymers) and the polymer systems with non-covalent bonds of different strength. Microphase separation (MS) into different ordered mesophases is known to be the principal property of such systems. It is shown that most of the theoretical approaches proposed for description of the MS are based on the simple random phase approximation (RPA). It turns out, however, that mean field RPA method applied to description of the systems with non-covalent bonds does not provide the whole picture of MS. We show that the problem here arises when one treats both Flory-Huggins non-associated interactions and non-covalent bonds (hydrogen, ionic) within the unified RPA scheme, which is obviously rough for description of the latter type of interactions. Such a theory was developed in a few recent papers for the systems involving weak hydrogen bonds between homopolymer chains and the low molecular weight oligomers (surfactants). However, it leaves some experimental data unaccounted. The purpose of this review is to consider more detailed theory which is able to explain not only all the experimental data for the above systems but also to take into account the strength variation of non-bonding interactions. In particular, we consider the strong ionic interactions, weak hydrogen bonding, and the interactions of intermediate strength between polymer chain and short oligomers within our unifying theory. To develop such a description in a self-consistent way we propose to use a general field theory of stochastic systems. The mesoscopic (lamellar) structure of the periodically alternating layers of stretched homopolymer chains surrounded by perpendicularly oriented oligomeric tails is studied for the systems with both strong (ionic) and weak (hydrogen

  18. Alzheimer's Therapeutics Targeting Amyloid Beta 1–42 Oligomers I: Abeta 42 Oligomer Binding to Specific Neuronal Receptors Is Displaced by Drug Candidates That Improve Cognitive Deficits

    PubMed Central

    Izzo, Nicholas J.; Staniszewski, Agnes; To, Lillian; Fa, Mauro; Teich, Andrew F.; Saeed, Faisal; Wostein, Harrison; Walko, Thomas; Vaswani, Anisha; Wardius, Meghan; Syed, Zanobia; Ravenscroft, Jessica; Mozzoni, Kelsie; Silky, Colleen; Rehak, Courtney; Yurko, Raymond; Finn, Patricia; Look, Gary; Rishton, Gilbert; Safferstein, Hank; Miller, Miles; Johanson, Conrad; Stopa, Edward; Windisch, Manfred; Hutter-Paier, Birgit; Shamloo, Mehrdad; Arancio, Ottavio; LeVine, Harry; Catalano, Susan M.

    2014-01-01

    Synaptic dysfunction and loss caused by age-dependent accumulation of synaptotoxic beta amyloid (Abeta) 1–42 oligomers is proposed to underlie cognitive decline in Alzheimer's disease (AD). Alterations in membrane trafficking induced by Abeta oligomers mediates reduction in neuronal surface receptor expression that is the basis for inhibition of electrophysiological measures of synaptic plasticity and thus learning and memory. We have utilized phenotypic screens in mature, in vitro cultures of rat brain cells to identify small molecules which block or prevent the binding and effects of Abeta oligomers. Synthetic Abeta oligomers bind saturably to a single site on neuronal synapses and induce deficits in membrane trafficking in neuronal cultures with an EC50 that corresponds to its binding affinity. The therapeutic lead compounds we have found are pharmacological antagonists of Abeta oligomers, reducing the binding of Abeta oligomers to neurons in vitro, preventing spine loss in neurons and preventing and treating oligomer-induced deficits in membrane trafficking. These molecules are highly brain penetrant and prevent and restore cognitive deficits in mouse models of Alzheimer's disease. Counter-screening these compounds against a broad panel of potential CNS targets revealed they are highly potent and specific ligands of the sigma-2/PGRMC1 receptor. Brain concentrations of the compounds corresponding to greater than 80% receptor occupancy at the sigma-2/PGRMC1 receptor restore cognitive function in transgenic hAPP Swe/Ldn mice. These studies demonstrate that synthetic and human-derived Abeta oligomers act as pharmacologically-behaved ligands at neuronal receptors - i.e. they exhibit saturable binding to a target, they exert a functional effect related to their binding and their displacement by small molecule antagonists blocks their functional effect. The first-in-class small molecule receptor antagonists described here restore memory to normal in multiple AD

  19. Alzheimer's therapeutics targeting amyloid beta 1-42 oligomers I: Abeta 42 oligomer binding to specific neuronal receptors is displaced by drug candidates that improve cognitive deficits.

    PubMed

    Izzo, Nicholas J; Staniszewski, Agnes; To, Lillian; Fa, Mauro; Teich, Andrew F; Saeed, Faisal; Wostein, Harrison; Walko, Thomas; Vaswani, Anisha; Wardius, Meghan; Syed, Zanobia; Ravenscroft, Jessica; Mozzoni, Kelsie; Silky, Colleen; Rehak, Courtney; Yurko, Raymond; Finn, Patricia; Look, Gary; Rishton, Gilbert; Safferstein, Hank; Miller, Miles; Johanson, Conrad; Stopa, Edward; Windisch, Manfred; Hutter-Paier, Birgit; Shamloo, Mehrdad; Arancio, Ottavio; LeVine, Harry; Catalano, Susan M

    2014-01-01

    Synaptic dysfunction and loss caused by age-dependent accumulation of synaptotoxic beta amyloid (Abeta) 1-42 oligomers is proposed to underlie cognitive decline in Alzheimer's disease (AD). Alterations in membrane trafficking induced by Abeta oligomers mediates reduction in neuronal surface receptor expression that is the basis for inhibition of electrophysiological measures of synaptic plasticity and thus learning and memory. We have utilized phenotypic screens in mature, in vitro cultures of rat brain cells to identify small molecules which block or prevent the binding and effects of Abeta oligomers. Synthetic Abeta oligomers bind saturably to a single site on neuronal synapses and induce deficits in membrane trafficking in neuronal cultures with an EC50 that corresponds to its binding affinity. The therapeutic lead compounds we have found are pharmacological antagonists of Abeta oligomers, reducing the binding of Abeta oligomers to neurons in vitro, preventing spine loss in neurons and preventing and treating oligomer-induced deficits in membrane trafficking. These molecules are highly brain penetrant and prevent and restore cognitive deficits in mouse models of Alzheimer's disease. Counter-screening these compounds against a broad panel of potential CNS targets revealed they are highly potent and specific ligands of the sigma-2/PGRMC1 receptor. Brain concentrations of the compounds corresponding to greater than 80% receptor occupancy at the sigma-2/PGRMC1 receptor restore cognitive function in transgenic hAPP Swe/Ldn mice. These studies demonstrate that synthetic and human-derived Abeta oligomers act as pharmacologically-behaved ligands at neuronal receptors--i.e. they exhibit saturable binding to a target, they exert a functional effect related to their binding and their displacement by small molecule antagonists blocks their functional effect. The first-in-class small molecule receptor antagonists described here restore memory to normal in multiple AD models

  20. (3-aminopropyl)-4-methylpiperazine end-capped poly(1,4-butanediol diacrylate-co-4-amino-1-butanol)-based multilayer films for gene delivery.

    PubMed

    Li, Cuicui; Tzeng, Stephany Y; Tellier, Liane E; Green, Jordan J

    2013-07-10

    Biodegradable polyelectrolyte surfaces for gene delivery were created through electrospinning of biodegradable polycations combined with iterative solution-based multilayer coating. Poly(β-amino ester) (PBAE) poly(1,4-butanediol diacrylate-co-4-amino-1-butanol) end-capped with 1-(3-aminopropyl)-4-methylpiperazine was utilized because of its ability to electrostatically interact with anionic molecules like DNA, its biodegradability, and its low cytotoxicity. A new DNA release system was developed for sustained release of DNA over 24 h, accompanied by high exogenous gene expression in primary human glioblastoma (GB) cells. Electrospinning a different PBAE, poly(1,4-butanediol diacrylate-co-4,4'-trimethylenedipiperidine), and its combination with polyelectrolyte 1-(3-aminopropyl)-4-methylpiperazine end-capped poly(1,4-butanediol diacrylate-co-4-amino-1-butanol)-based multilayers are promising for DNA release and intracellular delivery from a surface.

  1. X-ray Crystallographic Structure of Oligomers Formed by a Toxic β-Hairpin Derived from α-Synuclein: Trimers and Higher-Order Oligomers.

    PubMed

    Salveson, Patrick J; Spencer, Ryan K; Nowick, James S

    2016-04-06

    Oligomeric assemblies of the protein α-synuclein are thought to cause neurodegeneration in Parkinson's disease and related synucleinopathies. Characterization of α-synuclein oligomers at high resolution is an outstanding challenge in the field of structural biology. The absence of high-resolution structures of oligomers formed by α-synuclein impedes understanding the synucleinopathies at the molecular level. This paper reports the X-ray crystallographic structure of oligomers formed by a peptide derived from residues 36-55 of α-synuclein. The peptide 1a adopts a β-hairpin structure, which assembles in a hierarchical fashion. Three β-hairpins assemble to form a triangular trimer. Three copies of the triangular trimer assemble to form a basket-shaped nonamer. Two nonamers pack to form an octadecamer. Molecular modeling suggests that full-length α-synuclein may also be able to assemble in this fashion. Circular dichroism spectroscopy demonstrates that peptide 1a interacts with anionic lipid bilayer membranes, like oligomers of full-length α-synuclein. LDH and MTT assays demonstrate that peptide 1a is toxic toward SH-SY5Y cells. Comparison of peptide 1a to homologues suggests that this toxicity results from nonspecific interactions with the cell membrane. The oligomers formed by peptide 1a are fundamentally different than the proposed models of the fibrils formed by α-synuclein and suggest that α-Syn36-55, rather than the NAC, may nucleate oligomer formation.

  2. An investigation into the effect of amphiphilic siloxane oligomers on dermal fibroblasts.

    PubMed

    Farrugia, Brooke L; Keddie, Daniel J; George, Graeme A; Lynam, Emily C; Brook, Michael A; Upton, Zee; Dargaville, Tim R

    2012-07-01

    This study investigates the effect of well-defined poly(dimethylsiloxane)-poly(ethylene glycol) (PDMS-PEG) ABA linear block co-oligomers on the proliferation of human dermal fibroblasts. The co-oligomers assessed ranged in molecular weight (MW) from 1335 to 5208 Da and hydrophilic-lipophilic balance (HLB) from 5.9 to 16.6 by varying the number of both PDMS and PEG units. In general, it was found that co-oligomers of low MW or intermediate hydrophilicity significantly reduced fibroblast proliferation. A linear relationship between down-regulation of fibroblast proliferation, and the ratio HLB/MW was observed at concentrations of 0.1 and 1.0 wt % of the oligomers. This enabled the structures with highest efficiency to be determined. These results suggest the possible use of the PEG-PDMS-PEG block co-oligomers as an alternative to silicone gels for hypertrophic scar remediation.

  3. Direct PIP2 binding mediates stable oligomer formation of the serotonin transporter

    PubMed Central

    Anderluh, Andreas; Hofmaier, Tina; Klotzsch, Enrico; Kudlacek, Oliver; Stockner, Thomas; Sitte, Harald H.; Schütz, Gerhard J.

    2017-01-01

    The human serotonin transporter (hSERT) mediates uptake of serotonin from the synaptic cleft and thereby terminates serotonergic signalling. We have previously found by single-molecule microscopy that SERT forms stable higher-order oligomers of differing stoichiometry at the plasma membrane of living cells. Here, we report that SERT oligomer assembly at the endoplasmic reticulum (ER) membrane follows a dynamic equilibration process, characterized by rapid exchange of subunits between different oligomers, and by a concentration dependence of the degree of oligomerization. After trafficking to the plasma membrane, however, the SERT stoichiometry is fixed. Stabilization of the oligomeric SERT complexes is mediated by the direct binding to phosphoinositide phosphatidylinositol-4,5-biphosphate (PIP2). The observed spatial decoupling of oligomer formation from the site of oligomer operation provides cells with the ability to define protein quaternary structures independent of protein density at the cell surface. PMID:28102201

  4. Star-shaped tetrathiafulvalene oligomers towards the construction of conducting supramolecular assembly

    PubMed Central

    Hasegawa, Masashi

    2015-01-01

    Summary The construction of redox-active supramolecular assemblies based on star-shaped and radially expanded tetrathiafulvalene (TTF) oligomers with divergent and extended conjugation is summarized. Star-shaped TTF oligomers easily self-aggregate with a nanophase separation to produce supramolecular structures, and their TTF units stack face-to-face to form columnar structures using the fastener effect. Based on redox-active self-organizing supramolecular structures, conducting nanoobjects are constructed by doping of TTF oligomers with oxidants after the formation of such nanostructures. Although radical cations derived from TTF oligomers strongly interact in solution to produce a mixed-valence dimer and π-dimer, it seems to be difficult to produce nanoobjects of radical cations different from those of neutral TTF oligomers. In some cases, however, radical cations form nanostructured fibers and rods by controlling the supramolecular assembly, oxidation states, and counter anions employed. PMID:26664579

  5. Alginate gels with a combination of calcium and chitosan oligomer mixtures as crosslinkers.

    PubMed

    Feng, Yiming; Kopplin, Georg; Sato, Kimihiko; Draget, Kurt I; Vårum, Kjell M

    2017-01-20

    Alginates are polysaccharides that are widely used in relation to their ability to form gels. Recently we reported that alginates may also form gels with chitosan oligomers as crosslinkers (Khong, Aarstad, Skjåk-Bræk, Draget, & Vårum, 2013). The purpose of the present study was to characterize alginate gels crosslinked with calcium and chitosan oligomers. Using two different alginates of similar molecular weights but different chemical composition, i.e. guluronic acid content of 46 and 68%, we found that both alginates could form homogeneous gels with calcium and chitosan oligomers separately and without syneresis. Systematic combinations of calcium and chitosan oligomers as crosslinkers were tested, showing that up to 50% of the calcium could be substituted with chitosan oligomers without reduction in gel strength or increased syneresis for the alginate with the lowest guluronic acid content. Furthermore, the kinetics of the combined gels were different from pure calcium alginate gels.

  6. Preparation of Chito-Oligomers by Hydrolysis of Chitosan in the Presence of Zeolite as Adsorbent.

    PubMed

    Ibrahim, Khalid A; El-Eswed, Bassam I; Abu-Sbeih, Khaleel A; Arafat, Tawfeeq A; Al Omari, Mahmoud M H; Darras, Fouad H; Badwan, Adnan A

    2016-07-23

    An increasing interest has recently been shown to use chitin/chitosan oligomers (chito-oligomers) in medicine and food fields because they are not only water-soluble, nontoxic, and biocompatible materials, but they also exhibit numerous biological properties, including antibacterial, antifungal, and antitumor activities, as well as immuno-enhancing effects on animals. Conventional depolymerization methods of chitosan to chito-oligomers are either chemical by acid-hydrolysis under harsh conditions or by enzymatic degradation. In this work, hydrolysis of chitosan to chito-oligomers has been achieved by applying adsorption-separation technique using diluted HCl in the presence of different types of zeolite as adsorbents. The chito-oligomers were retrieved from adsorbents and characterized by differential scanning calorimetry (DSC), liquid chromatography/mass spectroscopy (LC/MS), and ninhydrin test.

  7. The Role of Amyloid-β Oligomers in Toxicity, Propagation, and Immunotherapy

    PubMed Central

    Sengupta, Urmi; Nilson, Ashley N.; Kayed, Rakez

    2016-01-01

    The incidence of Alzheimer's disease (AD) is growing every day and finding an effective treatment is becoming more vital. Amyloid-β (Aβ) has been the focus of research for several decades. The recent shift in the Aβ cascade hypothesis from all Aβ to small soluble oligomeric intermediates is directing the search for therapeutics towards the toxic mediators of the disease. Targeting the most toxic oligomers may prove to be an effective treatment by preventing their spread. Specific targeting of oligomers has been shown to protect cognition in rodent models. Additionally, the heterogeneity of research on Aβ oligomers may seem contradictory until size and conformation are taken into account. In this review, we will discuss Aβ oligomers and their toxicity in relation to size and conformation as well as their influence on inflammation and the potential of Aβ oligomer immunotherapy. PMID:27211547

  8. Preparation of Chito-Oligomers by Hydrolysis of Chitosan in the Presence of Zeolite as Adsorbent

    PubMed Central

    Ibrahim, Khalid A.; El-Eswed, Bassam I.; Abu-Sbeih, Khaleel A.; Arafat, Tawfeeq A.; Al Omari, Mahmoud M. H.; Darras, Fouad H.; Badwan, Adnan A.

    2016-01-01

    An increasing interest has recently been shown to use chitin/chitosan oligomers (chito-oligomers) in medicine and food fields because they are not only water-soluble, nontoxic, and biocompatible materials, but they also exhibit numerous biological properties, including antibacterial, antifungal, and antitumor activities, as well as immuno-enhancing effects on animals. Conventional depolymerization methods of chitosan to chito-oligomers are either chemical by acid-hydrolysis under harsh conditions or by enzymatic degradation. In this work, hydrolysis of chitosan to chito-oligomers has been achieved by applying adsorption-separation technique using diluted HCl in the presence of different types of zeolite as adsorbents. The chito-oligomers were retrieved from adsorbents and characterized by differential scanning calorimetry (DSC), liquid chromatography/mass spectroscopy (LC/MS), and ninhydrin test. PMID:27455287

  9. Structural Characteristics of the Alpha-Synuclein Oligomers Stabilized By the Flavonoid Baicalein

    SciTech Connect

    Hong, D.-P.; Fink, A.L.; Uversky, V.N.

    2009-05-18

    The flavonoid baicalein inhibits fibrillation of alpha-synuclein, which is a major component of Lewy bodies in Parkinson's disease. It has been known that baicalein induces the formation of alpha-synuclein oligomers and consequently prevents their fibrillation. In order to evaluate the structural properties of baicalein-stabilized oligomers, we purified oligomer species by HPLC and examined their stability and structure by CD, Fourier transform infrared spectroscopy, size exclusion chromatography HPLC, small-angle X-ray scattering, and atomic force microscopy. Baicalein-stabilized oligomers are beta-sheet-enriched according to CD and Fourier transform infrared spectroscopy analyses. They did not form fibrils even after very prolonged incubation. From small-angle X-ray scattering data and atomic force microscopy images, the oligomers were characterized as quite compact globular species. Oligomers were extremely stable, with a GdmCl C(m)=3.3 M. This high stability explains the previously observed inhibition properties of baicalein against alpha-synuclein fibrillation. These baicalein-stabilized oligomers, added to the solution of aggregating alpha-synuclein, were able to noticeably inhibit its fibrillation. After prolonged coincubation, short fibrils were formed, suggesting an effective interaction of oligomers with monomeric alpha-synuclein. Membrane permeability tests suggested that the baicalein-stabilized oligomers had a mild effect on the integrity of the membrane surface. This effect was rather similar to that of the monomeric protein, suggesting that targeted stabilization of certain alpha-synuclein oligomers might offer a potential strategy for the development of novel Parkinson's disease therapies.

  10. Effect of Degree of Imidization in Polyimide Thin Films Prepared by Vapor Deposition Polymerization on the Electrical Conduction

    NASA Astrophysics Data System (ADS)

    Ito, Yasuhiko; Hikita, Masayuki; Kimura, Toyoaki; Mizutani, Teruyosi

    1990-06-01

    Polyimide (PI) thin films of about 300 nm in thickness are fabricated by vapor deposition polymerization (VDP) from pyromellitic dianhydride (PMDA) and 4,4'-diaminodiphenylether (DDE). The structure of the films obtained is analyzed by means of infrared absorption spectra (IR spectra) and X-ray diffraction. The IR spectra show that the films are changed into PI by curing through the precursor, polyamic acid (PAA). The relation between the imidization of the films and the electrical conduction is examined. The results show that as imidization caused by curing the films proceeds, the current is decreased. It is therefore suggested that the residual PAA in PI thin films affects the electrical conduction. An attempt is also made to apply a model of ionic hopping conduction to the electrical conduction data.

  11. Spacer effect on nanostructures and self-assembly in organogels via some bolaform cholesteryl imide derivatives with different spacers

    NASA Astrophysics Data System (ADS)

    Jiao, Tifeng; Gao, Fengqing; Zhang, Qingrui; Zhou, Jingxin; Gao, Faming

    2013-10-01

    In this paper, new bolaform cholesteryl imide derivatives with different spacers were designed and synthesized. Their gelation behaviors in 23 solvents were investigated, and some of them were found to be low molecular mass organic gelators. The experimental results indicated that these as-formed organogels can be regulated by changing the flexible/rigid segments in spacers and organic solvents. Suitable combination of flexible/rigid segments in molecular spacers in the present cholesteryl gelators is favorable for the gelation of organic solvents. Scanning electron microscopy and atomic force microscopy observations revealed that the gelator molecules self-assemble into different aggregates, from wrinkle and belt to fiber with the change of spacers and solvents. Spectral studies indicated that there existed different H-bond formations between imide groups and assembly modes, depending on the substituent spacers in molecular skeletons. The present work may give some insight into the design and character of new organogelators and soft materials with special molecular structures.

  12. New Poly(amide-imide)/Nanocomposites Reinforced Silicate Nanoparticles Based on N-pyromellitimido-L-phenyl Alanine Containing Ether Moieties

    NASA Astrophysics Data System (ADS)

    Faghihi, Khalil; Shabanian, Meisam; Dadfar, Ehsan

    2012-02-01

    A series of Poly(amide-imide)/montmorillonite nanocomposites containing N-pyromellitimido-L-phenyl alanine moiety in the main chain were synthesized by a convenient solution intercalation technique. Poly(amide-imide) (PAI) 5 as a source of polymer matrix was synthesized by the direct polycondensation reaction of N-pyromellitimido-L-phenyl alanine 3 with 4,4'-diamino diphenyl ether 4 in the presence of triphenyl phosphite (TPP), CaCl2, pyridine and N-methyl-2-pyrrolidone (NMP). The resulting nanocomposite films were characterized by Fourier transform infrared spectra (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). The results showed that organo-modified clay was dispersed homogeneously in PAI matrix. TGA indicated an enhancement of thermal stability of new nanocomposites compared with the pure polymer.

  13. 1-Ethyl-1-methyl piperidinium bis(trifluoromethanesulfonyl)imide as a co-solvent in Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Kim, Ketack; Cho, Young-Hyun; Shin, Heon-Cheol

    2013-03-01

    1-Ethyl-1-methyl piperidinium bis(trifluoromethanesulfonyl)imide (EMP-TFSI) is an ionic liquid with a melting temperature of 85 °C. Although it is a solid salt, it shows good miscibility with carbonate solvents, which allows EMP-TFSI to be used as a co-solvent in these systems. Ethylene carbonate is another solid co-solvent used in Li-ion batteries. Due to its smaller cationic size, EMP-TFSI provides better conductivity as a co-solvent than 1-methyl-1-propyl piperidinium bis(trifluoromethanesulfonyl)imide (MPP-TFSI), which is the smallest room-temperature piperidinium liquid salt known. In cells with 50 wt% IL and 50 wt% carbonate electrolyte, an EMP-TFSI mixed electrolyte performs better than an MPP-TFSI mixed electrolyte. Additionally, the discharge capacity values obtained from rate capability tests carried out with mixed EMP-TFSI are as good as those conducted with a pure carbonate electrolyte.

  14. Brain amyloid-β oligomers in ageing and Alzheimer's disease.

    PubMed

    Lesné, Sylvain E; Sherman, Mathew A; Grant, Marianne; Kuskowski, Michael; Schneider, Julie A; Bennett, David A; Ashe, Karen H

    2013-05-01

    Alzheimer's disease begins about two decades before the onset of symptoms or neuron death, and is believed to be caused by pathogenic amyloid-β aggregates that initiate a cascade of molecular events culminating in widespread neurodegeneration. The microtubule binding protein tau may mediate the effects of amyloid-β in this cascade. Amyloid plaques comprised of insoluble, fibrillar amyloid-β aggregates are the most characteristic feature of Alzheimer's disease. However, the correspondence between the distribution of plaques and the pattern of neurodegeneration is tenuous. This discrepancy has stimulated the investigation of other amyloid-β aggregates, including soluble amyloid-β oligomers. Different soluble amyloid-β oligomers have been studied in several mouse models, but not systematically in humans. Here, we measured three amyloid-β oligomers previously described in mouse models-amyloid-β trimers, Aβ*56 and amyloid-β dimers-in brain tissue from 75 cognitively intact individuals, ranging from young children to the elderly, and 58 impaired subjects with mild cognitive impairment or probable Alzheimer's disease. As in mouse models, where amyloid-β trimers appear to be the fundamental amyloid-β assembly unit of Aβ*56 and are present in young mice prior to memory decline, amyloid-β trimers in humans were present in children and adolescents; their levels rose gradually with age and were significantly above baseline in subjects in their 70s. Aβ*56 levels were negligible in children and young adults, rose significantly above baseline in subjects in their 40s and increased steadily thereafter. Amyloid-β dimers were undetectable until subjects were in their 60s; their levels then increased sharply and correlated with plaque load. Remarkably, in cognitively intact individuals we found strong positive correlations between Aβ*56 and two pathological forms of soluble tau (tau-CP13 and tau-Alz50), and negative correlations between Aβ*56 and two postsynaptic

  15. Towards organic zeolites and inclusion catalysts: heptazine imide salts can exchange metal cations in the solid state.

    PubMed

    Antonietti, Markus; Savateev, Aleksandr; Pronkin, Sergey; Willinger, Marc; Dontsova, Dariya

    2017-02-15

    Highly crystalline potassium (heptazine imides) were prepared by the thermal condensation of substituted 1,2,4-triazoles in eutectic salt melts. These semiconducting salts are already known to be highly active photocatalysts, e.g. for the visible light driven generation of hydrogen from water. Herein, we show that within the solid state structure, potassium ions can be exchanged to other metal ions while the crystal habitus is essentially preserved.

  16. Thermosetting Poly(imide silsesquioxane)s Featuring Reduced Moisture Affinity and Improved Processability (Post-print)

    DTIC Science & Technology

    2013-09-11

    Journal Article 3. DATES COVERED (From - To) August 2013- October 2013 4. TITLE AND SUBTITLE Thermosetting Poly(imide silsesquioxane)s Featuring Reduced... Journal article published in the ACS Macromolecules Vol. #46, Issue #18 September 2013. PA Case Number: #13496; Clearance Date: 10 Oct 2013...from oligoamic acid to oligoimide is attributed to a lower degree of rotational freedom and thus more chemical environments. Rheology . Figure 5

  17. A Novel Amidase (Half-Amidase) for Half-Amide Hydrolysis Involved in the Bacterial Metabolism of Cyclic Imides

    PubMed Central

    Soong, Chee-Leong; Ogawa, Jun; Shimizu, Sakayu

    2000-01-01

    A novel amidase involved in bacterial cyclic imide metabolism was purified from Blastobacter sp. strain A17p-4. The enzyme physiologically functions in the second step of cyclic imide degradation, i.e., the hydrolysis of monoamidated dicarboxylates (half-amides) to dicarboxylates and ammonia. Enzyme production was enhanced by cyclic imides such as succinimide and glutarimide but not by amide compounds which are conventional substrates and inducers of known amidases. The purified amidase showed high catalytic efficiency toward half-amides such as succinamic acid (Km = 6.2 mM; kcat = 5.76 s−1) and glutaramic acid (Km = 2.8 mM; kcat = 2.23 s−1). However, the substrates of known amidases such as short-chain (C2 to C4) aliphatic amides, long-chain (above C16) aliphatic amides, amino acid amides, aliphatic diamides, α-keto acid amides, N-carbamoyl amino acids, and aliphatic ureides were not substrates for the enzyme. Based on its high specificity toward half-amides, the enzyme was named half-amidase. This half-amidase exists as a monomer with an Mr of 48,000 and was strongly inhibited by heavy metal ions and sulfhydryl reagents. PMID:10788365

  18. Formation of RNA oligomers on montmorillonite: site of catalysis

    NASA Technical Reports Server (NTRS)

    Ertem, G.; Ferris, J. P.

    1998-01-01

    Certain montmorillonites catalyze the self condensation of the 5'-phosphorimidazolide of nucleosides in pH 8 aqueous electrolyte solutions at ambient temperatures leading to formation of RNA oligomers. In order to establish the nature of the sites on montmorillonite responsible for this catalytic activity, oligomerization reactions were run with montmorillonites which had been selectively modified (I) at the edges by (a) fluoride treatment, (b) silylation, (c) metaphosphate treatment of the anion exchange sites (II) in the interlayer by (a) saturation with quaternary alkylammonium ions of increasing size, (b) aluminum polyoxo cations. High pressure liquid chromatography, HPLC, analysis of condensation products for their chain lengths and yields indicated that modification at the edges did not affect the catalytic activity to a significant extent, while blocking the interlayer strongly inhibited product formation.

  19. A Kinetic Model for Cell Damage Caused by Oligomer Formation.

    PubMed

    Hong, Liu; Huang, Ya-Jing; Yong, Wen-An

    2015-10-06

    It is well known that the formation of amyloid fiber may cause invertible damage to cells, although the underlying mechanism has not been fully understood. In this article, a microscopic model considering the detailed processes of amyloid formation and cell damage is constructed based on four simple assumptions, one of which is that cell damage is raised by oligomers rather than mature fibrils. By taking the maximum entropy principle, this microscopic model in the form of infinite mass-action equations together with two reaction-convection partial differential equations (PDEs) has been greatly coarse-grained into a macroscopic system consisting of only five ordinary differential equations (ODEs). With this simple model, the effects of primary nucleation, elongation, fragmentation, and protein and seeds concentration on amyloid formation and cell damage have been extensively explored and compared with experiments. We hope that our results will provide new insights into the quantitative linkage between amyloid formation and cell damage.

  20. VCD Studies on Chiral Characters of Metal Complex Oligomers

    PubMed Central

    Sato, Hisako; Yamagishi, Akihiko

    2013-01-01

    The present article reviews the results on the application of vibrational circular dichroism (VCD) spectroscopy to the study of stereochemical properties of chiral metal complexes in solution. The chiral characters reflecting on the vibrational properties of metal complexes are revealed by measurements of a series of β-diketonato complexes with the help of theoretical calculation. Attention is paid to the effects of electronic properties of a central metal ion on vibrational energy levels or low-lying electronic states. The investigation is further extended to the oligomers of β-diketonato complex units. The induction of chiral structures is confirmed by the VCD spectra when chiral inert moieties are connected with labile metal ions. These results have demonstrated how VCD spectroscopy is efficient in revealing the static and dynamic properties of mononuclear and multinuclear chiral metal complexes, which are difficult to clarify by means of other spectroscopes. PMID:23296273

  1. VCD studies on chiral characters of metal complex oligomers.

    PubMed

    Sato, Hisako; Yamagishi, Akihiko

    2013-01-07

    The present article reviews the results on the application of vibrational circular dichroism (VCD) spectroscopy to the study of stereochemical properties of chiral metal complexes in solution. The chiral characters reflecting on the vibrational properties of metal complexes are revealed by measurements of a series of β-diketonato complexes with the help of theoretical calculation. Attention is paid to the effects of electronic properties of a central metal ion on vibrational energy levels or low-lying electronic states. The investigation is further extended to the oligomers of β-diketonato complex units. The induction of chiral structures is confirmed by the VCD spectra when chiral inert moieties are connected with labile metal ions. These results have demonstrated how VCD spectroscopy is efficient in revealing the static and dynamic properties of mononuclear and multinuclear chiral metal complexes, which are difficult to clarify by means of other spectroscopes.

  2. EGFP oligomers as natural fluorescence and hydrodynamic standards

    PubMed Central

    Vámosi, György; Mücke, Norbert; Müller, Gabriele; Krieger, Jan Wolfgang; Curth, Ute; Langowski, Jörg; Tóth, Katalin

    2016-01-01

    EGFP oligomers are convenient standards for experiments on fluorescent protein-tagged biomolecules. In this study, we characterized their hydrodynamic and fluorescence properties. Diffusion coefficients D of EGFP1–4 were determined by analytical ultracentrifugation with fluorescence detection and by fluorescence correlation spectroscopy (FCS), yielding 83.4…48.2 μm2/s and 97.3…54.8 μm2/s from monomer to tetramer. A “barrels standing in a row” model agreed best with the sedimentation data. Oligomerization red-shifted EGFP emission spectra without any shift in absorption. Fluorescence anisotropy decreased, indicating homoFRET between the subunits. Fluorescence lifetime decreased only slightly (4%) indicating insignificant quenching by FRET to subunits in non-emitting states. FCS-measured D, particle number and molecular brightness depended on dark states and light-induced processes in distinct subunits, resulting in a dependence on illumination power different for monomers and oligomers. Since subunits may be in “on” (bright) or “off” (dark) states, FCS-determined apparent brightness is not proportional to that of the monomer. From its dependence on the number of subunits, the probability of the “on” state for a subunit was determined to be 96% at pH 8 and 77% at pH 6.38, i.e., protonation increases the dark state. These fluorescence properties of EGFP oligomeric standards can assist interpreting results from oligomerized EGFP fusion proteins of biological interest. PMID:27622431

  3. Fluorene- and benzofluorene-cored oligomers as low threshold and high gain amplifying media

    SciTech Connect

    Kazlauskas, Karolis Kreiza, Gediminas; Bobrovas, Olegas; Adomėnienė, Ona; Adomėnas, Povilas; Juršėnas, Saulius; Jankauskas, Vygintas

    2015-07-27

    Deliberate control of intermolecular interactions in fluorene- and benzofluorene-cored oligomers was attempted via introduction of different-length alkyl moieties to attain high emission amplification and low amplified spontaneous emission (ASE) threshold at high oligomer concentrations. Containing fluorenyl peripheral groups decorated with different-length alkyl moieties, the oligomers were found to express weak concentration quenching of emission, yet excellent carrier drift mobilities (close to 10{sup −2} cm{sup 2}/V/s) in the amorphous films. Owing to the larger radiative decay rates (>1.0 × 10{sup 9 }s{sup −1}) and smaller concentration quenching, fluorene-cored oligomers exhibited down to one order of magnitude lower ASE thresholds at higher concentrations as compared to those of benzofluorene counterparts. The lowest threshold (300 W/cm{sup 2}) obtained for the fluorene-cored oligomers at the concentration of 50 wt % in polymer matrix is among the lowest reported for solution-processed amorphous films in ambient conditions, what makes the oligomers promising for lasing application. Great potential in emission amplification was confirmed by high maximum net gain (77 cm{sup −1}) revealed for these compounds. Although the photostability of the oligomers was affected by photo-oxidation, it was found to be comparable to that of various organic lasing materials including some commercial laser dyes evaluated under similar excitation conditions.

  4. Study of radiation damage to the CMS Hadronic Endcap Calorimeter and investigation into new physics using multi-boson measurements

    SciTech Connect

    Belloni, Alberto

    2016-03-31

    This document is the final report for the U.S. D.O.E. Grant No. DE-SC0014088, which covers the period from May 15, 2015 to March 31, 2016. The funded research covered the study of multi-boson final states, culminated in the measurement of the W±γγ and, for the first time at an hadronic collider, of the Zγγ production cross sections. These processes, among the rarest multi-boson final states measurable by LHC experiments, allow us to investigate the possibility of new physics in a model-independent way, by looking for anomalies in the standard model couplings among electroweak bosons. In particular, these 3-boson final states access quartic gauge couplings; the W±γγ analysis performed as a part of this proposal sets limits on anomalies in the WWγγ quartic gauge coupling. The award also covered R&D activities to define a radiation-tolerant material to be used in the incoming upgrade of the CMS hadronic endcap calorimeter. In particular, the usage of a liquid-scintillator-based detector was investigated. The research work performed in this direction has been collected in a paper recently submitted for publication in the Journal of Instrumentation (JINST).

  5. Synthesis, optical properties and explosive sensing performances of a series of novel π-conjugated aromatic end-capped oligothiophenes.

    PubMed

    Liu, Taihong; Zhao, Keru; Liu, Ke; Ding, Liping; Yin, Shiwei; Fang, Yu

    2013-02-15

    Four novel terthiophene (3T) derivatives, have been synthesized by employing Grignard coupling reaction via end-capping of naphthyl (NA) or pyrenyl (Py) unit to the one or two ends of 3T. It has been shown that both increasing electron donating strength and extending conjugation are effective approaches to improve the photochemical stability of the oligothiophene. Fluorescence studies demonstrated that the emission of the 3T derivatives is sensitive to the presence of some important nitro-containing explosives in their ethanol solution, in particular, 2,4,6-trinitrophenol (PA) and 3,5-dinitro-2,6-bispicrylamino pyridine (PYX). As an example, the detection limits of 4 to PA and PYX were determined to be 6.21 × 10(-7)mol/L and 8.95 × 10(-7)mol/L, respectively. Based on the discovery, a colorimetric detection method has been developed. The sensitive and selective response of the modified 3T to the explosives have been tentatively attributed to the adsorptive affinity of the compounds to the explosives, and to the higher probability of the electron transfer from the electron-rich 3T derivatives to the electron-poor nitro-containing explosives. No doubt, present study broadens the family of fluorophores which may be employed for the development of fluorescent sensors.

  6. High-resolution atomic force microscopy of soluble Abeta42 oligomers.

    PubMed

    Mastrangelo, Iris A; Ahmed, Mahiuddin; Sato, Takeshi; Liu, Wei; Wang, Chengpu; Hough, Paul; Smith, Steven O

    2006-04-21

    Soluble oligomers and protofibrils are widely thought to be the toxic forms of the Abeta42 peptide associated with Alzheimer's disease. We have investigated the structure and formation of these assemblies using a new approach in atomic force microscopy (AFM) that yields high-resolution images of hydrated proteins and allows the structure of the smallest molecular weight (MW) oligomers to be observed and characterized. AFM images of monomers, dimers and other low MW oligomers at early incubation times (< 1h) are consistent with a hairpin structure for the monomeric Abeta42 peptide. The low MW oligomers are relatively compact and have significant order. The most constant dimension of these oligomers is their height (approximately 1-3 nm) above the mica surface; their lateral dimensions (width and length) vary between 5 nm and 10nm. Flat nascent protofibrils with lengths of over 40 nm are observed at short incubation times (< or = 3h); their lateral dimensions of 6-8 nm are consistent with a mass-per-length of 9 kDa/nm previously predicted for the elementary fibril subunit. High MW oligomers with lateral dimensions of 15-25 nm and heights ranging from 2-8 nm are common at high concentrations of Abeta. We show that an inhibitor designed to block the sheet-to-sheet packing in Abeta fibrils is able to cap the heights of these oligomers at approximately 4 nm. The observation of fine structure in the high MW oligomers suggests that they are able to nucleate fibril formation. AFM images obtained as a function of incubation time reveal a sequence of assembly from monomers to soluble oligomers and protofibrils.

  7. Self-assembly of organogels via new luminol imide derivatives: diverse nanostructures and substituent chain effect

    NASA Astrophysics Data System (ADS)

    Jiao, Tifeng; Huang, Qinqin; Zhang, Qingrui; Xiao, Debao; Zhou, Jingxin; Gao, Faming

    2013-06-01

    Luminol is considered as an efficient sycpstem in electrochemiluminescence (ECL) measurements for the detection of hydrogen peroxide. In this paper, new luminol imide derivatives with different alkyl substituent chains were designed and synthesized. Their gelation behaviors in 26 solvents were tested as novel low molecular mass organic gelators. It was shown that the length and number of alkyl substituent chains linked to a benzene ring in gelators played a crucial role in the gelation behavior of all compounds in various organic solvents. Longer alkyl chains in molecular skeletons in present gelators are favorable for the gelation of organic solvents. Scanning electron microscope and atomic force microscope observations revealed that the gelator molecules self-assemble into different micro/nanoscale aggregates from a dot, flower, belt, rod, and lamella to wrinkle with change of solvents. Spectral studies indicated that there existed different H-bond formations and hydrophobic forces, depending on the alkyl substituent chains in molecular skeletons. The present work may give some insight to the design and characteristic of new versatile soft materials and potential ECL biosensors with special molecular structures.

  8. Li+ ionic conductivities and diffusion mechanisms in Li-based imides and lithium amide.

    PubMed

    Li, Wen; Wu, Guotao; Xiong, Zhitao; Feng, Yuan Ping; Chen, Ping

    2012-02-07

    In this study, both experimental ionic conductivity measurements and the first-principles simulations are employed to investigate the Li(+) ionic diffusion properties in lithium-based imides (Li(2)NH, Li(2)Mg(NH)(2) and Li(2)Ca(NH)(2)) and lithium amide (LiNH(2)). The experimental results show that Li(+) ions present superionic conductivity in Li(2)NH (2.54 × 10(-4) S cm(-1)) and moderate ionic conductivity in Li(2)Ca(NH)(2) (6.40 × 10(-6) S cm(-1)) at room temperature; while conduction of Li(+) ions is hardly detectable in Li(2)Mg(NH)(2) and LiNH(2) at room temperature. The simulation results indicate that Li(+) ion diffusion in Li(2)NH may be mediated by Frenkel pair defects or charged vacancies, and the diffusion pathway is more likely via a series of intermediate jumps between octahedral and tetrahedral sites along the [001] direction. The calculated activation energy and pre-exponential factor for Li(+) ion conduction in Li(2)NH are well comparable with the experimentally determined values, showing the consistency of experimental and theoretical investigations. The calculation of the defect formation energy in LiNH(2) reveals that Li defects are difficult to create to mediate the Li(+) ion diffusion, resulting in the poor Li(+) ion conduction in LiNH(2) at room temperature.

  9. Interaction of thrombocytes with poly(ether imide): The influence of processing.

    PubMed

    Braune, S; Lange, M; Richau, K; Lützow, K; Weigel, T; Jung, F; Lendlein, A

    2010-01-01

    The processing of polymers for blood contacting devices can have a major influence on surface properties. In this study, we fabricated poly(ether imide) (PEI) membranes and films to investigate the effects of the processing on physicochemical surface properties by atomic force microscopy (AFM), scanning electron microscopy, contact angle as well as zeta potential measurements. A static platelet adhesion test was performed to analyze the thrombogenicity of both devices. While contact angle measurements showed similar levels of hydrophobicity and zeta potential values were equivalent, mean surface roughness as well as surface energies in the dispersive part were found to be increased for the PEI membrane. The static platelet adhesion test showed a significantly decreased number of adherent platelets per surface area on the PEI film (178.98 ± 102.70/45000 μm2) compared to the PEI membrane (504 ± 314.27/45000μm2) and, consequently, revealed evidence for higher thrombogenicity of the PEI membrane. This study shows that processing can have a significant effect on platelet adhesion to biomaterials, even though, molar weight was identical. Thrombogenicity of polymer-based cardiovascular devices, therefore, have to be evaluated at the final product level, following the entire processing procedure.

  10. Synthesis and characterization of new optically active poly(azo-ester-imide)s via interfacial polycondensation.

    PubMed

    Hajipour, Abdol R; Zahmatkesh, Saeed; Roosta, Parniyan; Ruoho, Arnold E

    2009-03-01

    N,N'-Pyromelliticdiimido-di-L-amino acids (1a-1d) were prepared from the reaction of pyromellitic dianhydride with the corresponding L-amino acids in a solution of glacial acetic acid/pyridine (3:2) at refluxing temperature. 4,4'-sulfonyl bis(4,1-phenylene) bis(diazene-2,1-diyl) diphenol, 4,4'-oxy bis(4,1-phenylene) bis(diazene-2,1-diyl) diphenol and 4,4'-methylene bis(4,1-phenylene) bis(diazene-2,1-diyl) diphenol, were prepared from 4,4'-diamino diphenyl sulfone, 4,4'-diamino diphenyl ether, 4,4'-diamino diphenyl methane, sodium nitrite and phenol following the general procedure of diazo coupling. Interfacial polycondensation method was used to prepare the corresponding poly(azo-ester-imid)s (PAEI(1-12)) in biphasic solution of water/dichloromethane. The resulting polymers (PAEIs) have been obtained in high yields having good inherent viscosities (0.32-0.57 dl g(-1)), optical activities and thermal stabilities.

  11. Adsorption capacity of poly(ether imide) microparticles to uremic toxins.

    PubMed

    Tetali, Sarada D; Jankowski, Vera; Luetzow, Karola; Kratz, Karl; Lendlein, Andreas; Jankowski, Joachim

    2016-01-01

    Uremia is a phenomenon caused by retention of uremic toxins in the plasma due to functional impairment of kidneys in the elimination of urinary waste products. Uremia is presently treated by dialysis techniques like hemofiltration, dialysis or hemodiafiltration. However, these techniques in use are more favorable towards removing hydrophilic than hydrophobic uremic toxins. Hydrophobic uremic toxins, such as hydroxy hipuric acid (OH-HPA), phenylacetic acid (PAA), indoxyl sulfate (IDS) and p-cresylsulfate (pCRS), contribute substantially to the progression of chronic kidney disease (CKD) and cardiovascular disease. Therefore, objective of the present study is to test adsorption capacity of highly porous microparticles prepared from poly(ether imide) (PEI) as an alternative technique for the removal of uremic toxins. Two types of nanoporous, spherically shaped microparticles were prepared from PEI by a spraying/coagulation process.PEI particles were packed into a preparative HPLC column to which a mixture of the four types of uremic toxins was injected and eluted with ethanol. Eluted toxins were quantified by analytical HPLC. PEI particles were able to adsorb all four toxins, with the highest affinity for PAA and pCR. IDS and OH-HPA showed a partially non-reversible binding. In summary, PEI particles are interesting candidates to be explored for future application in CKD.

  12. Influence of nanoporous poly(ether imide) particle extracts on human aortic endothelial cells (HAECs).

    PubMed

    Kumar, Reddi K; Basu, Sayantani; Lemke, Horst-Dieter; Jankowski, Joachim; Kratz, Karl; Lendlein, Andreas; Tetali, Sarada D

    2016-01-01

    Accumulated uremic toxins like indoxyl sulphate, hippuric acid and p-cresyl sulphates in renal failure patients stimulate proinflammatory effects, and consequently kidney and cardiovascular diseases. Low clearance rate of these uremic toxins from the blood of uremic patients by conventional techniques like hemodialysis is due to their strong covalent albumin binding (greater than 95%) and hydrophobic nature, which led to alternatives like usage of hydrophobic adsorber's in removing these toxins from the plasma of kidney patients. Polymers like polyethylene, polyurethane, polymethylmethacrylate, cellophane and polytetrafluoroethylene were already in use as substitutes for metal devices as dialysis membranes. Among new synthetic polymers, one such ideal adsorber material are highly porous microparticles of poly(ether imide) (PEI) with diameters in the range from 50-180μm and a porosity around 88±2% prepared by a spraying and coagulation process.It is essential to make sure that these synthetic polymers should not evoke any inflammatory or apoptotic response during dialysis. Therefore in our study we evaluated in vitro effect of PEI microparticle extracts in human aortic endothelial cells (HEACs) concerning toxicity, inflammation and apoptosis. No cell toxicity was observed when HAECs were treated with PEI extracts and inflammatory/apoptotic markers were not upregulated in presence of PEI extracts. Our results ensure biocompatibility of PEI particles and further hemocompatibility of particles will be tested.

  13. Processing and Properties of Vacuum Assisted Resin Transfer Molded Phenylethynyl Terminated Imide Composites

    NASA Technical Reports Server (NTRS)

    Cano, Roberto J.; Ghose, Sayata; Watson, Kent A.; Chunchu, Prasad B.; Jensen, Brian J.; Connell, John W.

    2012-01-01

    Polyimide composites are very attractive for applications that require a high strength to weight ratio and thermal stability. Recent work at NASA Langley Research Center (LaRC) has concentrated on developing new polyimide resin systems that can be processed without the use of an autoclave for advanced aerospace applications. Due to their low melt viscosities and long melt stability, certain phenylethynyl terminated imides (PETI) can be processed into composites using high temperature vacuum assisted resin transfer molding (HT-VARTM). VARTM has shown the potential to reduce the manufacturing cost of composite structures. In the current study, two PETI resins, LARC(Trademark) PETI-330 and LARC(Trademark) PETI-9, were infused into carbon fiber preforms at 260 C and cured at temperatures up to 371 C. Photomicrographs of polished cross sections were taken and void contents, determined by acid digestion, were below 4.5%. Mechanical properties including short block compression (SBC), compression after impact (CAI), and open hole compression (OHC) were determined at room temperature, 177 C, and 288 C. Both PETI-9 and PETI-330 composites demonstrated very good retention of mechanical properties at elevated temperatures. SBC and OHC properties after aging for 1000 hours at temperatures up to 288 C were also determined.

  14. Tribological behavior of blends of polyether ether ketone and polyether imide

    NASA Astrophysics Data System (ADS)

    Yoo, Jong H.; Eiss, Norman S., Jr.

    1993-04-01

    The friction and wear properties of injection-molded disks of PEEK/polyether imide (PEI) blends in dry sliding by a stainless steel ball were determined at room temperature at two normal loads and two sliding velocities for as-molded and annealed samples. The wear rates increased as the amount of PEI in the blends increased. The decrease in elongation to rupture caused by the increase in PEI content seemed to cause the wear mechanism to change from plastic grooving to fatigue wear. The wear rate increased as the normal load increased, although the relationship was nonlinear and related to the sliding speed and composition. The wear rate increased as the crystallinity of the PEEK component decreased. PEEK did not wear for the given test conditions. A steel ball plastically grooved the PEEK and there was no net loss of material. The wear rate was insensitive to change in velocity, except at the higher loads, for 50/50 and 0/100 blends. The friction coefficient was 0.1-0.16 when plastic grooving was occurring and 0.23-0.34 when wear particles were being formed.

  15. Synthesis of Perylene Imide Diones as Platforms for the Development of Pyrazine Based Organic Semiconductors.

    PubMed

    de Echegaray, Paula; Mancheño, María J; Arrechea-Marcos, Iratxe; Juárez, Rafael; López-Espejo, Guzmán; López Navarrete, J Teodomiro; Ramos, María Mar; Seoane, Carlos; Ortiz, Rocío Ponce; Segura, José L

    2016-11-18

    There is a great interest in peryleneimide (PI)-containing compounds given their unique combination of good electron accepting ability, high abosorption in the visible region, and outstanding chemical, thermal, and photochemical stabilities. Thus, herein we report the synthesis of perylene imide derivatives endowed with a 1,2-diketone functionality (PIDs) as efficient intermediates to easily access peryleneimide (PI)-containing organic semiconductors with enhanced absorption cross-section for the design of tunable semiconductor organic materials. Three processable organic molecular semiconductors containing thiophene and terthiophene moieties, PITa, PITb, and PITT, have been prepared from the novel PIDs. The tendency of these semiconductors for molecular aggregation have been investigated by NMR spectroscopy and supported by quantum chemical calculations. 2D NMR experiments and theoretical calculations point to an antiparallel π-stacking interaction as the most stable conformation in the aggregates. Investigation of the optical and electrochemical properties of the materials is also reported and analyzed in combination with DFT calculations. Although the derivatives presented here show modest electron mobilities of ∼10(-4) cm(2)V(-1)s(-1), these preliminary studies of their performance in organic field effect transistors (OFETs) indicate the potential of these new building blocks as n-type semiconductors.

  16. P-V-T Properties of Polyimides and Model Imide Compounds

    NASA Technical Reports Server (NTRS)

    Orwoll, Robert A.

    1997-01-01

    Aromatic polyimides are used as matrix resins in advanced composites, as high strength films, and as high-temperature adhesives, owing in part to their unusual thermal and chemical stability. The polyimides' desirable qualities of very high softening temperatures and negligibly small solubilities in and low permeabilities by most solvents have limited the kinds of fundamental studies that can be performed on these systems. Consequently, relationships between the molecular structure of polyimides and their bulk properties are not as well understood as might be expected given their widespread applications. In particular, the intermolecular forces in polyimides that play a critical role determining their densities, solubilities, viscosities, moduli, glass transitions, etc. are less well characterized for polyimides than for other widely used polymeric materials. The purpose of the present study is to obtain experimental data for establishing parameters that characterize the intermolecular forces in polyimides. We report here our studies on tractable low molecular-weight imides that contain the same structural features that are present in polyimide materials. We have measured equation-of-state properties and dipole moments for a variety of such systems in the liquid state. Both pure compounds and binary mixtures have been studied.

  17. Liquid structure of room-temperature ionic liquid, 1-Ethyl-3-methylimidazolium bis-(trifluoromethanesulfonyl) imide.

    PubMed

    Fujii, Kenta; Soejima, Yasufumi; Kyoshoin, Yasuhiro; Fukuda, Shuhei; Kanzaki, Ryo; Umebayashi, Yasuhiro; Yamaguchi, Toshio; Ishiguro, Shin-ichi; Takamuku, Toshiyuki

    2008-04-10

    The liquid structure of 1-ethyl-3-methylimidazolium bis-(trifluoromethanesulfonyl) imide (EMI(+)TFSI(-)) has been studied by means of large-angle X-ray scattering (LAXS), (1)H, (13)C, and (19)F NMR, and molecular dynamics (MD) simulations. LAXS measurements show that the ionic liquid is highly structured with intermolecular interactions at around 6, 9, and 15 A. The intermolecular interactions at around 6, 9, and 15 A are ascribed, on the basis of the MD simulation, to the nearest neighbor EMI(+)...TFSI(-) interaction, the EMI(+)...EMI(+) and TFSI(-)...TFSI(-) interactions, and the second neighbor EMI+...TFSI(-) interaction, respectively. The ionic liquid involves two conformers, C(1) (cis) and C(2) (trans), for TFSI(-), and two conformers, planar cis and nonplanar staggered, for EMI(+), and thus the system involves four types of the EMI(+)...TFSI(-) interactions in the liquid state by taking into account the conformers. However, the EMI(+)...TFSI(-) interaction is not largely different for all combinations of the conformers. The same applies alsoto the EMI(+)...EMI(+) and TFSI(-)...TFSI(-) interactions. It is suggested from the 13C NMR that the imidazolium C(2) proton of EMI(+) strongly interacts with the O atom of the -SO(2)(CF(3)) group of TFSI(-). The interaction is not ascribed to hydrogen-bonding, according to the MD simulation. It is shown that the liquid structure is significantly different from the layered crystal structure that involves only the nonplanar staggered EMI(+) and C(1) TFSI(-) conformers.

  18. Thermal properties and ionic conductivity of imidazolium bis(trifluoromethanesulfonyl)imide dicationic ionic liquids.

    PubMed

    Pitawala, Jagath; Matic, Aleksandar; Martinelli, Anna; Jacobsson, Per; Koch, Victor; Croce, Fausto

    2009-08-06

    We report on the thermal and transport properties of new dicationic ionic liquids. The new ionic liquids are based on the bis(trifluoromethanesulfonyl)imide [NTf(2)](-) anion and a cation that contains two imidazolium rings, connected by either a pentane or a decane hydrocarbon chain and different side groups. We have investigated the conductivity and the thermal properties by dielectric spectroscopy and differential scanning calorimetry, respectively. Our results show that the length of the alkyl chain on the cation has no, or weak, influence on the glass transition temperature, T(g), whereas the presence of rigid aromatic side groups has a strong influence increase T(g). The highest ionic conductivity is 5.9 x 10(-4) S cm(-1) at 298 K for an ionic liquid with a decane chain and one methyl group on each imidazolium ring. The conductivity results correlate well with the glass transition temperatures. This shows that the flexibility of the geminal cations is very important for the conductivity. However, the presence of nonflexible aromatic side groups on the imidazolium ring decreases the flexibility and hence the mobility.

  19. Properties of new low melting point quaternary ammonium salts with bis(trifluoromethanesulfonyl)imide anion

    NASA Astrophysics Data System (ADS)

    Kärnä, Minna; Lahtinen, Manu; Kujala, Anna; Hakkarainen, Pirkko-Leena; Valkonen, Jussi

    2010-11-01

    Eight new monocationic quaternary ammonium (QA) salts with the bis(trifluoromethanesulfonyl)imide (TFSI) anion were prepared by metathesis using our previously reported QA halides as precursors. New salts were characterized both in liquid and solid state using 1H and 13C NMR techniques, mass spectroscopy and elemental analysis together with X-ray diffraction and thermoanalytical methods. In addition, residual water content, viscosity and conductivity measurements were made for three of the room-temperature ionic liquids (RTILs). The crystal structures of three compounds were determined by X-ray single crystal diffraction. Powder diffraction was used to study the crystallinity of the solid salts and to compare structural similarities between the single crystals and the microcrystalline bulk powders. Three of the salts are liquid below room temperature, having broad liquid ranges (˜300 °C), and in total five out of eight salts melt below 100 °C. Moreover, powder diffraction data of the two RTILs were able to be measured at sub-ambient temperatures using in situ low-temperature powder X-ray diffraction revealing high crystallinity on both RTILs below their freezing point. The RTILs presented relatively high conductivities (˜0.1-0.2 S m -1) and moderate to relatively low viscosities. The determined physicochemical properties of the reported ILs suggest their applicability on various applications such as heat transfer fluids, high temperature synthesis and lubricants.

  20. Initial adhesive screening of novel polyamide-imides and their copolymers

    NASA Technical Reports Server (NTRS)

    Progar, Donald J.; Dezern, James F.

    1988-01-01

    Continued interest by the research community in thermally stable, tough, high temperature adhesives has resulted in the investigation by Langley Research Center of two linear aromatic polyamide-imide (PAI) homopolymers and two linear aromatic PAI copolymers. The homopolymers were made with either 3,3'=DABA or 4,4'-DABA and BTDA. The two polymers were prepared with a monomer ratio of 0.75 DABP:0.25 DABA:1.00 BTDA. These aromatic PAIs possess high thermal stability because of intermolecular hydrogen bonding and chain stiffness. Lap shear strength (LSS) was the main criteria used to evaluate the polymers as adhesives. LSS of bonded Ti-6Al-4V was determined at room temperature (RT), 177, 204 and 232 C. The glass transition temperature and the type of bond failure were also determined. The best LSS values of the four adhesive systems investigated were obtained with the PAI copolymer identified in the report as LARC-TPI (25 percent 3,3'-DABA); however, it did not produce LSSs nearly as high as LARC-TPI. The poor flow properties observed appear to be due to a combination of high molecular weight and the increased interchain electronic interactions associated with the amide group.

  1. Initial evaluation of novel polyamide-imides and their copolymers as adhesives

    NASA Technical Reports Server (NTRS)

    Progar, Donald J.; Dezern, James F.

    1989-01-01

    Continued interest by the research community in thermally stable, tough, high temperature adhesives has resulted in the investigation by Langley Research Center of two linear aromatic polyamide-imide (PAI) homopolymers and two linear aromatic PAI copolymers. The homopolymers were made with either 3,3'=DABA or 4,4'-DABA and BTDA. The two polymers were prepared with a monomer ratio of 0.75 DABP:0.25 DABA:1.00 BTDA. These aromatic PAIs possess high thermal stability because of intermolecular hydrogen bonding and chain stiffness. Lap shear strength (LSS) was the main criteria used to evaluate the polymers as adhesives. LSS of bonded Ti-6Al-4V was determined at room temperature (RT), 177, 204 and 232 C. The glass transition temperature and the type of bond failure were also determined. The best LSS values of the four adhesive systems investigated were obtained with the PAI copolymer identified in the report as LARC-TPI (25 percent 3,3'-DABA); however, it did not produce LSSs nearly as high as LARC-TPI. The poor flow properties observed appear to be due to a combination of high molecular weight and the increased interchain electronic interactions associated with the amide group.

  2. Friction and wear behavior of short fiber-reinforced poly(amide-imide) composites

    SciTech Connect

    Lee, K.H.; Youn, J.R. )

    1992-06-01

    Tribological behavior of short fiber-reinforced thermoplastic composites was investigated experimentally and theoretically. Short carbon fiber and glass fiber reinforced poly(amide-imide) composites were tested. Titanium oxide powder-filled composite was also tested for comparison with the fiber composites. Block-on-ring type wear testing was performed for 24 h at three different sliding conditions. Frictional force was measured and stored by a data acquisition system and wear was measured as weight loss after the test. Wear tracks on the specimen and the counterface were examined with an optical microscope to observe fiber damage and formation of wear film. The equivalent stress distribution around each fiber at the sliding surface was calculated by employing a finite element program. The lowest friction and wear was obtained for the carbon fiber composite, the highest friction for the glass fiber composite, and the highest wear for TiO2-filled one. It was observed that the glass fibers are damaged and removed from the surface more easily than the carbon fibers, and the finite element analysis also suggests easier debonding of glass fibers. 23 refs.

  3. Positively charged and bipolar layered poly(ether imide) nanofiltration membranes for water softening applications

    NASA Astrophysics Data System (ADS)

    Gassara, S.; Abdelkafi, A.; Quémener, D.; Amar, R. Ben; Deratani, A.

    2015-07-01

    Poly(ether imide) (PEI) ultrafiltration membranes were chemically modified with branched poly(ethyleneimine) to obtain nanofiltration (NF) membrane Cat PEI with a positive charge in the pH range below 9. An oppositely charged polyelectrolyte layer was deposited on the resulting membrane surface by using sodium polystyrene sulfonate (PSSNa) and sodium polyvinyl sulfonate (PVSNa) to prepare a bipolar layered membrane NF Cat PEI_PSS and Cat PEI_PVS having a negatively charged surface and positively charged pores. Cat PEI exhibited good performance to remove multivalent cations (more than 90% of Ca2+) from single salt solutions except in presence of sulfate ions. Adding an anionic polyelectrolyte layer onto the positively charged surface resulted in a significant enhancement of rejection performance even in presence of sulfate anions. Application of the prepared membranes in water softening of natural complex mixtures was successful for the different studied membranes and a large decrease of hardness was obtained. Moreover, Cat PEI_PSS showed a good selectivity for nitrate removal. Fouling experiments were carried out with bovine serum albumin, as model protein foulant. Cat PEI_PSS showed much better fouling resistance than Cat PEI with a quantitative flux recovery ratio.

  4. Thermal Reaction of Cinnamate Oligomers and Their Effect on the Orientational Stability of Liquid Crystals

    NASA Astrophysics Data System (ADS)

    Hah, Hyundae; Sung, Shi‑Joon; Park, Jung‑Ki

    2006-08-01

    Cinnamate groups are well-known for a dimerization reaction upon exposure to ultraviolet irradiation and a thermal reaction after being heated. In this study, to verify the thermal reaction of the cinnamate group in detail, we investigated the thermal crosslinking of cinnamate oligomers. The thermal reaction of cinnamate oligomers of low molecular weight is induced more readily by thermal energy compared with that of cinnamate polymers. This reaction is attributed to a radical reaction involving the carbon-carbon double bond in the cinnamate group. The orientation of the liquid crystal depended on the length of the spacers in the cinnamate oligomers.

  5. Studies on Oligomer Metal Complexes Derived from Bisamic Acid of Pyromellitic Dianhydride and 4-Bromoaniline

    PubMed Central

    Patel, Yogesh S.

    2014-01-01

    Novel oligomer metal complexes (2a–f) of the ligand 2,5-bis((4-bromophenyl)carbamoyl) terephthalic acid (1) were prepared using transition metal salts and characterized by various spectroscopic techniques. The geometry of oligomer metal complexes was carried out by electronic spectral analysis and magnetic measurement studies. Polymeric properties have also been carried out. Ligand was synthesized using pyromellitic dianhydride and 4-bromoaniline. It was duly characterized. All novel synthesized compounds 1 and 2a–f were evaluated for their antibacterial and antifungal activity. The results showed significantly higher antibacterial and antifungal activity of oligomer metal complexes compared to the ligand. PMID:27379295

  6. Studies on Oligomer Metal Complexes Derived from Bisamic Acid of Pyromellitic Dianhydride and 4-Bromoaniline.

    PubMed

    Patel, Yogesh S

    2014-01-01

    Novel oligomer metal complexes (2a-f) of the ligand 2,5-bis((4-bromophenyl)carbamoyl) terephthalic acid (1) were prepared using transition metal salts and characterized by various spectroscopic techniques. The geometry of oligomer metal complexes was carried out by electronic spectral analysis and magnetic measurement studies. Polymeric properties have also been carried out. Ligand was synthesized using pyromellitic dianhydride and 4-bromoaniline. It was duly characterized. All novel synthesized compounds 1 and 2a-f were evaluated for their antibacterial and antifungal activity. The results showed significantly higher antibacterial and antifungal activity of oligomer metal complexes compared to the ligand.

  7. Common structure and toxic function of amyloid oligomers implies a common mechanism of pathogenesis.

    PubMed

    Glabe, Charles G; Kayed, Rakez

    2006-01-24

    Recent findings indicate that soluble amyloid oligomers may represent the primary pathologic species in degenerative diseases. These amyloid oligomers share common structural features and the ability to permeabilize membranes, suggesting that they also share a common primary mechanism of pathogenesis. Membrane permeabilization by amyloid oligomers may initiate a common group of downstream pathologic processes, including intracellular calcium dyshomeostasis, production of reactive oxygen species, altered signaling pathways, and mitochondrial dysfunction that represent key effectors of cellular dysfunction and cell death in amyloid-associated degenerative disease, such as sporadic inclusion-body myositis.

  8. Red-emitting π-conjugated oligomers infused single-wall carbon nanotube sheets

    NASA Astrophysics Data System (ADS)

    Fujimori, Toshihiko; Urita, Koki

    2016-04-01

    We demonstrate the one-step thermal fusion and infusion of pyrene molecules inside single-wall carbon nanotubes (SWCNTs). Despite the presence of metallic-SWCNTs, which behave as a quencher due to gapless electronic states, the nanohybrids consisting of pyrene and/or azupyrene oligomers infused SWCNT sheets exhibit red fluorescence by the ultraviolet, blue, and green light excitations. The wavelength-independent light-emitting behavior is explained by (1) infused PAH oligomers inside semiconducting-SWCNTs and (2) the peculiar π-π interaction through mixed π-conjugated state between the π-conjugated oligomers and non-armchair metallic-SWCNTs.

  9. Phenylethynyl Terminated Arylene Ether Oxadiazole and Triazole Oligomers and Their Cured Polymers

    NASA Technical Reports Server (NTRS)

    Thompson, C. M.; Hergenrother, P. M.

    2001-01-01

    Several novel phenylethynyl terminated arylene ether oligomers containing oxadiazole and triazole rings were prepared as part of an effort to develop high performance polymers with an attractive combination of properties (e.g. processability and mechanical performance) for future NASA applications. The oligomers displayed low melt viscosities and good solubilities. Thin films cast from solutions of the oligomers and cured for one hour at 350 C in air gave good tensile properties. Titanium to titanium (6Al-4V) tensile shear specimens were readily fabricated and provided moderate strengths. The chemistry and properties of these new materials are discussed.

  10. Effect of molecular weight of oligomer on ionic diffusion in oligomer electrolytes and its implication for dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Park, Jong Hyuk; Choi, Kyu Jin; Kim, Junkyung; Kang, Yong Soo; Lee, Sang-Soo

    This study measures the diffusion coefficients of I - and I 3 - in oligomer electrolytes as a function of the molecular weight of oligomers and investigates their effect on the performance of dye-sensitized solar cells (DSSCs). The high-diffusion coefficients of ions in an oligomer electrolyte with a lower molecular weight can help to promote the redox mechanism in DSSCs and thereby increase the short-circuit current density. They can also cause a decrease in the open-circuit voltage since a high-diffusion coefficient of I 3 - is capable of reducing the lifetime of electrons in TiO 2 electrodes. To offset these effects, N-methyl-benzimidazole is added to the oligomer electrolytes, thereby improving the open-circuit voltage and fill factor and, consequently, the overall energy-conversion efficiency, which increases to over 5%. A further test involving storage at a high temperature of 75 °C demonstrates that DSSCs employing the oligomer electrolytes show excellent thermal stability over 200 h.

  11. Large Soluble Oligomers of Amyloid β-Protein from Alzheimer Brain Are Far Less Neuroactive Than the Smaller Oligomers to Which They Dissociate.

    PubMed

    Yang, Ting; Li, Shaomin; Xu, Huixin; Walsh, Dominic M; Selkoe, Dennis J

    2017-01-04

    Soluble oligomers of amyloid β-protein (oAβ) isolated from the brains of Alzheimer's disease (AD) patients have been shown experimentally (in the absence of amyloid plaques) to impair hippocampal synaptic plasticity, decrease synapses, induce tau hyperphosphorylation and neuritic dystrophy, activate microglial inflammation, and impair memory in normal adult rodents. Nevertheless, there has been controversy about what types of oligomers actually confer these AD-like phenotypes. Here, we show that the vast majority of soluble Aβ species obtained from brains of humans who died with confirmed AD elute at high molecular weight (HMW) on nondenaturing size-exclusion chromatography. These species have little or no cytotoxic activity in several bioassays. However, incubation of HMW oAβ in mildly alkaline buffer led to their quantitative dissociation into low molecular weight oligomers (∼8-70 kDa), and these were now far more bioactive: they impaired hippocampal LTP, decreased neuronal levels of β2-adrenergic receptors, and activated microglia in wt mice in vivo Thus, most soluble Aβ assemblies in AD cortex are large and inactive but under certain circumstances can dissociate into smaller, highly bioactive species. Insoluble amyloid plaques likely sequester soluble HMW oligomers, limiting their potential to dissociate. We conclude that conditions that destabilize HMW oligomers or retard the sequestration of their smaller, more bioactive components are important drivers of Aβ toxicity. Selectively targeting these small, cytotoxic forms should be therapeutically beneficial.

  12. Coulombic free energy and salt ion association per phosphate of all-atom models of DNA oligomer: dependence on oligomer size.

    PubMed

    Shkel, Irina A; Record, M Thomas

    2012-08-23

    We investigate how the coulombic Gibbs free energy and salt ion association per phosphate charge of DNA oligomers vary with oligomer size (i.e. number of charged residues ∣ZD∣) at 0.15 M univalent salt by non-linear Poisson Boltzmann (NLPB) analysis of all-atom DNA models. Calculations of these quantities ([Formula: see text], [Formula: see text]) are performed for short and long double-stranded (ds) and single-stranded (ss) DNA oligomers, ranging from 4 to 118 phosphates (ds) and from 2 to 59 phosphates (ss). Behaviors of [Formula: see text] and [Formula: see text] as functions of ∣ZD∣ provide a measure of the range of the coulombic end effect and determine the size of an oligomer at which an interior region with the properties (per charge) of the infinite-length polyelectrolyte first appears. This size (10-11 phosphates at each end for ds DNA and 6-9 for ss DNA at 0.15 M salt) is in close agreement with values obtained previously by Monte Carlo and NLPB calculations for cylindrical models of polyions, and by analysis of binding of oligocations to DNA oligomers. Differences in [Formula: see text] and in [Formula: see text] between ss and ds DNA are used to predict effects of oligomeric size and salt concentration on duplex stability in the vicinity of 0.15 M salt. Results of all-atom calculations are compared with results of less structurally detailed models and with experimental data.

  13. Synaptotoxic amyloid-β oligomers: a molecular basis for the cause, diagnosis, and treatment of Alzheimer's disease?

    PubMed

    Klein, William L

    2013-01-01

    The oligomer hypothesis for Alzheimer's disease (AD)was introduced in 1998. It was based on evidence that oligomers could exist free of amyloid fibrils, that fibril-free oligomer solutions rapidly inhibited long term potentiation, and that oligomers ultimately caused a highly selective nerve cell death. Fibrils no longer were the only toxins made by amyloid-β (Aβ), and likely not the most important ones. Oligomers provided a new basis for instigating AD. Since introduction of the hypothesis, more than 1,500 articles on oligomers have been published. Articles for this review were selected for contributions to oligomer theory at three different levels. The first set demonstrated new aspects of oligomer pathobiology in cell models, showing that exposure of neurons to oligomers is sufficient to cause key features of AD neuropathology. The second set confirmed the relationship between oligomers and salient AD neuropathology in animal models, consistent with other in vivo studies that overall have substantiated cell-based discoveries. The third set developed strategies for therapeutic targeting of oligomers, introducing both small molecule and antibody-based approaches. These and related findings from many groups have helped establish oligomers as central to the mechanism of AD pathogenesis. Comprising a ligand-based attack on specific synapses, the action of toxic oligomers gives a molecular basis to account for key features of AD neuropathology and to explain why early disease targets memory. Although there still is no effective treatment for AD, insights over the past five years raise hopes that new approaches targeting Aβ oligomers could finally bring disease-modifying therapeutics.

  14. Reactive Processing with Difunctional Oligomers to Increase Interfacial Adhesion in Polymer Blends

    NASA Astrophysics Data System (ADS)

    O'Brien, Charles; Rice+, Kevin; Dadmun, Mark

    2000-03-01

    The intoduction of blocky copolymers represents a possible method of compatibilizing two immiscible polymers in a blend. However, copolymers do not diffuse quickly to the interface of a polymer blend system. Therefore, reactive processing is being investigated as a means to form in-situ compatibilizers for polymer blends. A model system composed of poly(bisphenol A-co-epichlorohydrin) blended with poly(ethylene oxide) that is compatibilized with difunctional oligomers that are the same structure as the blend components is currently under investigation. It is expected that the oligomers can undergo an addition copolymerization during processing to create the blocky copolymers at the biphasic interface. Initial tensile measurements show that the addition of the reactive oligomers improves the properties of the blend. Additionally, preliminary results indicate that reactive oligomers may act as plasticizers and continue to polymerize at room temperature after the blend is removed from the melt mixer if insufficiently mixed.

  15. Enhanced Emission of Highly Labeled DNA Oligomers near Silver Metallic Surfaces

    PubMed Central

    Malicka, Joanna; Gryczynski, Ignacy; Lakowicz, Joseph R.

    2009-01-01

    Fluorescein is a widely used fluorescent probe in DNA analysis. One difficulty with fluorescein is its self-quenching due to resonance energy transfer between the residues, which results in decreased intensities with increasing labeling density. We examined the emission spectral properties of DNA oligomers labeled with one or five fluorescein residues. The emission intensity of the more highly labeled oligomer was decreased due to self-quenching. The self-quenching was mostly eliminated when this oligomer was held ~90 Å from the surface of metallic silver particles. The intensities increased 7- and 19-fold for the oligomers with one or five fluoresceins, respectively. The increased intensity did not result in increased photobleaching. These results suggest the use of substrates coated with silver particles for increased sensitivity on DNA arrays or for DNA analysis. PMID:14632044

  16. Microwave assisted synthesis of bithiophene based donor-acceptor-donor oligomers and their optoelectronic performances

    NASA Astrophysics Data System (ADS)

    Bathula, Chinna; Buruga, Kezia; Lee, Sang Kyu; Khazi, Imtiyaz Ahmed M.; Kang, Youngjong

    2017-07-01

    In this article we present the synthesis of two novel bithiophene based symmetrical π conjugated oligomers with donor-acceptor-donor (D-A-D) structures by microwave assisted PdCl2(dppf) catalyzed Suzuki coupling reaction. These molecules contain electron rich bithiophene as a donor, dithienothiadiazole[3,4-c]pyridine and phthalic anhydride units as acceptors. The shorter reaction time, excellent yields and easy product isolation are the advantages of this method. The photophysical prerequisites for electronic application such as strong and broad optical absorption, thermal stability, and compatible energy levels were determined for synthesized oligomers. Optical band gap for the oligomers is found to be 1.72-1.90 eV. The results demonstrated the novel oligomers to be promising candidates in organic optoelectronic applications.

  17. The Anti-Prion Antibody 15B3 Detects Toxic Amyloid-β Oligomers

    PubMed Central

    Stravalaci, Matteo; Tapella, Laura; Beeg, Marten; Rossi, Alessandro; Joshi, Pooja; Pizzi, Erika; Mazzanti, Michele; Balducci, Claudia; Forloni, Gianluigi; Biasini, Emiliano; Salmona, Mario; Diomede, Luisa; Chiesa, Roberto; Gobbi, Marco

    2016-01-01

    15B3 is a monoclonal IgM antibody that selectively detects pathological aggregates of the prion protein (PrP). We report the unexpected finding that 15B3 also recognizes oligomeric but not monomeric forms of amyloid-β (Aβ)42, an aggregating peptide implicated in the pathogenesis of Alzheimer’s disease (AD). The 15B3 antibody: i) inhibits the binding of synthetic Aβ42 oligomers to recombinant PrP and neuronal membranes; ii) prevents oligomer-induced membrane depolarization; iii) antagonizes the inhibitory effects of oligomers on the physiological pharyngeal contractions of the nematode Caenorhabditis elegans; and iv) counteracts the memory deficits induced by intracerebroventricular injection of Aβ42 oligomers in mice. Thus this antibody binds to pathologically relevant forms of Aβ, and offers a potential research, diagnostic, and therapeutic tool for AD. PMID:27392850

  18. Vesicle permeabilization by purified soluble oligomers of prion protein: a comparative study of the interaction of oligomers and monomers with lipid membranes.

    PubMed

    Chich, J-F; Chapuis, C; Henry, C; Vidic, J; Rezaei, H; Noinville, S

    2010-04-09

    The conversion of normal cellular prion protein (PrP) into its pathological isoform, scrapie PrP, may occur at the cell surface or, more probably, in late endosomes. The early events leading to the structural conversion of PrP appear to be related to the presence of more or less stable soluble oligomers, which might mediate neurotoxicity. In the current study, we investigate the interaction of alpha-rich PrP monomers and beta-rich size-exclusion-chromatography-purified PrP oligomers with lipid membranes. We compare their structural properties when associated with lipid bilayers and study their propensities to permeabilize the membrane at physiological pH. We also study the influence of the N-terminal flexible region (residues 24-103) by comparing full-length PrP(24-234) and N-terminally truncated PrP(104-234) oligomers. We showed that both 12-subunit oligomers cause an immediate and large increase in the permeability of the membrane, whereas equivalent amounts of monomeric forms cause no detectable leakage. Although the two monomeric PrP constructs undergo an alpha-to-beta conformational change when bound to the negatively charged membrane, only the full-length form of monomeric PrP has a weak fusogenic effect. Finally, the oligomers affect the integrity of the membrane differently from the monomers, independently of the presence of the N-terminal flexible domain. As for other forms of amyloidogenesis, a reasonable mechanism for the toxicity arising from PrP fibrillization must be associated with low-molecular-weight oligomeric intermediates, rather than with mature fibrils. Knowledge of the mechanism of action of these soluble oligomers would have a high impact on the development of novel therapeutic targets.

  19. Salt anions promote the conversion of HypF-N into amyloid-like oligomers and modulate the structure of the oligomers and the monomeric precursor state.

    PubMed

    Campioni, Silvia; Mannini, Benedetta; López-Alonso, Jorge P; Shalova, Irina N; Penco, Amanda; Mulvihill, Estefania; Laurents, Douglas V; Relini, Annalisa; Chiti, Fabrizio

    2012-12-07

    An understanding of the solution factors contributing to the rate of aggregation of a protein into amyloid oligomers, to the modulation of the conformational state populated prior to aggregation and to the structure/morphology of the resulting oligomers is one of the goals of present research in this field. We have studied the influence of six different salts on the conversion of the N-terminal domain of Escherichiacoli HypF (HypF-N) into amyloid-like oligomers under conditions of acidic pH. Our results show that salts having different anions (NaCl, NaClO(4), NaI, Na(2)SO(4)) accelerate oligomerization with an efficacy that follows the electroselectivity series of the anions (SO(4)(2-)≥ ClO(4)(-)>I(-)>Cl(-)). By contrast, salts with different cations (NaCl, LiCl, KCl) have similar effects. We also investigated the effect of salts on the structure of the final and initial states of HypF-N aggregation. The electroselectivity series does not apply to the effect of anions on the structure of the oligomers. By contrast, it applies to their effect on the content of secondary structure and on the exposure of hydrophobic clusters of the monomeric precursor state. The results therefore indicate that the binding of anions to the positively charged residues of HypF-N at low pH is the mechanism by which salts modulate the rate of oligomerization and the structure of the monomeric precursor state but not the structure of the resulting oligomers. Overall, the data contribute to rationalize the effect of salts on amyloid-like oligomer formation and to explain the role of charged biological macromolecules in protein aggregation processes.

  20. Bacterial Resistance to Antisense Peptide Phosphorodiamidate Morpholino Oligomers

    PubMed Central

    Puckett, Susan E.; Reese, Kaleb A.; Mitev, Georgi M.; Mullen, Valerie; Johnson, Rudd C.; Pomraning, Kyle R.; Mellbye, Brett L.; Tilley, Lucas D.; Iversen, Patrick L.; Freitag, Michael

    2012-01-01

    Peptide phosphorodiamidate morpholino oligomers (PPMOs) are synthetic DNA mimics that bind cRNA and inhibit bacterial gene expression. The PPMO (RFF)3RXB-AcpP (where R is arginine, F, phenylalanine, X is 6-aminohexanoic acid, B is β-alanine, and AcpP is acyl carrier protein) is complementary to 11 bases of the essential gene acpP (which encodes acyl carrier protein). The MIC of (RFF)3RXB-AcpP was 2.5 μM (14 μg/ml) in Escherichia coli W3110. The rate of spontaneous resistance of E. coli to (RFF)3RXB-AcpP was 4 × 10−7 mutations/cell division. A spontaneous (RFF)3RXB-AcpP-resistant mutant (PR200.1) was isolated. The MIC of (RFF)3RXB-AcpP was 40 μM (224 μg/ml) for PR200.1. The MICs of standard antibiotics for PR200.1 and W3110 were identical. The sequence of acpP was identical in PR200.1 and W3110. PR200.1 was also resistant to other PPMOs conjugated to (RFF)3RXB or peptides with a similar composition or pattern of cationic and nonpolar residues. Genomic sequencing of PR200.1 identified a mutation in sbmA, which encodes an active transport protein. In separate experiments, a (RFF)3RXB-AcpP-resistant isolate (RR3) was selected from a transposome library, and the insertion was mapped to sbmA. Genetic complementation of PR200.1 or RR3 with sbmA restored susceptibility to (RFF)3RXB-AcpP. Deletion of sbmA caused resistance to (RFF)3RXB-AcpP. We conclude that resistance to (RFF)3RXB-AcpP was linked to the peptide and not the phosphorodiamidate morpholino oligomer, dependent on the composition or repeating pattern of amino acids, and caused by mutations in sbmA. The data further suggest that (RFF)3R-XB PPMOs may be transported across the plasma membrane by SbmA. PMID:22985881

  1. Bacterial resistance to antisense peptide phosphorodiamidate morpholino oligomers.

    PubMed

    Puckett, Susan E; Reese, Kaleb A; Mitev, Georgi M; Mullen, Valerie; Johnson, Rudd C; Pomraning, Kyle R; Mellbye, Brett L; Tilley, Lucas D; Iversen, Patrick L; Freitag, Michael; Geller, Bruce L

    2012-12-01

    Peptide phosphorodiamidate morpholino oligomers (PPMOs) are synthetic DNA mimics that bind cRNA and inhibit bacterial gene expression. The PPMO (RFF)(3)RXB-AcpP (where R is arginine, F, phenylalanine, X is 6-aminohexanoic acid, B is β-alanine, and AcpP is acyl carrier protein) is complementary to 11 bases of the essential gene acpP (which encodes acyl carrier protein). The MIC of (RFF)(3)RXB-AcpP was 2.5 μM (14 μg/ml) in Escherichia coli W3110. The rate of spontaneous resistance of E. coli to (RFF)(3)RXB-AcpP was 4 × 10(-7) mutations/cell division. A spontaneous (RFF)(3)RXB-AcpP-resistant mutant (PR200.1) was isolated. The MIC of (RFF)(3)RXB-AcpP was 40 μM (224 μg/ml) for PR200.1. The MICs of standard antibiotics for PR200.1 and W3110 were identical. The sequence of acpP was identical in PR200.1 and W3110. PR200.1 was also resistant to other PPMOs conjugated to (RFF)(3)RXB or peptides with a similar composition or pattern of cationic and nonpolar residues. Genomic sequencing of PR200.1 identified a mutation in sbmA, which encodes an active transport protein. In separate experiments, a (RFF)(3)RXB-AcpP-resistant isolate (RR3) was selected from a transposome library, and the insertion was mapped to sbmA. Genetic complementation of PR200.1 or RR3 with sbmA restored susceptibility to (RFF)(3)RXB-AcpP. Deletion of sbmA caused resistance to (RFF)(3)RXB-AcpP. We conclude that resistance to (RFF)(3)RXB-AcpP was linked to the peptide and not the phosphorodiamidate morpholino oligomer, dependent on the composition or repeating pattern of amino acids, and caused by mutations in sbmA. The data further suggest that (RFF)(3)R-XB PPMOs may be transported across the plasma membrane by SbmA.

  2. Optically and redox-active ferroceneacetylene polymers and oligomers

    PubMed

    Plenio; Hermann; Sehring

    2000-05-15

    The palladium-catalyzed Sonogashira reaction can be used to build optically active, oligomeric 1,2,3-substituted ferrocenes up to the tetramer, as well as polymers, by sequential coupling of optically active (ee > 98 %), planar chiral iodoferroceneacetylenes and ferroceneacetylenes. (SFC)-1-Iodoferrocene-2-carbaldehyde (1) was reduced to the alcohol and methylated to give the corresponding methyl ether, which was Sonogashira-coupled with HC(triple bond)CSiEt3, resulting in (RFc)-1-(C(triple bond)CSiEt3)-2-methoxymethylferrocene (4) (79%, three steps). Orthometalation with tBuLi followed by quenching with 1,2-diodoethane gave (RFc)-1-(C(triple bond)CSiEt3)-2-methoxymethyl-3-iodoferrocene (5). Deprotection of the acetylene with nBu4NF resulted in (RFc)-1-ethynyl-2-methoxymethyl-3-iodoferrocene (6), which was Sonogashira-coupled with itself to produce an optically active polymer. Deprotection of 4 with nBu4NF and Sonogashira coupling of the product with 5 resulted in the dinuclear ferrocene 9. Deprotection of 9 and coupling with 5, followed by deprotection of the resulting acetylene 11, gave the trinuclear ferrocene 12. Another such sequence involving 11 and 5 produced a tetranuclear ferrocene 13. To study the electronic communication in such oligomers in more detail, two symmetrical, closely interrelated, trinuclear ferrocenes 18 and 19 were synthesized. The redox potentials of all the ferrocenes and the ferroceneacetylene polymer were determined by cyclic and square-wave voltammetry. All the metallocenes were investigated by UV/Vis spectroscopy. A linear relationship was found between lambdamax and l/n (n=number of ferrocene units in the oligomer). The polymer displayed two redox waves in the cyclic voltammogram, at 0.65 and 0.795 V. The corresponding mixed-valence oligoferrocene cations were synthesized from four ferroceneacetylenes, and their metal-metal charge transfer bands were examined by UV/Vis-NIR. The resonance exchange integrals Had, calculated on the

  3. Structural study on rodlike aromatic polyimides derived by solid-state thermal and chemical imidization of poly(amic n-dodecyl ester)

    NASA Astrophysics Data System (ADS)

    Inomata, Katsuhiro; Ozeki, Yuki; Shimomura, Sachi; Sakamoto, Yuhji; Nakanishi, Eiji

    2005-04-01

    Para-linked aromatic poly(amic n-dodecyl ester) (PA-12), in which long n-alkyl side chains are attached on rodlike aromatic polyamide, was prepared by polycondensation of 2,5-bis(1-dodecyloxycarbonyl)terephthaloyl chloride and 1,4-diaminobenzene. In as-cast PA-12 film, formation of layered structure with alternating main-chain-segregated and side-chain-segregated layers is suggested by X-ray diffraction measurement. PA-12 is a precursor of rodlike aromatic polyimide, poly(1,4-phenylene pyromellitimide) (PPPI). Solid-state thermal imidization and base-catalyzed chemical imidization of PA-12 film has been investigated. Although the layered structure of PA-12 was destroyed during the imidization reaction, the obtained PPPI exhibited lower density than densely packed PPPI. This result may indicate that the side chain-segregated domain was transformed to a cavity surrounded by PPPI after the imidization reaction. Chemical imidization in pyridine/toluene mixture and subsequent heating at 200 °C was the optimum condition to obtain low density PPPI.

  4. Styrene-terminated polysulfone oligomers as matrix material for graphite reinforced composites: An initial study

    NASA Technical Reports Server (NTRS)

    Garcia, Dana; Bowles, Kenneth J.; Vannucci, Raymond D.

    1987-01-01

    Styrene terminated polysulfone oligomers are part of an oligomeric class of compounds with end groups capable of thermal polymerization. These materials can be used as matrices for graphite reinforced composites. The initial evaluation of styrene terminated polysulfone oligomer based composites are summarized in terms of fabrication methods, and mechanical and environmental properties. In addition, a description and evaluation is provided of the NASA/Industry Fellowship Program for Technology Transfer.

  5. Soluble Prion Protein Binds Isolated Low Molecular Weight Amyloid-β Oligomers Causing Cytotoxicity Inhibition.

    PubMed

    Williams, Thomas L; Choi, Jin-Kyu; Surewicz, Krystyna; Surewicz, Witold K

    2015-12-16

    A growing number of observations indicate that soluble amyloid-β (Aβ) oligomers play a major role in Alzheimer's disease. Recent studies strongly suggest that at least some of the neurotoxic effects of these oligomers are mediated by cellular, membrane-anchored prion protein and that Aβ neurotoxicity can be inhibited by soluble recombinant prion protein (rPrP) and its fragments. However, the mechanism by which rPrP interacts with Aβ oligomers and prevents their toxicity is largely unknown, and studies in this regard are hindered by the large structural heterogeneity of Aβ oligomers. To overcome this difficulty, here we used photoinduced cross-linking of unmodified proteins (PICUP) to isolate well-defined oligomers of Aβ42 and characterize these species with regard to their cytotoxicity and interaction with rPrP, as well the mechanism by which rPrP inhibits Aβ42 cytotoxicity. Our data shows that the addition of rPrP to the assembling Aβ42 results in a shift in oligomer size distribution, decreasing the population of toxic tetramers and higher order oligomers and increasing the population of nontoxic (and possibly neuroprotective) monomers. Isolated oligomeric species of Aβ42 are cytotoxic to primary neurons and cause permeation of model lipid bilayers. These toxic effects, which are oligomer size-dependent, can be inhibited by the addition of rPrP, and our data suggest potential mechanisms of this inhibitory action. This insight should help in current efforts to develop PrP-based therapeutics for Alzheimer's disease.

  6. Oligomer formation of the gB glycoprotein of herpes simplex virus type 1.

    PubMed Central

    Highlander, S L; Goins, W F; Person, S; Holland, T C; Levine, M; Glorioso, J C

    1991-01-01

    Oligomer formation of the gB glycoprotein of herpes simplex virus type 1 was studied by sedimentation analysis of radioactively labeled infected cell and virion lysates. Fractions from sucrose gradients were precipitated with a pool of gB-specific monoclonal antibodies and analyzed by sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE). Pulse-labeled gB from infected cell was synthesized as monomers and converted to oligomers posttranslationally. The oligomers from infected cells and from virions sedimented as dimers, and there was no evidence of higher-molecular-weight forms. To identify amino acid sequences of gB that contribute to oligomer formation, pairs of mutant plasmids were transfected into Vero cells and superinfected with a gB-null mutant virus to stimulate plasmid-specified gene expression. Radioactively labeled lysates were precipitated with antibodies and examined by SDS-PAGE. Polypeptides from cotransfections were precipitated with an antibody that recognized amino acid sequences present in only one of the two polypeptides. A coprecipitated polypeptide lacking the antibody target epitope was presumed to contain the sequences necessary for oligomer formation. Using this technique, two noncontiguous sites for oligomer formation were detected. An upstream site was localized between residues 93 and 282, and a downstream site was localized between residues 596 and 711. Oligomer formation resulted from molecular interactions between two upstream sites, between two downstream sites, and between an upstream and a downstream site. A schematic diagram of a gB oligomer is presented that is consistent with these data. Images PMID:1649330

  7. A HRMS study of oligomer formation through aqueous phase photooxidation of methylvinyl-ketone and methacrolein

    NASA Astrophysics Data System (ADS)

    Salque-moreton, G.; Liu, Y.; Voisin, D.; Siekmann, F.; Renard, P.; Monod, A.; Thissen, R.

    2012-04-01

    Global estimates of secondary organic aerosol (SOA) formation flux show that the current descriptions miss a large fraction of the sources. Aqueous phase photochemistry in cloud droplets and deliquescent aerosol may provide some of this missing flux. Organic reactions in those media, particularly leading to higher molecular weight products thus need better understanding. Here, we investigated the aqueous phase photooxidation of methacrolein (MACR) and methylvinyl-ketone (MVK), which are the two main oxidation products of isoprene, the volatile organic compound (VOC) that is mostly emitted on the global scale. In our experiments, photolysis of H2O2 provided OH radicals whose reaction with MACR or MVK produced oligomers. Firstly, oligomers were analyzed using electrospray ionization coupled with high-resolution linear ion trap Orbitrap™ (Thermo Corp.) mass spectrometer (HRMS). This technique enabled to propose the unambiguous elemental composition of the produced compounds as data were collected for a mass range of m/z 50-2000 amu. The mass of oligomers increased strongly in positive and negative ionization modes when initial concentrations of MACR and MVK were increased from 2 to 20 mM. Typical regular patterns of oligomer formation were observed for both precursors, and extended up to 1400 amu. These patterns were very different from each other for the two precursors although both showed regular mass differences of 70 amu. In addition, we used a Kendrick analysis and identified more than 20 distinct chemical oligomer series produced by photooxidation of both MACR and MVK, some of which reaching more than 1400 amu. The HRMS investigations allowed us to propose a mechanism of production of oligomers. Upon nebulization, both oligomer systems produce SOA with a mass yield of 2-12%. This mass yield increases with reaction time and precursor concentration. Moreover, time evolution of the oligomer systems observed with the Orbitrap will be compared to HR

  8. KCTD Hetero-oligomers Confer Unique Kinetic Properties on Hippocampal GABAB Receptor-Induced K+ Currents.

    PubMed

    Fritzius, Thorsten; Turecek, Rostislav; Seddik, Riad; Kobayashi, Hiroyuki; Tiao, Jim; Rem, Pascal D; Metz, Michaela; Kralikova, Michaela; Bouvier, Michel; Gassmann, Martin; Bettler, Bernhard

    2017-02-01

    GABAB receptors are the G-protein coupled receptors for the main inhibitory neurotransmitter in the brain, GABA. GABAB receptors were shown to associate with homo-oligomers of auxiliary KCTD8, KCTD12, KCTD12b, and KCTD16 subunits (named after their T1 K(+)-channel tetramerization domain) that regulate G-protein signaling of the receptor. Here we provide evidence that GABAB receptors also associate with hetero-oligomers of KCTD subunits. Coimmunoprecipitation experiments indicate that two-thirds of the KCTD16 proteins in the hippocampus of adult mice associate with KCTD12. We show that the KCTD proteins hetero-oligomerize through self-interacting T1 and H1 homology domains. Bioluminescence resonance energy transfer measurements in live cells reveal that KCTD12/KCTD16 hetero-oligomers associate with both the receptor and the G-protein. Electrophysiological experiments demonstrate that KCTD12/KCTD16 hetero-oligomers impart unique kinetic properties on G-protein-activated Kir3 currents. During prolonged receptor activation (one min) KCTD12/KCTD16 hetero-oligomers produce moderately desensitizing fast deactivating K(+) currents, whereas KCTD12 and KCTD16 homo-oligomers produce strongly desensitizing fast deactivating currents and nondesensitizing slowly deactivating currents, respectively. During short activation (2 s) KCTD12/KCTD16 hetero-oligomers produce nondesensitizing slowly deactivating currents. Electrophysiological recordings from hippocampal neurons of KCTD knock-out mice are consistent with these findings and indicate that KCTD12/KCTD16 hetero-oligomers increase the duration of slow IPSCs. In summary, our data demonstrate that simultaneous assembly of distinct KCTDs at the receptor increases the molecular and functional repertoire of native GABAB receptors and modulates physiologically induced K(+) current responses in the hippocampus.

  9. Oligomers of the amyloid-beta protein disrupt working memory: confirmation with two behavioral procedures.

    PubMed

    Poling, Alan; Morgan-Paisley, Kineta; Panos, John J; Kim, Eun-Mee; O'Hare, Eugene; Cleary, James P; Lesné, Sylvain; Ashe, Karen H; Porritt, Matthew; Baker, Lisa E

    2008-11-21

    Converging lines of evidence suggest that oligomers of amyloid-beta play a role in the cognitive impairment characteristic of Alzheimer's disease, but only three studies have provided experimental evidence of such impairment. To provide additional information about the effects of these oligomers on memory, the present study examined the memory of groups of rats exposed to ICV injections of the culture media (CM) of Chinese Hamster Ovary cells that were (7PA2) and were not (CHO-) transfected with a human mutation of amyloid precursor protein that appears to cause early-onset Alzheimer's disease. The 7PA2 CM, which contained concentrations of soluble amyloid-beta oligomers physiologically relevant to those found in human brain, significantly disrupted working memory in rats tested in a radial-arm maze. In contrast, CHO- CM, which did not contain such oligomers, had no effect on memory. The disruptive effects of 7PA2-derived amyloid-beta oligomers, evident 2h after exposure, disappeared within a day. These findings are compared to results from 7PA2 CM tested under a complex procedure thought to measure aspects of executive function. The results confirm the disruptive effects of low-n amyloid-beta oligomers and extend them to a well-established rat model of memory.

  10. Low Molecular Weight Oligomers with Aromatic Backbone as Efficient Nonviral Gene Vectors.

    PubMed

    Luan, Chao-Ran; Liu, Yan-Hong; Zhang, Ji; Yu, Qing-Ying; Huang, Zheng; Wang, Bing; Yu, Xiao-Qi

    2016-05-04

    A series of oligomers were synthesized via ring-opening polymerization. Although the molecular weights of these oligomers are only ∼2.5 kDa, they could efficiently bind and condense DNA into nanoparticles. These oligomers gave comparable transfection efficiency (TE) to PEI 25 kDa, while their TE could even increase with the presence of serum, and up to 65 times higher TE than PEI was obtained. The excellent serum tolerance was also confirmed by TEM, flow cytometry, and BSA adsorption assay. Moreover, structure-activity relationship studies revealed some interesting factors. First, oligomers containing aromatic rings in the backbone showed better DNA binding ability. These materials could bring more DNA cargo into the cells, leading to much better TE. Second, the isomerism of the disubstituted phenyl group on the oligomer backbone has large effect on the transfection. The ortho-disubstituted ones gave at least 1 order of magnitude higher TE than meta- or para-disubstituted oligomers. Gel electrophoresis involving DNase and heparin indicated that the difficulty to release DNA might contribute to the lower TE of the latter. Such clues may help us to design novel nonviral gene vectors with high efficiency and biocompatibility.

  11. π-Conjugated Discrete Oligomers Containing Planar and Nonplanar Aromatic Motifs.

    PubMed

    Li, Ji; Terec, Anamaria; Wang, Yue; Joshi, Hrishikesh; Lu, Yunpeng; Sun, Handong; Stuparu, Mihaiela C

    2017-03-01

    A new family of π-conjugated oligomers featuring a nonplanar polycyclic aromatic hydrocarbon, corannulene, and a planar aromatic unit, thiophene, is synthesized through an iterative metal-catalyzed coupling protocol. The two structural motifs are connected through an acetylene linkage. In the shorter oligomers, a thiophene unit is attached to one or two corannulenes. In the higher analogues, two, three, and four thiophene units are placed in an alternating fashion with three, four, and five corannulene units, respectively. Photophysical studies reveal extended π-effects that initially increase and then attenuate as a function of the oligomer length. Notably, longer oligomers are found to be highly active for nonlinear absorption and emission properties. The oligomer with three corannulene and two thiophene units exhibits a two-photon absorption cross section of 600 GM and two-photon-excited intense green luminescence. This work, therefore, introduces the concept of combining planar and nonplanar aromatic motifs in the design of π-conjugated discrete oligomers, establishes synthetic feasibility of such hybrid materials, reports on their photophysical properties that is anticipated to have significant implications for future research targets, and features the discovery that corannulene derivatives can exhibit excellent nonlinear optical activity when extended through π-bridges.

  12. α-Synuclein Oligomers Induced by Docosahexaenoic Acid Affect Membrane Integrity

    PubMed Central

    Fecchio, Chiara; De Franceschi, Giorgia; Relini, Annalisa; Greggio, Elisa; Dalla Serra, Mauro; Bubacco, Luigi; Polverino de Laureto, Patrizia

    2013-01-01

    A key feature of Parkinson disease is the aggregation of α-synuclein and its intracellular deposition in fibrillar form. Increasing evidence suggests that the pathogenicity of α-synuclein is correlated with the activity of oligomers formed in the early stages of its aggregation process. Oligomers toxicity seems to be associated with both their ability to bind and affect the integrity of lipid membranes. Previously, we demonstrated that α-synuclein forms oligomeric species in the presence of docosahexaenoic acid and that these species are toxic to cells. Here we studied how interaction of these oligomers with membranes results in cell toxicity, using cellular membrane-mimetic and cell model systems. We found that α-synuclein oligomers are able to interact with large and small unilamellar negatively charged vesicles acquiring an increased amount of α-helical structure, which induces small molecules release. We explored the possibility that oligomers effects on membranes could be due to pore formation, to a detergent-like effect or to fibril growth on the membrane. Our biophysical and cellular findings are consistent with a model where α-synuclein oligomers are embedded into the lipid bilayer causing transient alteration of membrane permeability. PMID:24312431

  13. Effect of Zn(2+) ions on the assembly of amylin oligomers: insight into the molecular mechanisms.

    PubMed

    Wineman-Fisher, Vered; Miller, Yifat

    2016-08-03

    Amylin is an endocrine hormone and is a member of the family of amyloid peptides and proteins that emerge as potential scaffolds by self-assembly processes. Zn(2+) ions can bind to amylin peptides to form self-assembled Zn(2+)-amylin oligomers. In the current work the binding sites of Zn(2+) ions in the self-assembled amylin oligomers at various concentrations of zinc have been investigated. Our results yield two conclusions. First, in the absence of Zn(2+) ions polymorphic states (i.e. various classes of amylin oligomers) are obtained, but when Zn(2+) ions bind to amylin peptides to form Zn(2+)-amylin oligomers, the polymorphism is decreased, i.e. Zn(2+) ions bind only to specific classes of amylin. At low concentrations of Zn(2+) ions the polymorphism is smaller than at high concentrations. Second, the structural features of the self-assembled amylin oligomers are not affected by the presence of Zn(2+) ions. This study proposes new molecular mechanisms of the self-assembly of Zn(2+)-amylin oligomers.

  14. Effects of imidization and rubbing of polyimides on their surface free energy

    NASA Astrophysics Data System (ADS)

    Borycki, Jerzy; Okulska-Bozek, Malgorzata

    2002-06-01

    According to classical method polyimides were obtained in two-step polycondensation process via 10% solutions of poly(amic acid)s in dimethylformamide (DMF). Poly(amic acid)s were synthesized from chosen tetracarboxylic acids dianhydrides: pyromellitic (PMDA), 4,4'- (hexafluoroisopropylidene)diphthalic (6FDA), 4,4'- oxydiphthalic (ODPA) and aromatic diamines: 4,4'- oxydianiline (ODA), 1,4-phenylenediamine (PPD), 4,4'- ethylenedianiline (DAB), 4,4'-diaminodiphenylmethane (MDA), 4-methyl-1,3-phenylenediamine (MMPD) and 2,3,5,6- tetramethyl-1,4-phenylenediamine (DAD) in the first step of this reaction. The indium tin oxide (ITO)-glass plates or glass plates were spin-coated with the poly(amic acid)s solutions and dried. The polyimide layers were prepared by gradual heating in various temperatures (100 degree(s)C, 150 degree(s)C, 180 degree(s)C, 200 degree(s)C, 220 degree(s)C and 250 degree(s)C). The degree of imidization was estimated by means of IR spectroscopy. Obtained PI layers were mechanically modified by rubbing. Three various rubbing materials were used: cotton, silk and chamois leather. Surface free energy and its components of polymer layers were evaluated on the basis of their wet ability by standard liquids (diiodomethane, 1- bromonaphthalene, formamide, ethylene glycol, water). It was found that decrease of intensity of rubbing process yields to increase of contact angle for each of rubbing materials. Polyimide layers rubbed with chamois leather were characterized by the best wet ability. The rubbing process increase surface free energy of tested polyimide films.

  15. Infusion Processing of Phenylethynyl Terminated Imides by High Temperature RTM and VARTM

    NASA Technical Reports Server (NTRS)

    Ghose, Sayata; Lewis, Todd M.; Cano, Roberto J.; Watson, Kent A.; Isayev, Avraam I.

    2011-01-01

    Fabrication of composite structures using infusion processes such as resin transfer molding (RTM) and vacuum assisted resin transfer molding (VARTM) is generally more affordable than conventional autoclave techniques. Recent efforts have focused on adapting both technologies for the fabrication of high temperature (HT) resistant composites. Due to their low melt viscosity and long melt stability, certain phenylethynyl terminated imides (PETI) can be processed into composites using these high temperature out-of-autoclave processes. In the current study, two PETI resins, LARC(TradeMark) PETI-330 and LARC(TradeMark) PETI-8 have been used to make test specimens using both RTM and VARTM. For aerospace applications, a void fraction of less than 2% is desired. Traditionally, RTM has had the advantage over VARTM for generating composites with low void content. However, the process is limited in terms of size. Work at NASA LaRC has incorporated modifications to the thermal cycle used in laminate fabrication that have reduced the void content significantly (typically 1-3%) using the current HT-VARTM process. For composite fabrication by both RTM and VARTM, the resins were infused into three carbon fiber preforms (T650-35-3k 5HS, IM7-6k 5HS, and IM7-6k Uniweave) at 316 C and 260 C respectively and cured up to 371 C. The details of the RTM processing carried out at the University of Akron are discussed in this work along with a brief description of the HT-VARTM processing carried out at NASA-LaRC. Photomicrographs of the panels were taken and void contents were determined by acid digestion. Mechanical properties (short beam shear, SBS) of the panels fabricated by both infusion processes were determined at room temperature as well as at various elevated temperatures. The results of this work are presented herein.

  16. Fluorinated arene, imide and unsaturated pyrrolidinone based donor acceptor conjugated polymers: Synthesis, structure-property and device studies

    NASA Astrophysics Data System (ADS)

    Liyanage, Arawwawala Don Thilanga

    the structure-property study of imide functionalized D-A polymers. Here we used thiophene-imide (TPD) as the acceptor moiety and prepare several D-A polymers by varying the donor units. When selecting the donor units, more priority goes to the fused ring systems. One main reason to use imide functionality is due to the, open position of the imide nitrogen, which provides an attaching position to alkyl substituent. Through this we can easily manipulate solubility and solid state packing arrangement. Also these imide acceptors have low-lying LUMOs due to their electron deficient nature and this will allow tuning the optical energy gap by careful choice of donor materials with different electron donating ability. The fourth chapter mainly contribute to the synthesis and structure property study of a completely novel electron acceptor moiety consist of a unsaturated pyrrolidinone unit known as Pechmann dye (PD) core. Pechmann dyes are closely related to the Indigo family. This can refer as 3-butenolide dimer connected via an alkene bridge, containing a benzene ring at the 5 and 5' positions of the lactone rings. We have prepared several D-A polymers using this PD system with benzodithiophene (BDT) as the donor unit. Different to common D-A polymers the HOMO and LUMO of the PD acceptor moiety are energetically located within the gap of the BDT, so that the electronic and optical properties (HOMO-LUMO transition) are dictated by the PD properties. The promising electronic properties, band gaps, high absorption coefficients and broad absorption suggest this new D-A polymers as an interesting donor material for organic solar cell (OSC) applications. KEY WORDS: Organic semiconductor materials, Self assembly, (opto)-electronic properties, Donor-Acceptor conjugated polymers, Fluorinated arene, 3,3'-bithiophene donors, Thiophene-imide (TPD), Pechmann dye, benzodithiophene, organic solar cell.

  17. Cyclen-based lipidic oligomers as potential gene delivery vehicles.

    PubMed

    Yi, Wen-Jing; Zhang, Qin-Fang; Zhang, Ji; Liu, Qiang; Ren, Laifeng; Chen, Qian-Ming; Guo, Liandi; Yu, Xiao-Qi

    2014-03-01

    A series of cyclen-based linear oligomers bearing hydrophobic long chains (lipopolymers Cy-LC, where Cy and LC represent cyclen-based linear backbone and hydrophobic long chain substituents, respectively) were designed and synthesized. The effects of type and degree of substitution (DS) of hydrophobic long chains on the transfection efficiency were systematically studied. The nitrogen atoms with relatively strong basicity on the cyclen ensure their good DNA binding ability, which was confirmed by gel retardation and ethidium bromide exclusion assays. Lipopolyplexes could be formed as nanoparticles with suitable sizes and zeta potentials for gene transfection. In vitro gene delivery experiments revealed that the linoleic acid (LIN) substituted material Cy-LIN has better transfection efficiency than 25 kDa polyethylenimine in the absence or in the presence of serum. 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide and hemolysis assays showed low cytotoxicity and good biocompatibility of the lipopolyplexes. Fluorescent labeled DNA was used to study the cellular uptake and intracellular distribution of transfected DNA. Flow cytometry results suggested that a long chain is necessary for efficient cellular uptake, and images from confocal laser scanning microscopy showed that after 4h transfection, most of the fluorescent labeled DNA accumulated in the perinuclear region, which was required for efficient gene expression. Moreover, it was also found that the DS of the hydrophobic moiety can adjust the balance between DNA binding ability and dissociation of polyplexes, significantly affecting the transfection efficiency.

  18. Synthesis and Characterization of Poly (Arylene Ether Benzimidazole) Oligomers

    NASA Technical Reports Server (NTRS)

    Leonard, Michael J.

    1995-01-01

    Several poly(arylene ether benzimidazole) oligomers were prepared by the nucleophilic aromatic substitution reaction of a bisphenol benzimidazole and various alkyl-substituted aromatic bisphenols with an activated aromatic dihalide in N, N-dimethylacetarnide. Moderate to high molecular weight terpolymers were obtained in all cases, as shown by their inherent viscosities, which ranged from 0.50 to 0.87 dL g(sup -1). Glass transition temperatures (T(sub g)s) of polymer powders ranged from 267-280 C. Air-dried unoriented thin film T(sub g)s were markedly lower than those of the powders, whereas T(sub g)s of films dried in a nitrogen atmosphere were identical to those of the corresponding powders. In addition, air-dried films were dark amber and brittle, whereas nitrogen-dried films were yellow and creasable. Nitrogen-dried films showed slightly higher thin-film tensile properties than the air-dried films, as well.

  19. Amyloid beta oligomers induce impairment of neuronal insulin receptors.

    PubMed

    Zhao, Wei-Qin; De Felice, Fernanda G; Fernandez, Sara; Chen, Hui; Lambert, Mary P; Quon, Michael J; Krafft, Grant A; Klein, William L

    2008-01-01

    Recent studies have indicated an association between Alzheimer's disease (AD) and central nervous system (CNS) insulin resistance. However, the cellular mechanisms underlying the link between these two pathologies have not been elucidated. Here we show that signal transduction by neuronal insulin receptors (IR) is strikingly sensitive to disruption by soluble Abeta oligomers (also known as ADDLs). ADDLs are known to accumulate in AD brain and have recently been implicated as primary candidates for initiating deterioration of synapse function, composition, and structure. Using mature cultures of hippocampal neurons, a preferred model for studies of synaptic cell biology, we found that ADDLs caused a rapid and substantial loss of neuronal surface IRs specifically on dendrites bound by ADDLs. Removal of dendritic IRs was associated with increased receptor immunoreactivity in the cell body, indicating redistribution of the receptors. The neuronal response to insulin, measured by evoked IR tyrosine autophosphorylation, was greatly inhibited by ADDLs. Inhibition also was seen with added glutamate or potassium-induced depolarization. The effects on IR function were completely blocked by NMDA receptor antagonists, tetrodotoxin, and calcium chelator BAPTA-AM. Downstream from the IR, ADDLs induced a phosphorylation of Akt at serine473, a modification associated with neurodegenerative and insulin resistance diseases. These results identify novel factors that affect neuronal IR signaling and suggest that insulin resistance in AD brain is a response to ADDLs, which disrupt insulin signaling and may cause a brain-specific form of diabetes as part of an overall pathogenic impact on CNS synapses.

  20. Structure and stability of oligomer/α-cyclodextrin inclusion complexes.

    NASA Astrophysics Data System (ADS)

    Hunt, Marcus; Villar, Silvia; Gomez, Marian; Tonelli, Alan; Balik, Maury

    2007-03-01

    Cyclomaltohexaose (α-cyclodextrin, α-CD) can form inclusion complexes (ICs) with polymer molecules in the columnar crystal in which α-CD molecules stack to form a molecular tube. Complementary water vapor sorption and wide-angle X-ray diffractomery (WAXD) were performed on oligomer/α-CD ICs to probe their structures and stabilities. To discern the effect of guest molecule hydrophobicity on water adsorption isotherms, polyethylene glycol (PEG, MW = 600 g/mol) and hexatriacontane (HTC) guests were used. Sorption isotherms for PEG/α-CD IC are similar to those obtained for pure α-CD and PEG, suggesting the presence of dethreaded PEG in the sample. WAXD collected before and after water vapor sorption of PEG/α-CD IC indicated a partial conversion from columnar to cage crystal structure, the thermodynamically preferred structure for pure α-CD, due to dethreading of PEG. This behavior does not occur for HTC/α-CD IC. Sorption isotherms collected at 20, 30, 40 and 50 C allowed the calculation of differential heats of adsorption and integral entropies of adsorbed water, while solid-state ^13C NMR suggested a dramatic increase in HTC and α-CD mobilities upon complexation.

  1. Unique copper-induced oligomers mediate alpha-synuclein toxicity.

    PubMed

    Wright, Josephine A; Wang, Xiaoyan; Brown, David R

    2009-08-01

    Parkinson's disease and a number of other neurodegenerative diseases have been linked to either genetic mutations in the alpha-synuclein gene or show evidence of aggregates of the alpha-synuclein protein, sometimes in the form of Lewy bodies. There currently is no clear evidence of a distinct neurotoxic species of alpha-synuclein to explain the death of neurons in these diseases. We undertook to assess the toxicity of alpha-synuclein via exogenous application in cell culture. Initially, we showed that only aggregated alpha-synuclein is neurotoxic and requires the presence copper but not iron. Other members of the synuclein family showed no toxicity in any form and inherited point mutations did not alter the effective toxic concentration of alpha-synuclein. Through protein fractionation techniques, we were able to isolate an oligomeric species responsible for the toxicity of alpha-synuclein. This oligomeric species has a unique stellate appearance under EM and again, requires association with copper to induce cell death. The results allow us to suggest that the toxic species of alpha-synuclein in vivo could possibly be these stellate oligomers and not fibrils. Our data provide a link between the recently noted association of copper and alpha-synuclein and a potential role for the combination in causing neurodegeneration.

  2. GeneGenie: optimized oligomer design for directed evolution

    PubMed Central

    Swainston, Neil; Currin, Andrew; Day, Philip J.; Kell, Douglas B.

    2014-01-01

    GeneGenie, a new online tool available at http://www.gene-genie.org, is introduced to support the design and self-assembly of synthetic genes and constructs. GeneGenie allows for the design of oligonucleotide cohorts encoding the gene sequence optimized for expression in any suitable host through an intuitive, easy-to-use web interface. The tool ensures consistent oligomer overlapping melting temperatures, minimizes the likelihood of misannealing, optimizes codon usage for expression in a selected host, allows for specification of forward and reverse cloning sequences (for downstream ligation) and also provides support for mutagenesis or directed evolution studies. Directed evolution studies are enabled through the construction of variant libraries via the optional specification of ‘variant codons’, containing mixtures of bases, at any position. For example, specifying the variant codon TNT (where N is any nucleotide) will generate an equimolar mixture of the codons TAT, TCT, TGT and TTT at that position, encoding a mixture of the amino acids Tyr, Ser, Cys and Phe. This facility is demonstrated through the use of GeneGenie to develop and synthesize a library of enhanced green fluorescent protein variants. PMID:24782527

  3. Oligomer Formation of Tau Protein Hyperphosphorylated in Cells*

    PubMed Central

    Tepper, Katharina; Biernat, Jacek; Kumar, Satish; Wegmann, Susanne; Timm, Thomas; Hübschmann, Sabrina; Redecke, Lars; Mandelkow, Eva-Maria; Müller, Daniel J.; Mandelkow, Eckhard

    2014-01-01

    Abnormal phosphorylation (“hyperphosphorylation”) and aggregation of Tau protein are hallmarks of Alzheimer disease and other tauopathies, but their causative connection is still a matter of debate. Tau with Alzheimer-like phosphorylation is also present in hibernating animals, mitosis, or during embryonic development, without leading to pathophysiology or neurodegeneration. Thus, the role of phosphorylation and the distinction between physiological and pathological phosphorylation needs to be further refined. So far, the systematic investigation of highly phosphorylated Tau was difficult because a reliable method of preparing reproducible quantities was not available. Here, we generated full-length Tau (2N4R) in Sf9 cells in a well defined phosphorylation state containing up to ∼20 phosphates as judged by mass spectrometry and Western blotting with phospho-specific antibodies. Despite the high concentration in living Sf9 cells (estimated ∼230 μm) and high phosphorylation, the protein was not aggregated. However, after purification, the highly phosphorylated protein readily formed oligomers, whereas fibrils were observed only rarely. Exposure of mature primary neuronal cultures to oligomeric phospho-Tau caused reduction of spine density on dendrites but did not change the overall cell viability. PMID:25339173

  4. HAMLET forms annular oligomers when deposited with phospholipid monolayers.

    PubMed

    Baumann, Anne; Gjerde, Anja Underhaug; Ying, Ming; Svanborg, Catharina; Holmsen, Holm; Glomm, Wilhelm R; Martinez, Aurora; Halskau, Oyvind

    2012-04-20

    Recently, the anticancer activity of human α-lactalbumin made lethal to tumor cells (HAMLET) has been linked to its increased membrane affinity in vitro, at neutral pH, and ability to cause leakage relative to the inactive native bovine α-lactalbumin (BLA) protein. In this study, atomic force microscopy resolved membrane distortions and annular oligomers (AOs) produced by HAMLET when deposited at neutral pH on mica together with a negatively charged lipid monolayer. BLA, BAMLET (HAMLET's bovine counterpart) and membrane-binding Peptide C, corresponding to BLA residues 75-100, also form AO-like structures under these conditions but at higher subphase concentrations than HAMLET. The N-terminal Peptide A, which binds to membranes at acidic but not at neutral pH, did not form AOs. This suggests a correlation between the capacity of the proteins/peptides to integrate into the membrane at neutral pH-as observed by liposome content leakage and circular dichroism experiments-and the formation of AOs, albeit at higher concentrations. Formation of AOs, which might be important to HAMLET's tumor toxic action, appears related to the increased tendency of the protein to populate intermediately folded states compared to the native protein, the formation of which is promoted by, but not uniquely dependent on, the oleic acid molecules associated with HAMLET.

  5. Carboxybetaine methacrylate oligomer modified nylon for circulating tumor cells capture.

    PubMed

    Dong, Chaoqun; Wang, Huiyu; Zhang, Zhuo; Zhang, Tao; Liu, Baorui

    2014-10-15

    Circulating tumor cells (CTC) capture is one of the most effective approaches in diagnosis and treatment of cancers in the field of personalized cancer medicine. In our study, zwitterionic carboxybetaine methacrylate (CBMA) oligomers were grafted onto nylon via atomic transfer random polymerization (ATRP) which would serve as a novel material for the development of convenient CTC capture interventional medical devices. The chemical, physical and biological properties of pristine and modified nylon surfaces were assessed by Fourier transform infrared spectra, atomic force microscope, water contact angle measurements, X-ray photoelectron spectroscopy, protein adsorption, platelet adhesion, and plasma recalcification time (PRT) determinations, etc. The results, including the significant decrease of proteins adsorption and platelets adhesion, as well as prolonged PRTs demonstrated the extraordinary biocompatibility and blood compatibility of the modified surface. Furthermore, we showed that upon immobilization of anti-epithelial cell adhesion molecular (anti-EpCAM) antibody onto the CBMA moiety, the modified nylon surface can selectively capture EpCAM positive tumor cells from blood with high efficiency, indicating the potential of the modified nylon in the manufacture of convenient interventional CTC capture medical devices.

  6. Cloud forming potential of oligomers relevant to secondary organic aerosols

    NASA Astrophysics Data System (ADS)

    Xu, Wen; Guo, Song; Gomez-Hernandez, Mario; Zamora, Misti L.; Secrest, Jeremiah; Marrero-Ortiz, Wilmarie; Zhang, Annie L.; Collins, Don R.; Zhang, Renyi

    2014-09-01

    The hygroscopic growth factor (HGF) and cloud condensation nuclei (CCN) activity are measured for surrogates that mimic atmospherically relevant oligomers, including glyoxal trimer dihydrate, methyl glyoxal trimer dihydrate, sucrose, methyl glyoxal mixtures with sulfuric acid and glycolic acid, and 2,4-hexandienal mixtures with sulfuric acid and glycolic acid. For the single-component aerosols, the measured HGF ranges from 1.3 to 1.4 at a relative humidity of 90%, and the hygroscopicity parameter (κ) is in the range of 0.06 to 0.19 on the basis of the measured CCN activity and 0.13 to 0.22 on the basis of the measured HGF, compared to the calculated values of 0.08 to 0.16. Large differences exist in the κ values derived using the measured HGF and CCN data for the multi-component aerosols. Our results reveal that, in contrast to the oxidation process, oligomerization decreases particle hygroscopicity and CCN activity and provides guidance for analyzing the organic species in ambient aerosols.

  7. Observation of molecular ordering at the surface of trimethylpropylammonium bis(trifluoromethanesulfonyl)imide using high-resolution rutherford backscattering spectroscopy.

    PubMed

    Nakajima, Kaoru; Ohno, Atsushi; Suzuki, Motofumi; Kimura, Kenji

    2008-05-06

    The surface structure of trimethylpropylammonium bis(trifluoromethanesulfonyl)imide ([TMPA] [TFSI]) is studied by high-resolution Rutherford backscattering spectroscopy at room temperature. The results provide direct evidence of the molecular ordering at the surface. The C1 conformer of the [TFSI] anion is dominant among two stable conformers, and the anions are oriented with their CF3 groups pointing toward the vacuum in the outermost molecular layer. The anions in the second molecular layer also show preferred orientation although it is rather weak.

  8. Electrolyte Solvation and Ionic Association. V. Acetonitrile-Lithium Bis(fluorosulfonyl)imide (LiFSI) Mixtures

    SciTech Connect

    Han, Sang D.; Borodin, Oleg; Seo, D. M.; Zhou, Zhi B.; Henderson, Wesley A.

    2014-09-30

    Electrolytes with the salt lithium bis(fluorosulfonyl)imide (LiFSI) have been evaluated relative to comparable electrolytes with other lithium salts. Acetonitrile (AN) has been used as a model electrolyte solvent. The information obtained from the thermal phase behavior, solvation/ionic association interactions, quantum chemical (QC) calculations and molecular dynamics (MD) simulations (with an APPLE&P many-body polarizable force field for the LiFSI salt) of the (AN)n-LiFSI mixtures provides detailed insight into the coordination interactions of the FSI- anions and the wide variability noted in the electrolyte transport property (i.e., viscosity and ionic conductivity).

  9. Improvement of hydrophilic properties of electrospun polyamide-imide fibrous mats by atmospheric-pressure plasma treatment

    NASA Astrophysics Data System (ADS)

    Park, Soo-Jin; Yop Rhee, Kyong; Jin, Fan-Long

    2015-03-01

    Polyamide-imide (PAI) fibrous mats were fabricated through electrospinning and further treated with atmospheric-pressure plasma. The surface characteristics of the PAI fibrous mats were examined to determine the effect of plasma treatment on the hydrophilic properties. FT-IR, X-ray photoelectron spectroscopy, and contact-angle analysis indicated that the hydrophilicity of the PAI fibrous mats increased upon the introduction of hydrophilic groups by plasma treatment. The concentration of functional groups, including oxygen, and the surface roughness of the PAI fibrous mats increased with increasing treatment time. The optimum plasma treatment time for surface modification of the PAI fibrous mats under atmospheric pressure was 120 s.

  10. Intracellular soluble α‐synuclein oligomers reduce pyramidal cell excitability

    PubMed Central

    Kaufmann, Timothy J.; Harrison, Paul M.; Richardson, Magnus J. E.; Pinheiro, Teresa J. T.

    2016-01-01

    Key points The presynaptic protein α‐synuclein forms aggregates during Parkinson's disease.Accumulating evidence suggests that the small soluble oligomers of α‐synuclein are more toxic than the larger aggregates appearing later in the disease.The link between oligomer toxicity and structure still remains unclear.In the present study, we have produced two structurally‐defined oligomers that have a similar morphology but differ in secondary structure.These oligomers were introduced into neocortical pyramidal cells during whole‐cell recording and, using a combination of experimentation and modelling, electrophysiological parameters were extracted.Both oligomeric species had similar effects on neuronal properties reducing input resistance, time constant and increasing capacitance. The net effect was a marked reduction in neuronal excitability that could impact on network activity. Abstract The presynaptic protein α‐synuclein (αSyn) aggregates during Parkinson's disease (PD) to form large proteinaceous amyloid plaques, the spread of which throughout the brain clinically defines the severity of the disease. During early stages of aggregation, αSyn forms soluble annular oligomers that show greater toxicity than much larger fibrils. These oligomers produce toxicity via a number of possible mechanisms, including the production of pore‐forming complexes that permeabilize membranes. In the present study, two well‐defined species of soluble αSyn oligomers were produced by different protocols: by polymerization of monomer and by sonication of fibrils. The two oligomeric species produced were morphologically similar, with both having an annular structure and consisting of approximately the same number of monomer subunits, although they differed in their secondary structure. Oligomeric and monomeric αSyn were injected directly into the soma of pyramidal neurons in mouse neocortical brain slices during whole‐cell patch clamp recording. Using a combined

  11. A binary ionic liquid system composed of N-methoxyethyl- N-methylpyrrolidinium bis(trifluoromethanesulfonyl)-imide and lithium bis(trifluoromethanesulfonyl)imide: A new promising electrolyte for lithium batteries

    NASA Astrophysics Data System (ADS)

    Ferrari, S.; Quartarone, E.; Mustarelli, P.; Magistris, A.; Protti, S.; Lazzaroni, S.; Fagnoni, M.; Albini, A.

    Room temperature ionic liquids are nowadays the most appealing research target in the field of liquid electrolytes for lithium batteries, due to their high thermal stability, ionic conductivity and wide electrochemical windows. The cation structure of such solvents strictly influences their physical and chemical properties, in particular the viscosity and conductivity. In this paper we report on the preparation and characterization of a complete series of solutions between lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and the promising N-methoxyethyl- N-methylpyrrolidinium bis(trifluoromethanesulfonyl)-imide (PY 1,2O1) ionic liquid. A wide molality range has been explored in order to identify the optimal compositions in terms of conductivity and electrochemical stability. Our thermal results show that the solutions are amorphous independently on the LiTFSI content. Up to salt concentration of 0.4 mol kg -1 the solutions have a very low viscosity (η ∼ 36 cP), a high ionic conductivity, even at temperatures below 0 °C, and a good electrochemical stability. Cations transport numbers ranging between 0.05 and 0.39 have been determined as a function of LiTFSI content. The combination of these properties makes the PY 1,2O1-based solutions potentially attractive liquid electrolytes for lithium batteries.

  12. Electrochemical and in-situ scanning tunneling microscopy studies of bis(fluorosulfonyl)imide and bis(trifluoromethanesulfonyl)imide based ionic liquids on graphite and gold electrodes and lithium salt influence

    NASA Astrophysics Data System (ADS)

    Hu, Xiaoyan; Chen, Chunlei; Yan, Jiawei; Mao, Bingwei

    2015-10-01

    We report electrochemical and in-situ scanning tunneling microscopy (STM) studies of surface processes on graphite and Au(111) electrodes in N-methyl-N-propylpyrrolidinium bis(fluorosulfonyl)imide (Py13FSI) and N-methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)imide (Py13TFSI) ionic liquids in the absence and presence of LiTFSI salt. In both of neat ionic liquids, the intercalation of cations and exfoliation of HOPG layers occur during cathodic excursion. However, the surface decomposition of FSI anions can form an effective protection film on the surface, which suppresses the intercalation and exfoliation processes, while the surface decomposition of TFSI anions mainly causes etching of the surface, which makes the intercalation and exfoliation easier to proceed. The addition of Li salt can promote the formation of the protective film, especially in Py13FSI, and thus significantly suppress the intercalation and exfoliation processes. The discrepancies between these two ionic liquids are caused by the different anion interactions with graphite. Additionally, comparisons of the behaviors on HOPG and on Au(111) confirm that the surface processes are crucially dependent on the nature of the electrode. Trace amounts of oxygen and water can cause the formation of a film-like structure on Au(111), but show no apparent influence on HOPG.

  13. Liquid-crystalline and electron-deficient coronene oligocarboxylic esters and imides by twofold benzogenic Diels-Alder reactions on perylenes.

    PubMed

    Alibert-Fouet, Sonia; Seguy, Isabelle; Bobo, Jean-François; Destruel, Pierre; Bock, Harald

    2007-01-01

    Alkyl esters, imides and imido-esters of coronene-tri-, -tetra- and -octacarboxylic acids are accessible by a twofold oxidative benzogenic Diels-Alder reaction. Alkyl acrylates add to perylene, and maleic alkyl imides react twice with perylene as well as with perylene-tetracarboxylic tetraesters. Coronenes substituted with a greatly variable number of electron-withdrawing substituents are thus accessible, and di- and tetraimide derivatives are shown to be very pronounced electron-acceptor materials. The tri- and tetraalkyl esters and imidoesters self-assemble into columnar liquid-crystalline phases.

  14. Novel demonstration of amyloid-β oligomers in sporadic inclusion-body myositis muscle fibers.

    PubMed

    Nogalska, Anna; D'Agostino, Carla; Engel, W King; Klein, William L; Askanas, Valerie

    2010-11-01

    Accumulation of amyloid-β (Aβ) within muscle fibers has been considered an upstream step in the development of the s-IBM pathologic phenotype. Aβ42, which is considered more cytotoxic than Aβ40 and has a higher propensity to oligomerize, is preferentially increased in s-IBM muscle fibers. In Alzheimer disease (AD), low-molecular weight Aβ oligomers and toxic oligomers, also referred to as "Aβ-Derived Diffusible Ligands" (ADDLs), are considered strongly cytotoxic and proposed to play an important pathogenic role. ADDLs have been shown to be increased in AD brain. We now report for the first time that in s-IBM muscle biopsies Aβ-dimer, -trimer, and -tetramer are identifiable by immunoblots. While all the s-IBM samples we studied had Aβ-oligomers, their molecular weights and intensity varied between the patient samples. None of the control muscle biopsies had Aβ oligomers. Dot-immunoblots using highly specific anti-ADDL monoclonal antibodies also showed highly increased ADDLs in all s-IBM biopsies studied, while controls were negative. By immunofluorescence, in some of the abnormal s-IBM muscle fibers ADDLs were accumulated in the form of plaque-like inclusions, and were often increased diffusely in very small fibers. Normal and disease-controls were negative. By gold-immuno-electron microscopy, ADDL-immunoreactivities were in close proximity to 6-10 nm amyloid-like fibrils, and also were immunodecorating amorphous and floccular material. In cultured human muscle fibers, we found that inhibition of autophagy led to the accumulation of Aβ oligomers. This novel demonstration of Aβ42 oligomers in s-IBM muscle biopsy provides additional evidence that intra-muscle fiber accumulation of Aβ42 oligomers in s-IBM may contribute importantly to s-IBM pathogenic cascade.

  15. Self-propagative replication of Aβ oligomers suggests potential transmissibility in Alzheimer disease.

    PubMed

    Kumar, Amit; Pate, Kayla M; Moss, Melissa A; Dean, Dexter N; Rangachari, Vijayaraghavan

    2014-01-01

    The aggregation of amyloid-β (Aβ) peptide and its deposition in parts of the brain form the central processes in the etiology of Alzheimer disease (AD). The low-molecular weight oligomers of Aβ aggregates (2 to 30 mers) are known to be the primary neurotoxic agents whose mechanisms of cellular toxicity and synaptic dysfunction have received substantial attention in the recent years. However, how these toxic agents proliferate and induce widespread amyloid deposition throughout the brain, and what mechanism is involved in the amplification and propagation of toxic oligomer species, are far from clear. Emerging evidence based on transgenic mice models indicates a transmissible nature of Aβ aggregates and implicates a prion-like mechanism of oligomer propagation, which manifests as the dissemination and proliferation of Aβ toxicity. Despite accumulating evidence in support of a transmissible nature of Aβ aggregates, a clear, molecular-level understanding of this intriguing mechanism is lacking. Recently, we reported the characterization of unique replicating oligomers of Aβ42 (12-24 mers) in vitro called Large Fatty Acid-derived Oligomers (LFAOs) (Kumar et al., 2012, J. Biol. Chem). In the current report, we establish that LFAOs possess physiological activity by activating NF-κB in human neuroblastoma cells, and determine the experimental parameters that control the efficiency of LFAO replication by self-propagation. These findings constitute the first detailed report on monomer - oligomer lateral propagation reactions that may constitute potential mechanism governing transmissibility among Aβ oligomers. These data support the previous reports on transmissible mechanisms observed in transgenic animal models.

  16. Discrete Molecular Dynamics Study of Oligomer Formation by N-Terminally Truncated Amyloid β-Protein

    PubMed Central

    Meral, Derya; Urbanc, Brigita

    2013-01-01

    In Alzheimer’s disease (AD), amyloid β-protein (Aβ) self–assembles into toxic oligomers. Of the two predominant Aβ alloforms, Aβ1–40 and Aβ1–42, the latter is particularly strongly linked to AD. N-terminally truncated and pyroglutamated Aβ peptides were recently shown to seed Aβ aggregation and contribute significantly to Aβ–mediated toxicity, yet their folding and assembly were not explored computationally. Discrete molecular dynamics (DMD) approach previously captured in vitro–derived distinct Aβ1–40 and Aβ1–42 oligomer size distributions and predicted that the more toxic Aβ1–42 oligomers had more flexible and solvent exposed N-termini than Aβ1–40 oligomers. Here, we examined oligomer formation of Aβ3–40, Aβ3–42, Aβ11–40, and Aβ11–42 by the DMD approach. The four N-terminally truncated peptides showed increased oligomerization propensity relative to the full–length peptides, consistent with in vitro findings. Conformations formed by Aβ3–40/42 had significantly more flexible and solvent–exposed N-termini than Aβ1–40/42 conformations. In contrast, in Aβ11–40/42 conformations the N-termini formed more contacts and were less accessible to the solvent. The compactness of the Aβ11–40/42 conformations was in part facilitated by Val12. Two single amino acid substitutions that reduced and abolished hydrophobicity at position 12, respectively, resulted in a proportionally increased structural variability. Our results suggest that Aβ11–40 and Aβ11–42 oligomers might be less toxic than Aβ1–40 and Aβ1–42 oligomers and offer a plausible explanation for the experimentally–observed increased toxicity of Aβ3–40 and Aβ3–42 and their pyroglutamated forms. PMID:23500806

  17. Humanin Specifically Interacts with Amyloid-β Oligomers and Counteracts Their in vivo Toxicity.

    PubMed

    Romeo, Margherita; Stravalaci, Matteo; Beeg, Marten; Rossi, Alessandro; Fiordaliso, Fabio; Corbelli, Alessandro; Salmona, Mario; Gobbi, Marco; Cagnotto, Alfredo; Diomede, Luisa

    2017-03-06

    The 24-residue peptide humanin (HN) has been proposed as peptide-based inhibitors able to interact directly with amyloid-β (Aβ) oligomers and interfere with the formation and/or biological properties of toxic Aβ species. When administered exogenously HN, or its synthetic S14G-derivative (HNG), exerted multiple cytoprotective effects, counteracting the Aβ-induced toxicity. Whether these peptides interact directly with Aβ, particularly with the soluble oligomeric assemblies, remains largely unknown. We here investigated the ability of HN and HNG to interact directly with highly aggregating Aβ42, and interfere with the formation and toxicity of its oligomers. Experiments were run in cell-free conditions and in vivo in a transgenic C. elegans strain in which the Aβ toxicity was specifically due to oligomeric species. Thioflavin-T assay indicated that both HN and HNG delay the formation and reduce the final amount of Aβ42 fibrils. In vitro surface plasmon resonance studies indicated that they interact with Aβ42 oligomers favoring the formation of amorphous larger assemblies, observed with turbidity and electron microscopy. In vivo studies indicated that both HN and HNG decrease the relative abundance of A11-positive prefibrillar oligomers as well as OC-positive fibrillar oligomers and had similar protective effects. However, while HN possibly decreased the oligomers by promoting their assembly into larger aggregates, the reduction of oligomers caused by HNG can be ascribed to a marked decrease of the total Aβ levels, likely the consequence of the HNG-induced overexpression of the Aβ-degrading enzyme neprilysin. These findings provide information on the mechanisms underlying the anti-oligomeric effects of HN and HNG and illustrate the role of S14G substitution in regulating the in vivo mechanism of action.

  18. Self-assembly of conjugated oligomers and polymers at the interface: structure and properties.

    PubMed

    Xu, Lirong; Yang, Liu; Lei, Shengbin

    2012-08-07

    In this review, we give a brief account on the recent scanning tunneling microscopy investigation of interfacial structures and properties of π-conjugated semiconducting oligomers and polymers, either at the solid-air (including solid-vacuum) or at the solid-liquid interface. The structural aspects of the self-assembly of both oligomers and polymers are highlighted. Conjugated oligomers can form well ordered supramolecular assemblies either at the air-solid or liquid-solid interface, thanks to the relatively high mobility and structural uniformity in comparison with polymers. The backbone structure, substitution of side chains and functional groups can affect the assembling behavior significantly, which offers the opportunity to tune the supramolecular structure of these conjugated oligomers at the interface. For conjugated polymers, the large molecular weight limits the mobility on the surface and the distribution in size also prevents the formation of long range ordered supramolecular assembly. The submolecular resolution obtained on the assembling monolayers enables a detailed investigation of the chain folding at the interface, both the structural details and the effect on electronic properties. Besides the ability in studying the assembling structures at the interfaces, STM also provides a reasonable way to evaluate the distribution of the molecular weight of conjugated polymers by statistic of the contour length of the adsorbed polymer chains. Both conjugated oligomers and polymers can form composite assemblies with other materials. The ordered assembly of oligomers can act as a template to controllably disperse other molecules such as coronene or fullerene. These investigations open a new avenue to fine tune the assembling structure at the interface and in turn the properties of the composite materials. To summarize scanning tunneling microscopy has demonstrated its surprising ability in the investigation of the assembling structures and properties of

  19. Aromatic oligomers that form hetero duplexes in aqueous solution.

    PubMed

    Gabriel, Gregory J; Iverson, Brent L

    2002-12-25

    The electron-deficient 1,4,5,8-naphthalenetetracarboxylic diimide (Ndi) and electron-rich 1,5-dialkoxynaphthalene (Dan) have been shown to complex strongly with each other in water due to the hydrophobic effect as modulated through the electrostatic complementarity of the stacked dimer. Previously, oligomers of alternating Ndi and Dan units, termed aedamers, were the first foldamers to employ intramolecular aromatic stacking to effect the formation of secondary structure of nonnatural chains in aqueous solution. Described here is the use of this aromatic-aromatic (or pi-pi) interaction, this time in an intermolecular format, to demonstrate the self-assembly of stable hetero duplexes from a set of molecular strands (1a-4a) and (1b-4b) incorporating Ndi and Dan units, respectively. A 1-to-1 binding stoichiometry was determined from NMR and isothermal titration calorimetry (ITC) investigations, and these experiments indicated that association is enthalpically favored with the tetra-Ndi (4a) and tetra-Dan (4b) strands forming hetero duplexes (4a:4b) with a stability constant of 350 000 M-1 at T = 318 K. Polyacrylamide gel electrophoresis (PAGE) also illustrated the strong interaction between 4a and 4b and support a 1-to-1 binding mode even when one component is in slight excess. Overall, this system is the first to utilize complementary aromatic units to drive discrete self-assembly in aqueous solution. This new approach for designing assemblies is encouraging for future development of duplex systems with highly programmable modes of binding in solution or on surfaces.

  20. Synthesis of paucidisperse poly(gamma-benzyl-alpha,L-glutamate) oligomers and star polymers with rigid arms.

    PubMed

    Wang, X; Daly, W H; Russo, P; Ngu-Schwemlein, M

    2001-01-01

    The synthesis of highly uniform gamma-benzyl-alpha,L-glutamate (BLG) oligomers via a convergent solution phase approach is reported. BLG oligomers were produced with designed lengths of 4, 8, 12, and 16 as a first step to production of BLG-4-mer and BLG-8-mer rod stars. The star oligomers were purified by size-exclusion chromatography and reversed phase HPLC, and characterized by MALDI-TOF mass spectrometry and reversed phase HPLC. These star-shaped BLG oligomers could be used as initiators for growing larger stars.

  1. New glyme-cyclic imide lithium salt complexes as thermally stable electrolytes for lithium batteries

    NASA Astrophysics Data System (ADS)

    Tamura, Takashi; Hachida, Takeshi; Yoshida, Kazuki; Tachikawa, Naoki; Dokko, Kaoru; Watanabe, Masayoshi

    New glyme-Li salt complexes were prepared by mixing equimolar amounts of a novel cyclic imide lithium salt LiN(C 2F 4S 2O 4) (LiCTFSI) and a glyme (triglyme (G3) or tetraglyme (G4)). The glyme-Li salt complexes, [Li(G3)][CTFSI] and [Li(G4)][CTFSI], are solid and liquid, respectively, at room temperature. The thermal stability of [Li(G4)][CTFSI] is much higher than that of pure G4, and the vapor pressure of [Li(G4)][CTFSI] is negligible at temperatures lower than 100 °C. Although the viscosity of [Li(G4)][CTFSI] is high (132.0 mPa s at 30 °C), because of its high molar concentration (ca. 3 mol dm -3), its ionic conductivity at 30 °C is relatively high, i.e., 0.8 mS cm -1, which is slightly lower than that of a conventional organic electrolyte solution (1 mol dm -3 LiTFSI dissolved in propylene carbonate). The self-diffusion coefficients of a Li + cation, a CTFSI - anion, and a glyme molecule were measured by the pulsed gradient spin-echo NMR method (PGSE-NMR). The ionicity (dissociativity) of [Li(G4)][CTFSI] at 30 °C is ca. 0.5, as estimated from the PGSE-NMR diffusivity measurements and the ionic conductivity measurements. Results of linear sweep voltammetry revealed that [Li(G4)][CTFSI] is electrochemically stable in an electrode potential range of 0-4.5 V vs. Li/Li +. The reversible deposition-stripping behavior of lithium was observed by cyclic voltammetry. The [LiCoO 2|[Li(G4)][CTFSI]|Li metal] cell showed a stable charge-discharge cycling behavior during 50 cycles, indicating that the [Li(G4)][CTFSI] complex is applicable to a 4 V class lithium secondary battery.

  2. Homogeneous Liquid–Liquid Extraction of Rare Earths with the Betaine—Betainium Bis(trifluoromethylsulfonyl)imide Ionic Liquid System

    PubMed Central

    Hoogerstraete, Tom Vander; Onghena, Bieke; Binnemans, Koen

    2013-01-01

    Several fundamental extraction parameters such as the kinetics and loading were studied for a new type of metal solvent extraction system with ionic liquids. The binary mixture of the ionic liquid betainium bis(trifluoromethylsulfonyl)imide and water shows thermomorphic behavior with an upper critical solution temperature (UCST), which can be used to avoid the slower mass transfer due to the generally higher viscosity of ionic liquids. A less viscous homogeneous phase and mixing on a molecular scale are obtained when the mixture is heated up above 55 °C. The influence of the temperature, the heating and cooling times, were studied for the extraction of neodymium(III) with betaine. A plausible and equal extraction mechanism is proposed in bis(trifluoromethylsulfonyl)imide, nitrate, and chloride media. After stripping of the metals from the ionic liquid phase, a higher recovery of the ionic liquid was obtained by salting-out of the ionic liquid fraction lost by dissolution in the aqueous phase. The change of the upper critical solution temperature by the addition of HCl or betaine was investigated. In addition, the viscosity was measured below and above the UCST as a function of the temperature. PMID:24169434

  3. Ionic liquid and plastic crystalline phases of pyrazolium imide salts as electrolytes for rechargeable lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Abu-Lebdeh, Yaser; Abouimrane, Ali; Alarco, Pierre-Jean; Armand, Michel

    A new member of the plastic crystal, pyrazolium imide family, N, N‧-diethyl-3-methylpyrazolium bis-(trifluoromethanesulfonyl)imide (DEMPyr123) was prepared. It showed a single, plastic crystalline phase that extends from 4.2 °C to its melting at 11.3 °C. When 10 mol% LiTFSI salt was added, the mixture showed ionic conductivities reaching 1.7 × 10 -3 S cm -1 at 20 °C, in the liquid state and 6.9 × 10 -4 S cm -1 at 5 °C, in the solid, plastic phase. A wide electrochemical stability window's of 5.5 V was observed by cyclic voltammetry of the molten salt mixture. Batteries were assembled with LiFePO 4/Li 4Ti 5O 12 electrodes and the salt mixture as an electrolyte. They showed a charge/discharge efficiency of 93% and 87% in the liquid and the plastic phase, respectively. The capacity retention was very good in both states with 90% of the initial capacity still available after 40 cycles. In general, the batteries showed good rate capability and cycle life performance in the ionic liquid phase that were sustained when the electrolyte transformed to the plastic phase. Comparison of the battery results with those of a classic (non-plastic crystal) ionic liquid has proven the advantage of the dual state of matter character in this electrolyte.

  4. Properties of the lithium and graphite-lithium anodes in N-methyl- N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide

    NASA Astrophysics Data System (ADS)

    Lewandowski, Andrzej; Świderska-Mocek, Agnieszka

    The ternary [Li +] 0.09[MePrPyr +] 0.41[NTf 2 -] 0.50 room temperature ionic liquid was obtained by dissolution of solid lithium bis(trifluoromethanesulfonyl)imide (LiNTf 2) in liquid N-methyl- N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([MePrPyr +][NTf 2 -]), and studied as an electrolyte for lithium-ion batteries. The graphite-lithium (C 6Li) anode, working together with vinylene carbonate as an additive showed ca. 90% of its initial discharge capacity after 50 cycles. The addition of vinylene carbonate to the neat ionic liquid results in the formation of the protective coating (SEI) on both the lithium and graphite anodes. The SEI formation increases the rate of the charge transfer reaction as well as protects the anode from chemical passivation (corrosion). The graphite-lithium (C 6Li) anode shows good cyclability and Coulombic efficiency in the presence of 10 wt.% of vinylene carbonate as an additive to the ionic liquid.

  5. A simple method for the synthesis of a polar-embedded and polar-endcapped reversed-phase chromatographic packing with low activity of residue silanols.

    PubMed

    Liu, Hai-yan; Li, Zhi-yong; Liu, Dan; Xue, Ying-wen; Shi, Zhi-guo

    2016-04-22

    Octadecyl bonded silica (ODS) is the most popular packing for reversed-phase chromatography. However, it generally demonstrates bad resolution for polar analytes because of the residue silanols and its poor stability in aqueous mobile phase. To address the problem, a new reversed-phase packing containing both polar-embedded and polar-endcapped moieties was proposed. It was prepared by a very simple method, in which the epoxide addition reaction of 3-glycidoxypropyltrimethoxysilane with 1-octadecanethiol proceeded simultaneously with the reaction of silane coupling onto silica particles. By controlling the molecular ratio of 3-glycidoxypropyltrimethoxysilane to 1-octadecanethiol higher than 1.0 (1.56 for the present study), both polar-embedded and polar-endcapped moieties were achieved onto the packing. The performance of the packing was evaluated in detail. The results demonstrated that neutral, acidic and basic analytes were well separated on the packing. The column efficiency for phenanthrene was 34,200 theoretical plates per meter. In addition, four nucleotides can be separated in 100% phosphate buffered saline solution with good reproducibility, which indicates the packing has good stability in aqueous mobile phase. Amitriptyline, a typical basic analytes, was eluted out with relatively symmetric peak shape (asymmetry factor of 1.36), which implies that the packing has not suffered from the negative effect of residue silanols significantly. Good stability in buffer solution of pH ranging from 2.0 to 10.0 was also documented for the packing.

  6. Combatting Ionic Aggregation using Dielectric Forces Combining Modeling/Simulation and Experimental Results to Explain End-capping of Primary Amine Functionalized Polystyrene

    SciTech Connect

    Messman, Jamie M; Goswami, Monojoy; Pickel, Deanna L; Uhrig, David; Sumpter, Bobby G; Mays, Jimmy

    2011-01-01

    Chain-end functionalization of living poly(styryl)lithium using 1-(3-bromopropyl)-2,2,5,5-tetramethyl-1-aza-2,5-disilacyclo-pentane (BTDP) to generate primary amine end-functionalized polystyrene was investigated using high vacuum anionic polymerization techniques. 13C NMR spectroscopy and Matrix Assisted Laser Desorption Ionization Time of Flight Mass Spectrometry (MALDI-TOF MS) were used to evaluate polymer end-groups and demonstrated that quantitative amine functionalized polymer was attained under appropriate reaction conditions. In general, the polymerization of styrene was conducted in benzene and the end-capping reaction was performed by adding tetrahydrofuran (THF) to the reaction prior to the addition of BTDP in THF at room temperature. Results indicated that approximately 20% THF by volume is required to obtain 100% end-capping free from side reactions. When too little or no THF was present, side reactions such as lithium halogen exchange followed by Wurtz coupling resulted in unfunctionalized head-to-head dimer as well as other byproducts. Modeling and simulation of the solvent effects using hybrid methods (the so-called QM/MM method) suggest that THF effectively dissociated the anionic chain-end aggregation, thereby resulting in the desired primary amine functionalized polymer. Molecular dynamics (MD) simulations were conducted to develop an understanding of the physics of counterions involved in the end-functionalization process.

  7. In vitro release of a water-soluble agent from low viscosity biodegradable, injectable oligomers.

    PubMed

    Sharifpoor, Soroor; Amsden, Brian

    2007-03-01

    Low-molecular-weight poly(epsilon-caprolactone-co-1,3-trimethylene carbonate) and poly(1,3-trimethylene carbonate) are potential vehicles for the regio-specific delivery of water-soluble agents. In this paper, the characteristics and the mechanism governing the in vitro release of a model water-soluble drug, vitamin B12, from these polymer vehicles were determined. The loading of vitamin B12 was kept to 1 w/w%. The oligomers examined ranged from amorphous, high viscosity to crystalline but low viscosity. The oligomers did not degrade appreciably in vitro. The total fraction of vitamin B12 released increased as the crystallinity of the oligomers decreased, reaching nearly total release only for the completely amorphous oligomers. The rate of release was fastest for the amorphous oligomers and dependent on their viscosity. Inclusion of a more osmotically active agent, trehalose, into the vitamin B12 particles through co-lyophilization resulted in enhanced total fraction released and a faster release rate. The results are consistent with an osmotically driven release mechanism.

  8. Alzheimer's-associated Abeta oligomers show altered structure, immunoreactivity and synaptotoxicity with low doses of oleocanthal.

    PubMed

    Pitt, Jason; Roth, William; Lacor, Pascale; Smith, Amos B; Blankenship, Matthew; Velasco, Pauline; De Felice, Fernanda; Breslin, Paul; Klein, William L

    2009-10-15

    It now appears likely that soluble oligomers of amyloid-beta1-42 peptide, rather than insoluble fibrils, act as the primary neurotoxin in Alzheimer's disease (AD). Consequently, compounds capable of altering the assembly state of these oligomers (referred to as ADDLs) may have potential for AD therapeutics. Phenolic compounds are of particular interest for their ability to disrupt Abeta oligomerization and reduce pathogenicity. This study has focused on oleocanthal (OC), a naturally-occurring phenolic compound found in extra-virgin olive oil. OC increased the immunoreactivity of soluble Abeta species, when assayed with both sequence- and conformation-specific Abeta antibodies, indicating changes in oligomer structure. Analysis of oligomers in the presence of OC showed an upward shift in MW and a ladder-like distribution of SDS-stable ADDL subspecies. In comparison with control ADDLs, oligomers formed in the presence of OC (Abeta-OC) showed equivalent colocalization at synapses but exhibited greater immunofluorescence as a result of increased antibody recognition. The enhanced signal at synapses was not due to increased synaptic binding, as direct detection of fluorescently-labeled ADDLs showed an overall reduction in ADDL signal in the presence of OC. Decreased binding to synapses was accompanied by significantly less synaptic deterioration assayed by drebrin loss. Additionally, treatment with OC improved antibody clearance of ADDLs. These results indicate oleocanthal is capable of altering the oligomerization state of ADDLs while protecting neurons from the synaptopathological effects of ADDLs and suggest OC as a lead compound for development in AD therapeutics.

  9. Nitrogen Containing Organic Compounds and Oligomers in Secondary Organic Aerosol Formed by Photooxidation of Isoprene

    SciTech Connect

    Nguyen, Tran B.; Laskin, Julia; Laskin, Alexander; Nizkorodov, Serguei

    2011-07-06

    Electrospray ionization high-resolution mass spectrometry (ESI HR-MS) was used to probe molecular structures of oligomers in secondary organic aerosol (SOA) generated in laboratory experiments on isoprene photooxidation at low- and high-NOx conditions. Up to 80-90% of the observed products are oligomers and up to 33% are nitrogen-containing organic compounds (NOC). We observe oligomers with up to 8 monomer units in length. Tandem mass spectrometry (MSn) confirms NOC compounds are organic nitrates and elucidates plausible chemical building blocks contributing to oligomer formation. Most organic nitrates are comprised of methylglyceric acid units. Other important multifunctional C2-C5 monomer units are identified including methylglyoxal, hydroxyacetone, hydroxyacetic acid, glycolaldehyde, and 2-methyltetrols. The majority of the NOC oligomers contain only one nitrate moiety resulting in a low average N:C ratio of 0.019. Average O:C ratios of the detected SOA compounds are 0.54 under the low-NOx conditions and 0.83 under the high-NOx conditions. Our results underscore the importance of isoprene photooxidation as a source of NOC in organic particulate matter.

  10. Oligomer and SOA formation through aqueous phase photooxidation of methacrolein and methyl vinyl ketone

    NASA Astrophysics Data System (ADS)

    Liu, Yao; Siekmann, Frank; Renard, Pascal; El Zein, Atallah; Salque, Guillaume; El Haddad, Imad; Temime-Roussel, Brice; Voisin, Didier; Thissen, Roland; Monod, Anne

    2012-03-01

    This work investigates the ability of methacrolein (MACR) and methyl vinyl ketone (MVK) (the two main gas phase atmospheric oxidation products of isoprene) to form oligomers and secondary organic aerosol (SOA) upon aqueous phase OH-oxidation and subsequent water evaporation. For the two precursors, electrospray mass spectrometry (in infusion and coupled to liquid chromatography) analysis of the reacting solutions brought clear evidence for the formation of oligomer systems having a mass range of up to 1400 Da. More than 11 series of oligomers were found. For MVK, the intensity and masses of oligomers became increasingly important as MVK initial concentrations increased from 0.2 to 20 mM. For both precursors, the oligomers were responsible for the SOA formation during nebulization experiments. The evaluated SOA mass yield ranged from 3.9 to 9.9% for MVK. These yields were time dependent and were in good agreement with the range (1.6-11.7%) obtained for MACR under the same conditions by El Haddad et al. (2009).

  11. The Effect of Difunctional Oligomer Concentration and Processing Temperature on the Reactive Processing of Polymer Blends

    NASA Astrophysics Data System (ADS)

    O'Brien, Charles; Rice, Kevin; Dadmun, Mark

    2001-03-01

    Reactive processing is an interesting method to form compatibilizers for polymer blends in-situ. A model blend composed of poly(bisphenol A-co-epichlorohydrin) and poly(ethylene oxide) that is compatibilized with difunctional oligomers that are the same structure as the homopolymers is currently under investigation. It is expected that blocky copolymers will form at the bipahasic interface during processing as the difunctional oligomers undergo an addition copolymerization. Previous results have shown that the addition of the reactive oligomers improves the properties of the blend and thus this reactive process scheme is feasible. Additionally, these results indicate that the difunctioanal oligomers may act as plasticizers and continue to polymerize at room temperature after the blend is removed from the melt mixer. In this presentation, we will discuss our research that is focused on optimizing the reactive compatibilization process by controlling the amount of reactive oligomer added and the processing temperature and evaluating the effect of these parameters on the ultimate properties of the blend.

  12. Large-scale motif discovery using DNA Gray code and equiprobable oligomers

    PubMed Central

    Ichinose, Natsuhiro; Yada, Tetsushi; Gotoh, Osamu

    2012-01-01

    Motivation: How to find motifs from genome-scale functional sequences, such as all the promoters in a genome, is a challenging problem. Word-based methods count the occurrences of oligomers to detect excessively represented ones. This approach is known to be fast and accurate compared with other methods. However, two problems have hampered the application of such methods to large-scale data. One is the computational cost necessary for clustering similar oligomers, and the other is the bias in the frequency of fixed-length oligomers, which complicates the detection of significant words. Results: We introduce a method that uses a DNA Gray code and equiprobable oligomers, which solve the clustering problem and the oligomer bias, respectively. Our method can analyze 18 000 sequences of ~1 kbp long in 30 s. We also show that the accuracy of our method is superior to that of a leading method, especially for large-scale data and small fractions of motif-containing sequences. Availability: The online and stand-alone versions of the application, named Hegma, are available at our website: http://www.genome.ist.i.kyoto-u.ac.jp/~ichinose/hegma/ Contact: ichinose@i.kyoto-u.ac.jp; o.gotoh@i.kyoto-u.ac.jp PMID:22057160

  13. Chain-length and mode-delocalization dependent amide-I anharmonicity in peptide oligomers.

    PubMed

    Zhao, Juan; Wang, Jianping

    2012-06-07

    The diagonal anharmonicities of the amide-I mode in the alanine oligomers are examined in the normal-mode basis by ab initio calculations. The selected oligomers range from dimer to heptamer, in either the α-helical or β-sheet conformations. It is found that the anharmonicity varies from mode to mode within the same oligomer. For a given amide-I mode, the anharmonicity is closely related to the delocalization extent of the mode: the less it delocalizes, the larger the anharmonicity it has. Thus, the single-mode potential energy distribution (PED(max)) can be used as an indicator of the magnitude of the anharmonicity. It is found that as the peptide chain length increases, the averaged diagonal anharmonicity generally decreases; however, the sum of the averaged diagonal and off-diagonal anharmonicities within a peptide roughly remains a constant for all the oligomers examined, indicating the excitonic characteristics of the amide-I modes. Excitonic coupling tends to decrease the diagonal anharmonicities in a coupled system with multiple chromophores, which explains the observed behavior of the anharmonicities. The excitonic nature of the amide-I band in peptide oligomers is thus verified by the anharmonic computations. Isotopic substitution effect on the anharmonicities and mode localizations of the amide-I modes in peptides is also discussed.

  14. Amyloid Oligomers and Mature Fibrils Prepared from an Innocuous Protein Cause Diverging Cellular Death Mechanisms*

    PubMed Central

    Harte, Níal P.; Klyubin, Igor; McCarthy, Eoin K.; Min, Soyoung; Garrahy, Sarah Ann; Xie, Yongjing; Davey, Gavin P.; Boland, John J.; Rowan, Michael J.; Mok, K. Hun

    2015-01-01

    Despite significant advances, the molecular identity of the cytotoxic species populated during in vivo amyloid formation crucial for the understanding of neurodegenerative disorders is yet to be revealed. In this study lysozyme prefibrillar oligomers and fibrils in both mature and sonicated states have been isolated through an optimized ultrafiltration/ultracentrifugation method and characterized with various optical spectroscopic techniques, atomic force microscopy, and transmission electron microscopy. We examined their level and mode of toxicity on rat pheochromocytoma (PC12) cells in both differentiated and undifferentiated states. We find that oligomers and fibrils display cytotoxic capabilities toward cultured cells in vitro, with oligomers producing elevated levels of cellular injury toward undifferentiated PC12 cells (PC12undiff). Furthermore, dual flow cytometry staining experiments demonstrate that the oligomers and mature fibrils induce divergent cellular death pathways (apoptosis and secondary necrosis, respectively) in these PC12 cells. We have also shown that oligomers but not sonicated mature fibrils inhibit hippocampal long term potentiation, a form of synaptic plasticity implicated in learning and memory, in vivo. We conclude that our in vitro and in vivo findings confer a level of resistance toward amyloid fibrils, and that the PC 12-based comparative cytotoxicity assay can provide insights into toxicity differences between differently aggregated protein species. PMID:26221033

  15. Prefibrillar transthyretin oligomers and cold stored native tetrameric transthyretin are cytotoxic in cell culture

    SciTech Connect

    Soergjerd, Karin; Klingstedt, Therese; Lindgren, Mikael; Kagedal, Katarina; Hammarstroem, Per

    2008-12-26

    Recent studies suggest that soluble, oligomeric species, which are intermediates in the fibril formation process in amyloid disease, might be the key species in amyloid pathogenesis. Soluble oligomers of human wild type transthyretin (TTR) were produced to elucidate oligomer properties. Employing ThT fluorescence, time-resolved fluorescence anisotropy of pyrene-labeled TTR, chemical cross-linking, and electron microscopy we demonstrated that early formed soluble oligomers (within minutes) from A-state TTR comprised on the average 20-30 TTR monomers. When administered to neuroblastoma cells these early oligomers proved highly cytotoxic and induced apoptosis after 48 h of incubation. More mature fibrils (>24 h of fibrillation) were non-toxic. Surprisingly, we also found that native tetrameric TTR, when purified and stored under cold conditions (4 deg. C) was highly cytotoxic. The effect could be partially restored by increasing the temperature of the protein. The cytotoxic effects of native tetrameric TTR likely stems from a hitherto unexplored low temperature induced rearrangement of the tetramer conformation that possibly is related to the conformation of misfolded TTR in amyloigogenic oligomers.

  16. Sugar monomer and oligomer solubility: data and predictions for application to biomass hydrolysis.

    PubMed

    Gray, Matthew C; Converse, Alvin O; Wyman, Charles E

    2003-01-01

    Oligomer solubility could potentially play an important role in controlling the rates and yields in the thermochemical hydrolysis of hemicellulose as a pretreatment for subsequent enzymatic conversion of cellulose. However, limited data or models are available to describe the aqueous solubility of sugar monomers and oligomers. In this work, we measured the solubilities of sugars common to many biomass feedstocks in the temperature range of 25-30 degrees C. Then we reviewed solubility models for sugars from the open literature. Finally, we applied models to test their ability to describe this and other data reported in the literature. It was found that the solubility of sugar monomers was not well described by the ideal solubility law or other more complex models. However, with an empirical adjustment to the enthalpy of fusion, the ideal solubility law was able to approximately predict the solubility of cello-oligomers. Based on these results, solubilities for low molecular weight xylo-oligomers are predicted to investigate their possible importance in pretreatment and define further experimental measurements needed to improve our understanding of sugar and oligomer solubility.

  17. Comparison of mass spectrometric techniques for generating molecular weight information on a class of ethoxylated oligomers.

    PubMed

    Parees, D M; Hanton, S D; Clark, P A; Willcox, D A

    1998-04-01

    The results of fast atom bombardment (FAB), time-of-flight secondary ion mass spectrometry (ToF-SIMS), matrix-assisted laser desorption/ionization (MALD/I), electrospray ionization (ESI), and field desorption (FD) analyses of ethoxylated oligomers of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (Surfynol(®) 104) were compared.Each of these desorption mass spectrometry (MS) techniques can produce spectra of unfragmented cationized oligomers. From the observed ion series we calculate average molecular weight information. We have compared the results of mass spectrometric analyses of a series of ethoxylated Surfynol surfactants. Our data indicate that FAB, ToF-SIMS, MALDI/I, and ESI produce similar results for the lower molecular weight species, but that as the average molecular weight increases FAB and SIMS produce slightly lower results than MALD/I and FD. This could be due to increased fragmentation. ESI produced a result similar to FAB and SIMS for the highest average molecular weight material. Further experiments compare the mass spectral results with gas chromatographic quantitative data. Although gas chromatography is not expected to accurately analyze the higher mass oligomers, we observe significant differences in intensities of the short-chain oligomers (especially the 0- and 1-mers) when compared to the desorption mass spectrometer results. These differences may reflect poor cationization efficiency for very short oligomer chains in the mass spectrometric analyses.

  18. Construction of a lithium ion transport network in cathode with lithiated bis(benzene sulfonyl)imide based single ion polymer ionomers

    NASA Astrophysics Data System (ADS)

    Pan, Qiyun; Zhang, Wenchao; Pan, Meize; Zhang, Baodan; Zeng, Danli; Sun, Yubao; Cheng, Hansong

    2015-06-01

    We demonstrate a novel method to construct a lithium ion transport network in cathode materials by replacing PVDF with lithiated poly(bis(4-carbonyl benzene sulfonyl)imide-co-bis(4-amino benzene sulfonyl)imide) as the binder. The single ion conducting polymer was synthesized via polycondensation of bis(4-carbonyl benzene sulfonyl)imide and bis(4-amino benzene sulfonyl)imide followed by lithium ion exchange. By blending the ionomers with LiFePO4 and acetylene carbon, the ionic network was well constructed, resulting in a maximum use of active cathode material inside the cathode. The membrane of the polymer electrolyte exhibits an ionic conductivity of 0.14 mS cm-1 at room temperature, a high ion transference number of 0.92 and a wide electrochemical window of 4.5 V (vs. Li+/Li). A lithium ion battery assembled with the single ion conducting polymer electrolyte delivers excellent performance at room temperature with various C-rates.

  19. Biodegradable polyester-based eco-composites containing hemp fibers modified with macrocyclic oligomers

    NASA Astrophysics Data System (ADS)

    Conzatti, Lucia; Utzeri, Roberto; Hodge, Philip; Stagnaro, Paola

    2016-05-01

    An original compatibilizing pathway for hemp fibers/poly(1,4-butylene adipate-co-terephtalate) (PBAT) eco-composites was explored exploiting the capability of macrocyclic oligomers (MCOs), obtained by cyclodepolymerization (CDP) of PBAT at high dilution, of being re-converted into linear chains by entropically-driven ring-opening polymerization (ED-ROP) that occurs simply heating the MCOS in the bulk. CDP reaction of PBAT was carried out varying solvent, catalyst and reaction time. Selected MCOs were used to adjust the conditions of the ED-ROP reaction. The best experimental conditions were then adopted to modify hemp fibers. Eco-composites based on PBAT and hemp fibers as obtained or modified with PBAT macrocyclics or oligomers were prepared by different process strategies. The best fiber-PBAT compatibility was observed when the fibers were modified with PBAT oligomers before incorporation in the polyester matrix.

  20. Mitochondrial oligomers boost glycolysis in cancer stem cells to facilitate blebbishield-mediated transformation after apoptosis

    PubMed Central

    Jinesh, GG; Molina, JR; Huang, L; Laing, NM; Mills, GB; Bar-Eli, M; Kamat, AM

    2016-01-01

    Apoptosis culminates in secondary necrosis due to lack of ATP. Cancer stem cells form spheres after apoptosis by evoking the blebbishield emergency program. Hence, determining how blebbishields avoid secondary necrosis is crucial. Here we demonstrate that N-Myc and VEGFR2 control transformation from blebbishields, during which oligomers of K-Ras, p27, BAD, Bax, and Bak boost glycolysis to avoid secondary necrosis. Non-apoptotic cancer cells also utilize oligomers to boost glycolysis, which differentiates the glycolytic function of oligomers from their apoptotic action. Smac mimetic in combination with TNF-α or TRAIL but not in combination with FasL abrogates transformation from blebbishields by inducing secondary necrosis. Thus blebbishield-mediated transformation is dependent on glycolysis, and Smac mimetics represent potential candidates to abrogate the blebbishield emergency program. PMID:27551498

  1. Exploring the assembly mechanism of tetrapeptide oligomers using the Activation-Relaxation Technique

    NASA Astrophysics Data System (ADS)

    Wei, Guanghong; Mousseau, Normand; Derreumaux, Philippe

    2004-03-01

    Alzheimer's disease and Parkinson's disease are associated with formation of amyloid fibrils. All amyloid fibrils seem to share a common cross β-sheet structure. Experimental studies have shown that peptides as short as 4 amino acids can form amyloid fibrils. It has also been shown that the oligomers that form early in the aggregation process of even non-disease-related proteins may be cytotoxic. We report a detailed study of the assembly mechanisms of the tetrapeptides into different size oligomers: trimers, hexamers and more. The assembly of the oligomers, in which the peptides form β-sheets through interpeptide interactions, are studied using the activation-relaxation technique (ART) in combination with a reduced off-lattice energy model (OPEP). We also describe the multiple pathways of oligomerization as well as categorize the various oligomeric intermediates, providing information of the early events of β-sheet formation.

  2. New insight into the dynamical system of αB-crystallin oligomers

    PubMed Central

    Inoue, Rintaro; Takata, Takumi; Fujii, Norihiko; Ishii, Kentaro; Uchiyama, Susumu; Sato, Nobuhiro; Oba, Yojiro; Wood, Kathleen; Kato, Koichi; Fujii, Noriko; Sugiyama, Masaaki

    2016-01-01

    α-Crystallin possesses a dynamic quaternary structure mediated by its subunit dynamics. Elucidation of a mechanism of subunit dynamics in homo-oligomers of αB-crystallin was tackled through deuteration-assisted small-angle neutron scattering (DA-SANS) and electrospray ionization (ESI) native mass spectrometry (nMS). The existence of subunit exchange was confirmed with DA-SANS, and monomers liberated from the oligomers were observed with nMS. With increasing temperature, an increase in both the exchange rate and monomer population was observed despite the absence of oligomer collapse. It is proposed that transiently liberated subunits, namely, “traveling subunits,” play a role in subunit exchange. Moreover, we propose that protein function is regulated by these traveling subunits. PMID:27381175

  3. Simple extrapolation method to predict the electronic structure of conjugated polymers from calculations on oligomers

    SciTech Connect

    Larsen, Ross E.

    2016-04-12

    In this study, we introduce two simple tight-binding models, which we call fragment frontier orbital extrapolations (FFOE), to extrapolate important electronic properties to the polymer limit using electronic structure calculations on only a few small oligomers. In particular, we demonstrate by comparison to explicit density functional theory calculations that for long oligomers the energies of the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), and of the first electronic excited state are accurately described as a function of number of repeat units by a simple effective Hamiltonian parameterized from electronic structure calculations on monomers, dimers and, optionally, tetramers. For the alternating copolymer materials that currently comprise some of the most efficient polymer organic photovoltaic devices one can use these simple but rigorous models to extrapolate computed properties to the polymer limit based on calculations on a small number of low-molecular-weight oligomers.

  4. Excitonic Coupling and Femtosecond Relaxation of Zinc Porphyrin Oligomers Linked with Triazole Bridge: Dynamics and Modeling.

    PubMed

    Bukreev, Alexey; Mikhailov, Konstantin; Shelaev, Ivan; Gostev, Fedor; Polevaya, Yuliya; Tyurin, Vladimir; Beletskaya, Irina; Umansky, Stanislav; Nadtochenko, Victor

    2016-03-31

    The synthesis of new zinc porphyrin oligomers linked by a triazole bridge was carried out via "click" reaction. A split in the porphyrin oligomer B-band was observed. It was considered as evidence of exciton-excitonic coupling. The relaxation of excited states in Q-band porphyrin oligomers was studied by the femtosecond laser spectroscopy technique with a 20 fs pump pulse. The transient oscillations of two B-band excitonic peaks have a π-radian shift. For explanation of the coherent oscillation, a theoretical model was developed. The model considered the combination of the exciton-excitonic coupling between porphyrin rings in dimer and weak exciton-vibronic coupling in one porphyrin ring. By varying the values of the structural parameters of porphyrins (the strength values of this couplings and measure of symmetry breaking), we obtained correspondence between the experimental data (phase shift and amplitudes of the spectrum oscillations) and the predictions of the model developed here.

  5. Simple extrapolation method to predict the electronic structure of conjugated polymers from calculations on oligomers

    DOE PAGES

    Larsen, Ross E.

    2016-04-12

    In this study, we introduce two simple tight-binding models, which we call fragment frontier orbital extrapolations (FFOE), to extrapolate important electronic properties to the polymer limit using electronic structure calculations on only a few small oligomers. In particular, we demonstrate by comparison to explicit density functional theory calculations that for long oligomers the energies of the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), and of the first electronic excited state are accurately described as a function of number of repeat units by a simple effective Hamiltonian parameterized from electronic structure calculations on monomers, dimers and, optionally,more » tetramers. For the alternating copolymer materials that currently comprise some of the most efficient polymer organic photovoltaic devices one can use these simple but rigorous models to extrapolate computed properties to the polymer limit based on calculations on a small number of low-molecular-weight oligomers.« less

  6. Solution state structure determination of silicate oligomers by 29SI NMR spectroscopy and molecular modeling.

    PubMed

    Cho, Herman; Felmy, Andrew R; Craciun, Raluca; Keenum, J Patrick; Shah, Neil; Dixon, David A

    2006-02-22

    Evidence for nine new solution state silicate oligomers has been discovered by (29)Si NMR homonuclear correlation experiments of (29)Si-enriched samples. In addition to enhancing signal sensitivity, the isotopic enrichment increases the probability of the (29)Si-(29)Si two-bond scalar couplings that are necessary for the observation of internuclear correlations in 2-D experiments. The proposed assignments are validated by comparisons of experimental and simulated cross-peaks obtained with high digital resolution. The internuclear connectivity indicated by the NMR data suggests that several of these oligomers can have multiple stereoisomers, including conformers and/or diastereomers. The stabilities of these oligomers and their possible stereoisomers have been investigated by electronic structure calculations.

  7. A mechanistic model of tau amyloid aggregation based on direct observation of oligomers

    NASA Astrophysics Data System (ADS)

    Shammas, Sarah L.; Garcia, Gonzalo A.; Kumar, Satish; Kjaergaard, Magnus; Horrocks, Mathew H.; Shivji, Nadia; Mandelkow, Eva; Knowles, Tuomas P. J.; Mandelkow, Eckhard; Klenerman, David

    2015-04-01

    Protein aggregation plays a key role in neurodegenerative disease, giving rise to small oligomers that may become cytotoxic to cells. The fundamental microscopic reactions taking place during aggregation, and their rate constants, have been difficult to determine due to lack of suitable methods to identify and follow the low concentration of oligomers over time. Here we use single-molecule fluorescence to study the aggregation of the repeat domain of tau (K18), and two mutant forms linked with familial frontotemporal dementia, the deletion mutant ΔK280 and the point mutant P301L. Our kinetic analysis reveals that aggregation proceeds via monomeric assembly into small oligomers, and a subsequent slow structural conversion step before fibril formation. Using this approach, we have been able to quantitatively determine how these mutations alter the aggregation energy landscape.

  8. Solution State Structure Determination of Silicate Oligomers by 29Si NMR Spectroscopy and Molecular Modeling

    SciTech Connect

    Cho, Herman M.; Felmy, Andrew R.; Craciun, Raluca; Keenum, Johnathan P.; Shah, Neil K.; Dixon, David A.

    2006-02-22

    Evidence for nine new solution state silicate oligomers has been discovered by 29Si NMR homonuclear correlation experiments of 29Si-enriched samples. In addition to enhancing signal sensitivity, the isotopic enrichment increases the probability of the 29Si–29Si two-bond scalar couplings that are necessary for the observation of internuclear correlations in 2-D experiments. The proposed assignments are validated by comparisons of experimental and simulated crosspeaks obtained with high digital resolution. The internuclear connectivity indicated by the NMR data suggests that several of these oligomers can have multiple stereoisomers, including conformers and/or diastereomers. The stability of these oligomers and their possible stereoisomers have been investigated by electronic structure calculations.

  9. Thio-urethane oligomers improve the properties of light-cured resin cements

    PubMed Central

    Bacchi, Ataís; Consani, Rafael L.; Martim, Gedalias C.; Pfeifer, Carmem S.

    2015-01-01

    Thio-urethanes were synthesized by combining 1,6-Hexanediol-diissocyante (aliphatic) with pentaerythritol tetra-3-mercaptopropionate (PETMP) or 1,3-bis(1-isocyanato-1-methylethyl)benzene (aromatic) with trimethylol-tris-3-mercaptopropionate (TMP), at 1:2 isocyanate:thiol, leaving pendant thiols. Oligomers were added at 10–30 phr to BisGMA-UDMA-TEGDMA (5:3:2, BUT). 25wt% silanated inorganic fillers were added. Commercial cement (Relyx Veneer, 3M-ESPE) was also evaluated with 10–20 phr of aromatic oligomer. Near-IR was used to follow methacrylate conversion (DC) and rate of polymerization (Rpmax). Mechanical properties were evaluated in three-point bending (ISO 4049) for flexural strength/modulus (FS/FM, and toughness), and notched specimens (ASTM Standard E399-90) for fracture toughness (KIC). Polymerization stress (PS) was measured on the Bioman. Volumetric shrinkage (VS, %) was measured with the bonded disk technique. Results were analyzed with ANOVA/Tukey’s test (α=5%). In general terms, for BUT cements, conversion and mechanical properties in flexure increased for selected groups with the addition of thio-urethane oligomers. The aromatic versions resulted in greater FS/FM than aliphatic. Fracture toughness increased by twofold in the experimental groups (from 1.17±0.36 to around 3.23±0.22 MPa.m1/2). Rpmax decreased with the addition of thio-urethanes, though the vitrification point was not statistically different from the control. VS and PS decreased with both oligomers. For the commercial cement, 20 phr of oligomer increased DC, vitrification, reduced Rpmax and also significantly increased KIC, and reduced PS and FM. Thio-urethane oligomers were shown to favorably modify conventional dimethacrylate networks. Significant reductions in polymerization stress were achieved at the same time conversion and fracture toughness increased. PMID:25740124

  10. Air-Stable n-channel Diketopyrrolopyrrole-Diketopyrrolopyrrole Oligomers for High Performance Ambipolar Organic Transistors.

    PubMed

    Mukhopadhyay, Tushita; Puttaraju, Boregowda; Senanayak, Satyaprasad P; Sadhanala, Aditya; Friend, Richard; Faber, Hendrik A; Anthopoulos, Thomas D; Salzner, Ulrike; Meyer, Andreas; Patil, Satish

    2016-09-28

    n-channel organic semiconductors are prone to oxidation upon exposed to ambient conditions. Herein, we report design and synthesis of diketopyrrolopyrrole (DPP)-based oligomers for ambipolar organic thin-film transistors (OFETs) with excellent air and bias stability at ambient conditions. The cyclic voltammetry measurements reveal exceptional electrochemical stability during the redox cycle of oligomers. Structural properties including aggregation, crystallinity, and morphology in thin film were investigated by UV-visible spectroscopy, atomic force microscopy (AFM), thin-film X-ray diffraction (XRD), and grazing incidence small-angle X-ray scattering (GISAXS) measurements. AFM reveals morphological changes induced by different processing conditions whereas GISAXS measurements show an increase in the population of face-on oriented crystallites in films subjected to a combination of solvent and thermal treatments. These measurements also highlight the significance of chalcogen atom from sulfur to selenium on the photophysical, optical, electronic, and solid-state properties of DPP-DPP oligomers. Charge carrier mobilities of the oligomers were investigated by fabricating top-gate bottom-contact (TG-BC) thin-film transistors by annealing the thin films under various conditions. Combined solvent and thermal annealing of DPP-DPP oligomer thin films results in consistent electron mobilities as high as ∼0.2 cm(2) V(-1) s(-1) with an on/off ratio exceeding 10(4). Field-effect behavior was retained for up to ∼4 weeks, which illustrates remarkable air and bias stability. This work paves the way toward the development of n-channel DPP-DPP-based oligomers exhibiting retention of field-effect behavior with superior stability at ambient conditions.

  11. Folding and self-assembly of aromatic and aliphatic urea oligomers: towards connecting structure and function.

    PubMed

    Fischer, Lucile; Guichard, Gilles

    2010-07-21

    Folding and self-assembly of biomacromolecules has inspired the development of discrete, non-natural oligomers that fold and/or self-assemble in a controlled manner. Though aromatic and aliphatic oligoamides remain unmatched for structural diversity and synthetic versatility, oligomers based on amide bond surrogates, such as urea backbones, also demonstrated a propensity for folding and self-assembly. In this Perspective, we review the advances in the design of oligomeric aromatic and aliphatic urea sequences (essentially N,N'-linked) that fold and/or self-assemble. Whenever applicable, the relationship between structure and function will be highlighted.

  12. Synthesis and incorporation of thienylene vinylene oligomers in main-chain copolymers

    SciTech Connect

    Madrigal, L.G.; Elandaloussi, E.H.; Spangler, C.W.

    1998-07-01

    Poly [2,5-thienylene vinylene] (PTV) has been studied extensively over the past decade for both its metallic conductivity behavior upon chemical doping, as well as its interesting third order nonlinear optical properties. PTV oligomers have been synthesized by the group, as well as others, and the formation of polaron-like radical-cations or bipolaron-like dications by oxidative doping has been demonstrated. In this paper the authors describe a general synthetic approach to PTV oligomers functionalized for copolymer formation by step-growth reaction.

  13. Energy Aspects of Thermal Molecular Switching: Molecular Thermal Hysteresis of Helicene Oligomers.

    PubMed

    Shigeno, Masanori; Kushida, Yo; Yamaguchi, Masahiko

    2015-07-20

    Molecular switching is a phenomenon by which a molecule reversibly changes its structure and state in response to external stimuli or energy. Herein, molecular switching is discussed from thermodynamic and kinetic aspects in terms of energy supply with an emphasis on the thermal switching exhibited by helicene oligomers. It includes the inversion of relative thermodynamic stability induced by temperature changes and molecular thermal hysteresis in a closed system. The thermal phenomenon associated with the oligomers involves population/concentration changes between metastable states under nonequilibrium thermodynamic control.

  14. Asymmetric synthesis of vinylogous β-amino acids and their incorporation into mixed backbone oligomers.

    PubMed

    Wu, Hao; An, Hongchan; Mo, Shuting Cynthia; Kodadek, Thomas

    2017-03-27

    Chiral vinylogous β-amino acids (VBAA) were synthesized using enantioselective Mannich reactions of aldehydes with in situ generated N-carbamoyl imines followed by a Horner-Wadsworth-Emmons reaction. The efficiency with which these units could be incorporated into oligomers with different moieties on the C- and N-terminal sides was established, as was the feasibility of sequencing oligomers containing VBAAs by tandem mass spectrometry. The data show that VBAAs will be useful building blocks for the construction of combinatorial libraries of peptidomimetic compounds.

  15. Synthesis and G-Quadruplex-Binding Properties of Defined Acridine Oligomers

    PubMed Central

    Ferreira, Rubén; Aviñó, Anna; Pérez-Tomás, Ricardo; Gargallo, Raimundo; Eritja, Ramon

    2010-01-01

    The synthesis of oligomers containing two or three acridine units linked through 2-aminoethylglycine using solid-phase methodology is described. Subsequent studies on cell viability showed that these compounds are not cytotoxic. Binding to several DNA structures was studied by competitive dialysis, which showed a clear affinity for DNA sequences that form G-quadruplexes and parallel triplexes. The fluorescence spectra of acridine oligomers were affected strongly upon binding to DNA. These spectral changes were used to calculate the binding constants (K). Log K were found to be in the order of 4–6. PMID:20725626

  16. Thermo-reversible gelation of atactic poly(methyl methacrylate) in poly(ethylene glycol) oligomers.

    PubMed

    Gao, Yun; Yu, Chunhong; Chen, Minzhi; Wang, Xiaoliang; Zhou, Dongshan; Xue, Gi

    2013-04-01

    The temperature-concentration behavior of physical gel by atactic poly(methyl methacrylate) (aPMMA) in poly(ethylene glycol) oligomer (PEG400) was investigated. A liquid-liquid demixing interferes with a glass transition during cooling. The combination of demixing and T g leads to the formation of amorphous gels at low temperature. We suggest that the gelation of aPMMA/PEG400 is a glassy gel, in which short-range attractive depletion interaction in the polymer/oligomer system was the driving force at molecular level.

  17. Absorption enhancing effects of chitosan oligomers on the intestinal absorption of low molecular weight heparin in rats.

    PubMed

    Zhang, Hailong; Mi, Jie; Huo, Yayu; Huang, Xiaoyan; Xing, Jianfeng; Yamamoto, Akira; Gao, Yang

    2014-05-15

    Absorption enhancing effects of chitosan oligomers with different type and varying concentration on the intestinal absorption of low molecular weight heparin (LMWH) were examined by an in situ closed loop method in different intestinal sections of rats. Chitosan hexamer with the optimal concentration of 0.5% (w/v) showed the highest absorption enhancing ability both in the small intestine and large intestine. The membrane toxicities of chitosan oligomers were evaluated by morphological observation and determining the biological markers including amount of protein and activity of lactate dehydrogenase (LDH) released from intestinal epithelium cells. There was no obvious change both in levels of protein and LDH and morphology in the intestinal membrane between control and various chitosan oligomers groups, suggesting that chitosan oligomers did not induce any significant membrane damage to the intestinal epithelium. In addition, zeta potentials became less negative and amount of free LMWH gradually decreased when various chitosan oligomers were added to LMWH solution, revealing that electrostatic interaction between positively charged chitosan oligomers and negative LMWH was included in the absorption enhancing mechanism of chitosan oligomers. In conclusion, chitosan oligomers, especially chitosan hexamer, are safe and efficient absorption enhancers and can be used promisingly to improve oral absorption of LMWH.

  18. Single-Molecule Imaging Reveals Aβ42:Aβ40 Ratio-Dependent Oligomer Growth on Neuronal Processes

    PubMed Central

    Johnson, Robin D.; Schauerte, Joseph A.; Chang, Chun-Chieh; Wisser, Kathleen C.; Althaus, John Christian; Carruthers, Cynthia J.L.; Sutton, Michael A.; Steel, Duncan G.; Gafni, Ari

    2013-01-01

    Soluble oligomers of the amyloid-β peptide have been implicated as proximal neurotoxins in Alzheimer’s disease. However, the identity of the neurotoxic aggregate(s) and the mechanisms by which these species induce neuronal dysfunction remain uncertain. Physiologically relevant experimentation is hindered by the low endogenous concentrations of the peptide, the metastability of Aβ oligomers, and the wide range of observed interactions between Aβ and biological membranes. Single-molecule microscopy represents one avenue for overcoming these challenges. Using this technique, we find that Aβ binds to primary rat hippocampal neurons at physiological concentrations. Although amyloid-β(1–40) as well as amyloid-β(1–42) initially form larger oligomers on neurites than on glass slides, a 1:1 mix of the two peptides result in smaller neurite-bound oligomers than those detected on-slide or for either peptide alone. With 1 nM peptide in solution, Aβ40 oligomers do not grow over the course of 48 h, Aβ42 oligomers grow slightly, and oligomers of a 1:1 mix grow substantially. Evidently, small Aβ oligomers are capable of binding to neurons at physiological concentrations and grow at rates dependent on local Aβ42:Aβ40 ratios. These results are intriguing in light of the increased Aβ42:Aβ40 ratios shown to correlate with familial Alzheimer’s disease mutations. PMID:23442968

  19. The effects of a multifunctional oligomer and its incorporation strategies on the gene delivery efficiency of poly(L-lysine).

    PubMed

    Zhou, Dezhong; Li, Congxin; Hu, Yuling; Zhou, Hao; Chen, Jiatong; Zhang, Zhengpu; Guo, Tianying

    2012-05-14

    A novel multifunctional oligomer is synthesized and incorporated to enhance the gene delivery efficiency of PLL via non-electrostatic assembly and covalent grafting strategies. The improvement of the gene delivery efficiency is dependent on the gene carrying complex properties, and the properties are dependent on the oligomer incorporation strategy.

  20. Enzymatic production of defined chitosan oligomers with a specific pattern of acetylation using a combination of chitin oligosaccharide deacetylases

    NASA Astrophysics Data System (ADS)

    Hamer, Stefanie Nicole; Cord-Landwehr, Stefan; Biarnés, Xevi; Planas, Antoni; Waegeman, Hendrik; Moerschbacher, Bruno Maria; Kolkenbrock, Stephan

    2015-03-01

    Chitin and chitosan oligomers have diverse biological activities with potentially valuable applications in fields like medicine, cosmetics, or agriculture. These properties may depend not only on the degrees of polymerization and acetylation, but also on a specific pattern of acetylation (PA) that cannot be controlled when the oligomers are produced by chemical hydrolysis. To determine the influence of the PA on the biological activities, defined chitosan oligomers in sufficient amounts are needed. Chitosan oligomers with specific PA can be produced by enzymatic deacetylation of chitin oligomers, but the diversity is limited by the low number of chitin deacetylases available. We have produced specific chitosan oligomers which are deacetylated at the first two units starting from the non-reducing end by the combined use of two different chitin deacetylases, namely NodB from Rhizobium sp. GRH2 that deacetylates the first unit and COD from Vibrio cholerae that deacetylates the second unit starting from the non-reducing end. Both chitin deacetylases accept the product of each other resulting in production of chitosan oligomers with a novel and defined PA. When extended to further chitin deacetylases, this approach has the potential to yield a large range of novel chitosan oligomers with a fully defined architecture.

  1. Enzymatic production of defined chitosan oligomers with a specific pattern of acetylation using a combination of chitin oligosaccharide deacetylases

    PubMed Central

    Hamer, Stefanie Nicole; Cord-Landwehr, Stefan; Biarnés, Xevi; Planas, Antoni; Waegeman, Hendrik; Moerschbacher, Bruno Maria; Kolkenbrock, Stephan

    2015-01-01

    Chitin and chitosan oligomers have diverse biological activities with potentially valuable applications in fields like medicine, cosmetics, or agriculture. These properties may depend not only on the degrees of polymerization and acetylation, but also on a specific pattern of acetylation (PA) that cannot be controlled when the oligomers are produced by chemical hydrolysis. To determine the influence of the PA on the biological activities, defined chitosan oligomers in sufficient amounts are needed. Chitosan oligomers with specific PA can be produced by enzymatic deacetylation of chitin oligomers, but the diversity is limited by the low number of chitin deacetylases available. We have produced specific chitosan oligomers which are deacetylated at the first two units starting from the non-reducing end by the combined use of two different chitin deacetylases, namely NodB from Rhizobium sp. GRH2 that deacetylates the first unit and COD from Vibrio cholerae that deacetylates the second unit starting from the non-reducing end. Both chitin deacetylases accept the product of each other resulting in production of chitosan oligomers with a novel and defined PA. When extended to further chitin deacetylases, this approach has the potential to yield a large range of novel chitosan oligomers with a fully defined architecture. PMID:25732514

  2. Enzymatic production of defined chitosan oligomers with a specific pattern of acetylation using a combination of chitin oligosaccharide deacetylases.

    PubMed

    Hamer, Stefanie Nicole; Cord-Landwehr, Stefan; Biarnés, Xevi; Planas, Antoni; Waegeman, Hendrik; Moerschbacher, Bruno Maria; Kolkenbrock, Stephan

    2015-03-03

    Chitin and chitosan oligomers have diverse biological activities with potentially valuable applications in fields like medicine, cosmetics, or agriculture. These properties may depend not only on the degrees of polymerization and acetylation, but also on a specific pattern of acetylation (PA) that cannot be controlled when the oligomers are produced by chemical hydrolysis. To determine the influence of the PA on the biological activities, defined chitosan oligomers in sufficient amounts are needed. Chitosan oligomers with specific PA can be produced by enzymatic deacetylation of chitin oligomers, but the diversity is limited by the low number of chitin deacetylases available. We have produced specific chitosan oligomers which are deacetylated at the first two units starting from the non-reducing end by the combined use of two different chitin deacetylases, namely NodB from Rhizobium sp. GRH2 that deacetylates the first unit and COD from Vibrio cholerae that deacetylates the second unit starting from the non-reducing end. Both chitin deacetylases accept the product of each other resulting in production of chitosan oligomers with a novel and defined PA. When extended to further chitin deacetylases, this approach has the potential to yield a large range of novel chitosan oligomers with a fully defined architecture.

  3. Solvent free, catalyst free, microwave or grinding assisted synthesis of bis-cyclic imide derivatives and their evaluation for anticancer activity.

    PubMed

    Kumar, Anuj; Banerjee, Somesh; Roy, Partha; Sondhi, S M; Sharma, Anuj

    2017-02-01

    Cyclic imides are well known to be very important antitumor agents such as mitonafide and amonafide etc. Based on this fact, we have synthesized two series of cyclic imide derivatives containing two cyclic imide moiety in their structures (bis-cyclic imides) and screened them for in vitro anticancer activity against five human cancer cell lines i.e. breast (T47D), lung (NCl H-522), colon (HCT-15), ovary (PA-1) and liver (Hep G2). One series of bis-cyclic imide derivatives (3a-h) have been synthesized by condensation of acid anhydrides (1a-b) with diamines (2a-d) and another series (9a-f, 10a-f, 11a-f and 12a-f) by condensation of various diamines (4a-f) with diacids (5-8) in good yields. Structures assigned to 3a-h, 9a-f, 10a-f, 11a-f and 12a-f were fully characterized by spectroscopic means and elemental analysis. On screening for in vitro anticancer activity, compounds 3a (breast T47D), 3d (breast T47D, liver Hep G2), 3e (breast T47D, liver Hep G2), 3h (colon HCT-15), 10f (liver Hep G2) and 11a (colon HCT-15, ovary PA-1) exhibited good anticancer activities with IC50 values range from 12.41±3.2 to 17.9±2.5μM.

  4. Solubilities of carbon dioxide and oxygen in the ionic liquids methyl trioctyl ammonium bis(trifluoromethylsulfonyl)imide, 1-butyl-3-methyl imidazolium bis(trifluoromethylsulfonyl)imide, and 1-butyl-3-methyl imidazolium methyl sulfate.

    PubMed

    Bahadur, Indra; Osman, Khalid; Coquelet, Christophe; Naidoo, Paramespri; Ramjugernath, Deresh

    2015-01-29

    Ionic liquids (ILs) are being considered as solvents for gas absorption processes as they have the potential, in general, for improved efficiency of gas separations, as well as lower capital and operating costs compared to current commercial processes. In this study the solvent properties of ILs are investigated for use in the absorption of carbon dioxide (CO2) and oxygen (O2). The absorption of these gases in ILs was measured in the temperature range 303.15-333.15 K and at pressures up to 1.5 MPa by gravimetric analysis. The ILs used were methyl trioctyl ammonium bis (trifluoromethylsulfonyl) imide ([MOA][Tf2N]), 1-butyl-3-methyl imidazolium bis (trifluoromethylsulfonyl) imide ([BMIM][Tf2N]), and 1-butyl-3-methyl imidazolium methyl sulfate ([BMIM][MeSO4]). The measurement technique employed in this study is fast and accurate, and requires small quantities of solvent. The results indicated that absorption of both gases increased with a decrease in operating temperature and an increase in pressure. [MOA][Tf2N] had the highest CO2 and O2 solubility. [BMIM][Tf2N] was determined to have the highest selectivity for CO2 absorption. [BMIM][MeSO4] achieved the lowest CO2 absorption with a moderate O2 absorption, revealing this IL to be the least desirable for CO2 and O2 absorption. Calculation of Henry's law constants for all systems confirmed the deductions made from absorption data analysis. Calculation of enthalpy and entropy of absorption for each system revealed CO2 absorption in [MOA][Tf2N] to be the least sensitive to temperature increases. The absorption data was modeled using the generic Redlich-Kwong cubic equation of state (RK-EOS) coupled with a group contribution method.

  5. Optimization of a ligand immobilization and azide group endcapping concept via "Click-Chemistry" for the preparation of adsorbents for antibody purification.

    PubMed

    Horak, Jeannie; Hofer, Stefan; Lindner, Wolfgang

    2010-12-15

    This report describes and compares different strategies to deactivate (endcap) epoxide groups and azide groups on bio-chromatographic support surfaces, before and after ligand attachment. Adsorbents possessing epoxide groups were deactivated using acidic hydrolysis or were endcapped with 2-mercaptoethanol or 2-ethanolamine. The influence of surface-bound 2-ethanolamine was demonstrated for the triazine-type affinity adsorbent B14-2LP-FractoAIMs-1, which was tested in combination with the weak anion exchange material 3-aminoquinuclidine-FractoAIMs-3 (AQ-FA3). Azide groups were modified with 2-propargylalcohol using Click-Chemistry. Besides the conventional one-pot Click reaction, an alternative approach was introduced. This optimized Click protocol was employed (i) for the preparation of the weak anion exchange material AdQ-triazole-Fractogel (AdQ-TRZ-FG) and (ii) for the endcapping of residual azide groups with 3-propargyl alcohol. Using the new Click reaction protocol the ligand immobilization rate was doubled from 250 to 500 μmol/g dry adsorbent. Furthermore, the modified support surface was proven to be inert towards the binding of immunoglobulin G (IgG) as well as feed impurities. A thorough evaluation of modified surfaces and adsorbents was performed with dynamic binding experiments using cell culture supernatant containing monoclonal human immunoglobulin G (h-IgG-1). Besides SDS-Page, a recently introduced Protein A-size exclusion HPLC method (PSEC-HPLC) was used to visualize the feed impurity composition and the IgG content of all collected sample fractions in simple PSEC-Plots. A surprising outcome of this study was the irreversible binding of IgG to azide modified surfaces. It was found that organic azide compounds, e.g. 1-azide-3-(2-propen-1-yloxy)-2-propanol (AGE-N3) promote antibody aggregation to a slightly higher extent than the inorganic sodium azide. The possibility that the Hofmeister Series of salt anions may be applicable to predict the

  6. Glycosyl-Templated Chiral Helix Stapling of Ethynylpyridine Oligomers by Alkene Metathesis between Inter-Pitch Side Chains.

    PubMed

    Abe, Hajime; Kayamori, Fumihiro; Inouye, Masahiko

    2015-06-22

    Ethynylpyridine polymers and oligomers consisting of 4-substituted pyridine rings linked by acetylene bonds at the 2- and 6-positions have been investigated. Ethynylpyridine oligomers covalently linked with a glycosyl chiral template form chiral helical complexes by intramolecular hydrogen bonding, in which the chirality of the template is translated to the helix. With a view to fixation of the chiral architecture, D/L-galactosyl- and D/L-mannosyl-linked ethynylpyridine oligomers have been developed with 4-(3-butenyloxy)pyridine units having alkene side chains. The helical structures are successfully stapled by alkene metathesis of the side chains. Subsequent removal of the chiral templates by acidolysis produces template-free stapled oligomers. The chiral, template-free, stapled oligomers show chiral helicity, which is resistant to polar solvents and heating.

  7. Crystallization and preliminary crystallographic study of oligomers of the haemolytic lectin CEL-III from the sea cucumber Cucumaria echinata.

    PubMed

    Unno, Hideaki; Hisamatsu, Keigo; Nagao, Tomonao; Tateya, Yuki; Matsumoto, Naoki; Goda, Shuichiro; Hatakeyama, Tomomitsu

    2013-04-01

    CEL-III is a Ca(2+)-dependent haemolytic lectin isolated from the marine invertebrate Cucumaria echinata. This lectin binds to Gal/GalNAc-containing carbohydrate chains on the cell surface and, after conformational changes, oligomerizes to form ion-permeable pores in cell membranes. CEL-III also forms soluble oligomers similar to those formed in cell membranes upon binding of specific carbohydrates in high-pH and high-salt solutions. These soluble and membrane CEL-III oligomers were crystallized and X-ray diffraction data were collected. Crystals of soluble oligomers and membrane oligomers diffracted X-rays to 3.3 and 4.2 Å resolution, respectively, using synchrotron radiation and the former was found to belong to space group C2. Self-rotation functional analysis of the soluble oligomer crystal suggested that it might be composed of heptameric CEL-III.

  8. N-ethyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide-electrospun polyvinylidene fluoride composite electrolytes: characterization and lithium cell studies.

    PubMed

    Zhou, Yundong; Wang, Xiaoen; Zhu, Haijin; Armand, Michel; Forsyth, Maria; Greene, George W; Pringle, Jennifer M; Howlett, Patrick C

    2017-01-18

    Using the organic ionic plastic crystal N-ethyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide ([C2mpyr][FSI]) with electrospun nanofibers, LiFSI doped [C2mpyr][FSI]-PVdF composites were developed as solid state, self-standing electrolyte membranes. Different lithium salt concentration were investigated, with 10 mol% LiFSI found to be optimal amongst those assessed. Composites with different weight ratios of plastic crystal and polymer were prepared and 10 wt% polymer gave the highest conductivity. In addition, the effects of PVdF incorporation on the morphological, thermal, and structural properties of the organic ionic plastic crystal were investigated. Ion mobilities were also studied using solid-state nuclear magnetic resonance techniques. The electrolytes were then assembled into lithium symmetric cells and cycled galvanostatically at 0.13 mA cm(-2) at both ambient temperature and at 50 °C, for more than 500 cycles.

  9. Polymer electrolyte based on crosslinked poly(glycidyl methacrylate) and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

    SciTech Connect

    Fei, Beatrice Wong Chui; Hanifah, Sharina Abu; Ahmad, Azizan; Hassan, Nur Hasyareeda

    2015-09-25

    Polymer electrolytes based on crosslinked poly(glycidyl methacrylate) as polymer host and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BmimTFSI) as incorporated salt were prepared by in-situ photopolymerization technique. The complexes with different mass ratio of glycidyl methacrylate (GMA) monomer to BmimTFSI were investigated. The ionic conductivity of the polymer electrolyte was increased and reach the highest value of 7.50 × 10{sup −4} S cm{sup −1} at the ratio of 3:7 (GMA: BmimTFSI). The interaction between the polymer host and ionic liquid was proved by Attenuated Total Reflectance-Fourier Transformation Infra-Red Spectroscopy (ATR-FTIR). Meanwhile, the X-ray diffraction analysis shows the amorphousity of the polymer electrolyte film increase with the ionic liquid ratio.

  10. Synthesis and biological evaluation of cyclic imides incorporating benzenesulfonamide moieties as carbonic anhydrase I, II, IV and IX inhibitors.

    PubMed

    Abdel-Aziz, Alaa A-M; Angeli, Andrea; El-Azab, Adel S; Abu El-Enin, Mohamed A; Supuran, Claudiu T

    2017-03-01

    A group of cyclic imides was synthesized by reaction of amino-substituted benzenesulfonamides with a series of acid anhydrides such as succinic, maleic, tetrahydrophthalic, pyrazine-2,3-dicarboxylic acid anhydride, and substituted phthalic anhydrides. The synthesized sulfonamides were evaluated as carbonic anhydrase (CA, EC 4.2.1.1) inhibitors against the human (h) isoforms hCA I, II, IV and IX, involved in a variety of diseases among which glaucoma, retinitis pigmentosa, etc. Some of these sulfonamides showed effective inhibitory action (in the nanomolar range) against the cytosolic isoform hCA II and the transmembrane, tumor-associated one hCA IX, making them interesting candidates for preclinical evaluation in glaucoma or various tumors in which the two enzymes are involved. hCA I and IV were on the other hand less inhibited by these sulfonamides, with inhibition constants in the micromolar range.

  11. Regulation of substituent groups on morphologies and self-assembly of organogels based on some azobenzene imide derivatives

    NASA Astrophysics Data System (ADS)

    Jiao, Tifeng; Wang, Yujin; Zhang, Qingrui; Zhou, Jingxin; Gao, Faming

    2013-04-01

    In this paper, new azobenzene imide derivatives with different substituent groups were designed and synthesized. Their gelation behaviors in 21 solvents were tested as novel low-molecular-mass organic gelators. It was shown that the alkyl substituent chains and headgroups of azobenzene residues in gelators played a crucial role in the gelation behavior of all compounds in various organic solvents. More alkyl chains in molecular skeletons in present gelators are favorable for the gelation of organic solvents. Scanning electron microscopy and atomic force microscopy observations revealed that the gelator molecules self-assemble into different aggregates, from wrinkle, lamella, and belt to fiber with the change of solvents. Spectral studies indicated that there existed different H-bond formations between amide groups and conformations of methyl chains. The present work may give some insight to the design and character of new organogelators and soft materials with special molecular structures.

  12. “Newton’s cradle” proton relay with amide–imidic acid tautomerization in inverting cellulase visualized by neutron crystallography

    PubMed Central

    Nakamura, Akihiko; Ishida, Takuya; Kusaka, Katsuhiro; Yamada, Taro; Fushinobu, Shinya; Tanaka, Ichiro; Kaneko, Satoshi; Ohta, Kazunori; Tanaka, Hiroaki; Inaka, Koji; Higuchi, Yoshiki; Niimura, Nobuo; Samejima, Masahiro; Igarashi, Kiyohiko

    2015-01-01

    Hydrolysis of carbohydrates is a major bioreaction in nature, catalyzed by glycoside hydrolases (GHs). We used neutron diffraction and high-resolution x-ray diffraction analyses to investigate the hydrogen bond network in inverting cellulase PcCel45A, which is an endoglucanase belonging to subfamily C of GH family 45, isolated from the basidiomycete Phanerochaete chrysosporium. Examination of the enzyme and enzyme-ligand structures indicates a key role of multiple tautomerizations of asparagine residues and peptide bonds, which are finally connected to the other catalytic residue via typical side-chain hydrogen bonds, in forming the “Newton’s cradle”–like proton relay pathway of the catalytic cycle. Amide–imidic acid tautomerization of asparagine has not been taken into account in recent molecular dynamics simulations of not only cellulases but also general enzyme catalysis, and it may be necessary to reconsider our interpretation of many enzymatic reactions. PMID:26601228

  13. Composite poly(ethylene oxide) electrolytes plasticized by N-alkyl-N-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide for lithium batteries.

    PubMed

    Wetjen, Morten; Navarra, Maria Assunta; Panero, Stefania; Passerini, Stefano; Scrosati, Bruno; Hassoun, Jusef

    2013-06-01

    We report a new class of quaternary polymer electrolyte membranes that comprise poly(ethylene oxide) (PEO), lithium trifluoromethanesulfonylimide (LiTFSI), N-alkyl-N-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PyrA,4 TFSI) as an ionic liquid, and a SiO₂ filler. The results of differential scanning calorimetry indicate that the addition of SiO₂ and different ionic liquids induces a decrease in the PEO melting enthalpy, which thereby increases the ionic conductivity and the Li transference number. The electrochemical stability is proved by using impedance spectroscopy and cyclic voltammetry. Galvanostatic cycling of Li/LiFePO₄ cells, which comprise the quaternary polymer electrolytes, revealed their superior performance compared to conventional PEO-Li salt electrolytes. In the course of this investigation, a synergistic effect of the combined ionic liquid-ceramic filler modification could be proved at temperatures close to 50 °C.

  14. Cellulose acetate-lithium bis(trifluoromethanesulfonyl)imide solid polymer electrolyte: ATR-FTIR and ionic conductivity behavior

    NASA Astrophysics Data System (ADS)

    Mohd Razalli, Siti Masyitah; Sheikh Mohd Saaid, Siti Irma Yuana; Marwan Ali, Ab Malik; Hassan, Oskar Hasdinor; Yahya, Muhd Zu Azhan

    2015-05-01

    Solid polymer electrolytes (SPEs) based on cellulose acetate (CA) doped with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt are prepared by solution cast technique. Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy of the polymer salt complexes are recorded in the frequency range between 400 cm-1 and 4000 cm-1. The shifting of carbonyl band (C=O) at 1737 cm-1 to a lower wavenumber confirms the occurrence of complexation between the polymer and the salt. The electrochemical impedance spectroscopy (EIS) analysis discovered that the film with 25 wt.% of salt shows the highest ionic conductivity at room temperature. The change in real dielectric permittivity (ɛr) as a function of frequency at different salt concentrations which exhibits a dispersive behavior at low frequencies and decays at higher frequencies, shows the electrode polarization and space charge effect. The real modulus formalism (Mr) analysis shows that the polymer electrolytes in this work are ionic conductors.

  15. "Newton's cradle" proton relay with amide-imidic acid tautomerization in inverting cellulase visualized by neutron crystallography.

    PubMed

    Nakamura, Akihiko; Ishida, Takuya; Kusaka, Katsuhiro; Yamada, Taro; Fushinobu, Shinya; Tanaka, Ichiro; Kaneko, Satoshi; Ohta, Kazunori; Tanaka, Hiroaki; Inaka, Koji; Higuchi, Yoshiki; Niimura, Nobuo; Samejima, Masahiro; Igarashi, Kiyohiko

    2015-08-01

    Hydrolysis of carbohydrates is a major bioreaction in nature, catalyzed by glycoside hydrolases (GHs). We used neutron diffraction and high-resolution x-ray diffraction analyses to investigate the hydrogen bond network in inverting cellulase PcCel45A, which is an endoglucanase belonging to subfamily C of GH family 45, isolated from the basidiomycete Phanerochaete chrysosporium. Examination of the enzyme and enzyme-ligand structures indicates a key role of multiple tautomerizations of asparagine residues and peptide bonds, which are finally connected to the other catalytic residue via typical side-chain hydrogen bonds, in forming the "Newton's cradle"-like proton relay pathway of the catalytic cycle. Amide-imidic acid tautomerization of asparagine has not been taken into account in recent molecular dynamics simulations of not only cellulases but also general enzyme catalysis, and it may be necessary to reconsider our interpretation of many enzymatic reactions.

  16. Microwave-Assisted Synthesis of Defects Metal-Imidazolate-Amide-Imidate Frameworks and Improved CO2 Capture.

    PubMed

    Behrens, Karsten; Mondal, Suvendu Sekhar; Nöske, Robert; Baburin, Igor A; Leoni, Stefano; Günter, Christina; Weber, Jens; Holdt, Hans-Jürgen

    2015-10-19

    In this work, we report three isostructural 3D frameworks, named IFP-11 (R = Cl), IFP-12 (R = Br), and IFP-13 (R = Et) (IFP = Imidazolate Framework Potsdam) based on a cobalt(II) center and the chelating linker 2-substituted imidazolate-4-amide-5-imidate. These chelating ligands were generated in situ by partial hydrolysis of 2-substituted 4,5-dicyanoimidazoles under microwave (MW)-assisted conditions in DMF. Structure determination of these IFPs was investigated by IR spectroscopy and a combination of powder X-ray diffraction (PXRD) with structure modeling. The structural models were initially built up from the single-crystal X-ray structure determination of IFP-5 (a cobalt center and 2-methylimidazolate-4-amide-5-imidate linker based framework) and were optimized by using density functional theory calculations. Substitution on position 2 of the linker (R = Cl, Br, and Et) in the isostructural IFP-11, -12, and -13 allowed variation of the potential pore window in 1D hexagonal channels (3.8 to 1.7 Å). The potential of the materials to undergo specific interactions with CO2 was measured by the isosteric heat of adsorption. Further, we resynthesized zinc based IFPs, namely IFP-1 (R = Me), IFP-2 (R = Cl), IFP-3 (R = Br), and IFP-4 (R = Et), and cobalt based IFP-5 under MW-assisted conditions with higher yield. The transition from a nucleation phase to the pure crystalline material of IFP-1 in MW-assisted synthesis depends on reaction time. IFP-1, -3, and -5, which are synthesized by MW-assisted conditions, showed an enhancement of N2 and CO2, compared to the analogous conventional electrical (CE) heating method based materials due to crystal defects.

  17. The Complex Dance of the Two Conformers of Bis(trifluoromethanesulfonyl)imide as a Function of Pressure and Temperature.

    PubMed

    Capitani, F; Gatto, S; Postorino, P; Palumbo, O; Trequattrini, F; Deutsch, M; Brubach, J-B; Roy, P; Paolone, A

    2016-02-25

    Absorbance spectra of two ionic liquids, the short alkyl chain N-trimethyl-N-propylammonium bis(trifluoromethanesulfonyl)imide (TMPA-TFSI) and the longer chain N-trimethyl-N-hexylammonium bis(trifluoromethanesulfonyl)imide (TMHA-TFSI) are reported as a function of pressure and temperature. The occurrence of various phase transitions is evidenced by the changes in the relative concentration of the cisoid and transoid conformers of their common TFSI anion. The infrared spectrum of TMPA-TFSI was measured at 300 K with an applied pressure varying over the 0-5 GPa range. Above 0.2 GPa only the trans conformer is detected, suggesting the occurrence of a pressure induced crystallization. When pressure is applied to TMHA-TFSI at T = 310 K, both TFSI conformers subsist up to ∼11 GPa. However, the clear change of their intensity ratio observed around 2 GPa, suggests the onset of a glass phase as supported by measurements carried out at 4.2 GPa along a cooling/heating cycle. A careful analysis of the spectra collected along different p-T thermodynamic paths shows the occurrence of a cold crystallization at 295 K on heating from 139 K along the p = 0.5 GPa isobar. The rich phase diagrams of the two ionic liquids is the result of the competition among the anion-cation intermolecular interactions, the lower energy of trans-TFSI with respect to cis-TFSI and the smaller volume of cis-TFSI with respect to trans-TFSI.

  18. Anion conformation of low-viscosity room-temperature ionic liquid 1-ethyl-3-methylimidazolium bis(fluorosulfonyl) imide.

    PubMed

    Fujii, Kenta; Seki, Shiro; Fukuda, Shuhei; Kanzaki, Ryo; Takamuku, Toshiyuki; Umebayashi, Yasuhiro; Ishiguro, Shin-ichi

    2007-11-08

    Anion conformation of a low-viscosity room-temperature ionic liquid 1-ethyl-3-methylimidazolium bis(fluorosulfonyl) imide (EMI+FSI-) has been studied by Raman spectra and theoretical DFT calculations. Three strong Raman bands were found at 293, 328, and 360 cm(-1), which are ascribed to the FSI- ion. These Raman bands show significant temperature dependence, implying that two FSI- conformers coexist in equilibrium. This is supported by theoretical calculations that the FSI- ion is present as either C2 (trans) or C1 (cis) conformer; the former gives the global minimum, and the latter has a higher SCF energy of about 4 kJ mol(-1). Full geometry optimizations followed by normal frequency analyses show that the observed bands at 293, 328, and 360 cm(-1) are ascribed to the C2 conformer. The corresponding vibrations at 305, 320, and 353 cm(-1) were extracted according to deconvolution of the observed Raman bands in the range280-400 cm(-1 )and are ascribed to the C1 conformer. The enthalpy DeltaH degrees of conformational change from C2 to C1 was experimentally evaluated to be ca. 4.5 kJ mol(-1), which is in good agreement with the predicted value by theoretical calculations. The bis(trifluoromethanesulfonyl) imide anion (TFSI-) shows a conformational equilibrium between C1 and C2 analogues (DeltaH degrees = 3.5 kJ mol(-1)). However, the profile of the potential energy surface of the conformational change for FSI- (the F-S-N-S dihedral angle) is significantly different from that for TFSI- (the C-S-N-S dihedral angle).

  19. Enhanced surface segregation of poly(methyl methacrylate) end-capped with 2-perfluorooctylethyl methacrylate by introduction of a second block.

    PubMed

    Ni, Huagang; Gao, Jie; Li, Xuehua; Hu, Yanyan; Yan, Donghuan; Ye, XiuYun; Wang, Xinping

    2012-01-01

    New fluorinated copolymers of poly(methyl methacrylate)-b-poly(butyl methacrylate) or poly(n-octadecyl methacrylate) end-capped with 2-perfluorooctylethyl methacrylate (PMMA(x)-b-PBMA(y)-ec-PFMA(z) or PMMA(x)-b-PODMA(y)-ec-PFMA(z)) were synthesized by living atom transfer radical polymerization. Thin films made of PMMA(230)-b-PODMA(y)-ec-PFMA(1) were characterized by differential scanning calorimetry, angle-resolved X-ray photoelectron spectroscopy and X-ray diffraction. These films were found to exhibit robust surface segregation of the end groups. Furthermore, the fluorine enrichment factor at the film surface was found to increase linearly with increasing degree of polymerization of poly(n-octadecyl methacrylate) and its increasing fusion enthalpy in the second block, which enhances the segregation of the fluorinated moieties.

  20. A strategy for designing a peptide probe for detection of β-amyloid oligomers.

    PubMed

    Hu, Yang; Su, Baihao; Kim, Chung-Sei; Hernandez, Michael; Rostagno, Agueda; Ghiso, Jorge; Kim, Jin Ryoun

    2010-11-22

    Aggregation of β-amyloid (Aβ) is implicated in the pathology of Alzheimer's disease. Development of a robust strategy to detect Aβ oligomeric intermediates, which have been identified as significant toxic agents, would be highly beneficial in the screening of drug candidates as well as enhancing our understanding of Aβ oligomerization. Rapid, specific and quantitative detection, currently unavailable, would be highly preferred for accurate and reliable probing of transient Aβ oligomers. Here, we report the development of a novel peptide probe, PG46, based on the nature of Aβ self-assembly and the conformation-sensitive fluorescence of the biarsenical dye, FlAsH. PG46 was found to bind to Aβ oligomers and displayed an increase in FlAsH fluorescence upon binding. No such event was observed when PG46 was co-incubated with Aβ low-molecular-weight species or Aβ fibrils. Aβ oligomer detection was fast, and occurred within one hour without any additional sample incubation or preparation. We anticipate that the development of a strategy for detection of amyloid oligomers described in this study will be directly relevant to a host of other amyloidogenic proteins.

  1. Methyl-esterified 3-hydroxybutyrate oligomers protect bacteria from hydroxyl radicals.

    PubMed

    Koskimäki, Janne J; Kajula, Marena; Hokkanen, Juho; Ihantola, Emmi-Leena; Kim, Jong H; Hautajärvi, Heidi; Hankala, Elina; Suokas, Marko; Pohjanen, Johanna; Podolich, Olga; Kozyrovska, Natalia; Turpeinen, Ari; Pääkkönen, Mirva; Mattila, Sampo; Campbell, Bruce C; Pirttilä, Anna Maria

    2016-05-01

    Bacteria rely mainly on enzymes, glutathione and other low-molecular weight thiols to overcome oxidative stress. However, hydroxyl radicals are the most cytotoxic reactive oxygen species, and no known enzymatic system exists for their detoxification. We now show that methyl-esterified dimers and trimers of 3-hydroxybutyrate (ME-3HB), produced by bacteria capable of polyhydroxybutyrate biosynthesis, have 3-fold greater hydroxyl radical-scavenging activity than glutathione and 11-fold higher activity than vitamin C or the monomer 3-hydroxybutyric acid. We found that ME-3HB oligomers protect hypersensitive yeast deletion mutants lacking oxidative stress-response genes from hydroxyl radical stress. Our results show that phaC and phaZ, encoding polymerase and depolymerase, respectively, are activated and polyhydroxybutyrate reserves are degraded for production of ME-3HB oligomers in bacteria infecting plant cells and exposed to hydroxyl radical stress. We found that ME-3HB oligomer production is widespread, especially in bacteria adapted to stressful environments. We discuss how ME-3HB oligomers could provide opportunities for numerous applications in human health.

  2. High-resolution NMR characterization of low abundance oligomers of amyloid-β without purification.

    PubMed

    Kotler, Samuel A; Brender, Jeffrey R; Vivekanandan, Subramanian; Suzuki, Yuta; Yamamoto, Kazutoshi; Monette, Martine; Krishnamoorthy, Janarthanan; Walsh, Patrick; Cauble, Meagan; Holl, Mark M Banaszak; Marsh, E Neil G; Ramamoorthy, Ayyalusamy

    2015-07-03

    Alzheimer's disease is characterized by the misfolding and self-assembly of the amyloidogenic protein amyloid-β (Aβ). The aggregation of Aβ leads to diverse oligomeric states, each of which may be potential targets for intervention. Obtaining insight into Aβ oligomers at the atomic level has been a major challenge to most techniques. Here, we use magic angle spinning recoupling (1)H-(1)H NMR experiments to overcome many of these limitations. Using (1)H-(1)H dipolar couplings as a NMR spectral filter to remove both high and low molecular weight species, we provide atomic-level characterization of a non-fibrillar aggregation product of the Aβ1-40 peptide using non-frozen samples without isotopic labeling. Importantly, this spectral filter allows the detection of the specific oligomer signal without a separate purification procedure. In comparison to other solid-state NMR techniques, the experiment is extraordinarily selective and sensitive. A resolved 2D spectra could be acquired of a small population of oligomers (6 micrograms, 7% of the total) amongst a much larger population of monomers and fibers (93% of the total). By coupling real-time (1)H-(1)H NMR experiments with other biophysical measurements, we show that a stable, primarily disordered Aβ1-40 oligomer 5-15 nm in diameter can form and coexist in parallel with the well-known cross-β-sheet fibrils.

  3. A simple procedure for preparing chitin oligomers through acetone precipitation after hydrolysis in concentrated hydrochloric acid.

    PubMed

    Kazami, Nao; Sakaguchi, Masayoshi; Mizutani, Daisuke; Masuda, Tatsuhiko; Wakita, Satoshi; Oyama, Fumitaka; Kawakita, Masao; Sugahara, Yasusato

    2015-11-05

    Chitin oligomers are of interest because of their numerous biologically relevant properties. To prepare chitin oligomers containing 4-6 GlcNAc units [(GlcNAc)4-6], α- and β-chitin were hydrolyzed with concentrated hydrochloric acid at 40 °C. The reactant was mixed with acetone to recover the acetone-insoluble material, and (GlcNAc)4-6 was efficiently recovered after subsequent water extraction. Composition analysis using gel permeation chromatography and MALDI-TOF mass spectrometry indicated that (GlcNAc)4-6 could be isolated from the acetone-insoluble material with recoveries of approximately 17% and 21% from the starting α-chitin and β-chitin, respectively. The acetone precipitation method is highly useful for recovering chitin oligomers from the acid hydrolysate of chitin. The changes in the molecular size and higher-order structure of chitin during the course of hydrolysis were also analyzed, and a model that explains the process of oligomer accumulation is proposed.

  4. A method for the 32P labeling of peptides or peptide nucleic acid oligomers

    NASA Technical Reports Server (NTRS)

    Kozlov, I. A.; Nielsen, P. E.; Orgel, L. E.; Bada, J. L. (Principal Investigator)

    1998-01-01

    A novel approach to the radioactive labeling of peptides and PNA oligomers is described. It is based on the conjugation of a deoxynucleoside 3'-phosphate with the terminal amine of the substrate, followed by phosphorylation of the 5'-hydroxyl group of the nucleotide using T4 polynucleotide kinase and [gamma-32P]ATP.

  5. Efficient synthesis of oxygenated terphenyls and other oligomers: sequential arylation reactions through phenol oxidation-rearomatization.

    PubMed

    Dohi, Toshifumi; Kamitanaka, Tohru; Watanabe, Shohei; Hu, Yinjun; Washimi, Naohiko; Kita, Yasuyuki

    2012-10-22

    One by one: starting from simple phenols, a diverse series of oxygenated terphenyl compounds can be prepared in a concise and practical manner using sequential arylation reactions involving phenol oxidation/rearomatization and quinone monoacetal intermediates. Many of the terphenyl products can be used for preparing well-defined oligomers and, furthermore, contain valuable functional groups that can be transformed for further diversification.

  6. Conformational Flexibility of Soluble Cellulose Oligomers: Chain Length and Temperature Dependence

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Structures, dynamics, and stabilities of different sized cellulosic oligomers need to be considered when designing enzymatic cocktails for the conversion of biomass to biofuels since they can be both productive substrates and inhibitors of the overall process. In the present work, the conformational...

  7. Complement Protein C1q Forms a Complex with Cytotoxic Prion Protein Oligomers

    PubMed Central

    Erlich, Paul; Dumestre-Pérard, Chantal; Ling, Wai Li; Lemaire-Vieille, Catherine; Schoehn, Guy; Arlaud, Gérard J.; Thielens, Nicole M.; Gagnon, Jean; Cesbron, Jean-Yves

    2010-01-01

    A growing number of studies have investigated the interaction between C1q and PrP, but the oligomeric form of PrP involved in this interaction remains to be determined. Aggregation of recombinant full-length murine PrP in the presence of 100 mm NaCl allowed us to isolate three different types of oligomers by size-exclusion chromatography. In contrast to PrP monomers and fibrils, these oligomers activate the classical complement pathway, the smallest species containing 8–15 PrP protomers being the most efficient. We used Thioflavine T fluorescence to monitor PrP aggregation and showed that, when added to the reaction, C1q has a cooperative effect on PrP aggregation and leads to the formation of C1q-PrP complexes. In these complexes, C1q interacts through its globular domains preferentially with the smallest oligomers, as shown by electron microscopy, and retains the ability to activate the classical complement pathway. Using two cell lines, we also provide evidence that C1q inhibits the cytotoxicity induced by the smallest PrP oligomers. The cooperative interaction between C1q and PrP could represent an early step in the disease, where it prevents elimination of the prion seed, leading to further aggregation. PMID:20410306

  8. UV curable lens production using molecular weight controlled PEEK based acrylic oligomer (Ac-PEEK).

    PubMed

    İnan, Tulay Y; Yıldız, Emel; Karaca, Birsen; Dogan, Hacer; Vatansever, Alican; Nalbant, Muhammed; Eken, Koray

    2014-08-01

    We produced UV curable lenses with properties blocking short wave UV light. In the UV-curable formulations, we used an oligomer (Ac-PEEK) with another urethan oligomer (Mw = 2000). Radically active, molecular weight controlled Ac-PEEK was obtained by reacting 2-hydroxyl ethyl methacrylate with molecular- weight- controlled and isocyanate terminated PEEK (Mn = 4500). We characterized all synthesized monomer, oligomer and optical materials with UV/Vis spectrophotometer with interferogram, elemental analyser, mass spectrophotometer, proton nuclear magnetic resonance, Fourier transform infrared spectroscopy, thermal gravimetric analyzer, differential scanning calorimeter, scanning electron microscopy and gas chromatography. Results suggested that newly synthesized oligomer with the structure of PEEK absorbs short wave UV-light. Ageing tests [ISO 11979-5, Ophthalmic implants-intraocular lenses (IOL)-Part 5: Biocompatibility] performed on the IOL materials were successful. High contact angle of the obtained lenses suggests that all lenses were hydrophobic and SEM results revealed that lenses are morphologically homogeneous. Based on all positive properties just mentioned, we safely conclude that the lenses produced in this study are very promising for IOL production.

  9. Structural characterization of toxic oligomers that are kinetically trapped during α-synuclein fibril formation

    PubMed Central

    Chen, Serene W.; Drakulic, Srdja; Deas, Emma; Ouberai, Myriam; Aprile, Francesco A.; Arranz, Rocío; Ness, Samuel; Roodveldt, Cintia; Guilliams, Tim; De-Genst, Erwin J.; Klenerman, David; Wood, Nicholas W.; Knowles, Tuomas P.J.; Alfonso, Carlos; Rivas, Germán; Abramov, Andrey Y.; Valpuesta, José María; Dobson, Christopher M.; Cremades, Nunilo

    2015-01-01

    We describe the isolation and detailed structural characterization of stable toxic oligomers of α-synuclein that have accumulated during the process of amyloid formation. Our approach has allowed us to identify distinct subgroups of oligomers and to probe their molecular architectures by using cryo-electron microscopy (cryoEM) image reconstruction techniques. Although the oligomers exist in a range of sizes, with different extents and nature of β-sheet content and exposed hydrophobicity, they all possess a hollow cylindrical architecture with similarities to certain types of amyloid fibril, suggesting that the accumulation of at least some forms of amyloid oligomers is likely to be a consequence of very slow rates of rearrangement of their β-sheet structures. Our findings reveal the inherent multiplicity of the process of protein misfolding and the key role the β-sheet geometry acquired in the early stages of the self-assembly process plays in dictating the kinetic stability and the pathological nature of individual oligomeric species. PMID:25855634

  10. Structural characterization of toxic oligomers that are kinetically trapped during α-synuclein fibril formation.

    PubMed

    Chen, Serene W; Drakulic, Srdja; Deas, Emma; Ouberai, Myriam; Aprile, Francesco A; Arranz, Rocío; Ness, Samuel; Roodveldt, Cintia; Guilliams, Tim; De-Genst, Erwin J; Klenerman, David; Wood, Nicholas W; Knowles, Tuomas P J; Alfonso, Carlos; Rivas, Germán; Abramov, Andrey Y; Valpuesta, José María; Dobson, Christopher M; Cremades, Nunilo

    2015-04-21

    We describe the isolation and detailed structural characterization of stable toxic oligomers of α-synuclein that have accumulated during the process of amyloid formation. Our approach has allowed us to identify distinct subgroups of oligomers and to probe their molecular architectures by using cryo-electron microscopy (cryoEM) image reconstruction techniques. Although the oligomers exist in a range of sizes, with different extents and nature of β-sheet content and exposed hydrophobicity, they all possess a hollow cylindrical architecture with similarities to certain types of amyloid fibril, suggesting that the accumulation of at least some forms of amyloid oligomers is likely to be a consequence of very slow rates of rearrangement of their β-sheet structures. Our findings reveal the inherent multiplicity of the process of protein misfolding and the key role the β-sheet geometry acquired in the early stages of the self-assembly process plays in dictating the kinetic stability and the pathological nature of individual oligomeric species.

  11. An update on the physiological and therapeutic relevance of GPCR oligomers.

    PubMed

    Farran, Batoul

    2017-03-01

    The traditional view on GPCRs held that they function as single monomeric units composed of identical subunits. This notion was overturned by the discovery that GPCRs can form homo- and hetero-oligomers, some of which are obligatory, and can further assemble into receptor mosaics consisting of three or more protomers. Oligomerisation exerts significant impacts on receptor function and physiology, offering a platform for the diversification of receptor signalling, pharmacology, regulation, crosstalk, internalization and trafficking. Given their involvement in the modulation of crucial physiological processes, heteromers could constitute important therapeutic targets for a wide range of diseases, including schizophrenia, Parkinson's disease, substance abuse or obesity. This review aims at depicting the current developments in GPCR oligomerisation research, documenting various class A, B and C GPCR heteromers detected in vitro and in vivo using biochemical and biophysical approaches, as well as recently identified higher-order oligomeric complexes. It explores the current understanding of dimerization dynamics and the possible interaction interfaces that drive oligomerisation. Most importantly, it provides an inventory of the wide range of physiological processes and pathophysiological conditions to which GPCR oligomers contribute, surveying some of the oligomers that constitute potential drug targets. Finally, it delineates the efforts to develop novel classes of ligands that specifically target and tether to receptor oligomers instead of a single monomeric entity, thus ameliorating their ability to modulate GPCR function.

  12. The Role of Initial Oligomers in Amyloid Fibril Formation by Human Stefin B

    PubMed Central

    Taler-Verčič, Ajda; Kirsipuu, Tiina; Friedemann, Merlin; Noormägi, Andra; Polajnar, Mira; Smirnova, Julia; Žnidarič, Magda Tušek; Žganec, Matjaž; Škarabot, Miha; Vilfan, Andrej; Staniforth, Rosemary A.; Palumaa, Peep; Žerovnik, Eva

    2013-01-01

    Oligomers are commonly observed intermediates at the initial stages of amyloid fibril formation. They are toxic to neurons and cause decrease in neural transmission and long-term potentiation. We describe an in vitro study of the initial steps in amyloid fibril formation by human stefin B, which proved to be a good model system. Due to relative stability of the initial oligomers of stefin B, electrospray ionization mass spectrometry (ESI MS) could be applied in addition to size exclusion chromatography (SEC). These two techniques enabled us to separate and detect distinguished oligomers from the monomers: dimers, trimers, tetramers, up to decamers. The amyloid fibril formation process was followed at different pH and temperatures, including such conditions where the process was slow enough to detect the initial oligomeric species at the very beginning of the lag phase and those at the end of the lag phase. Taking into account the results of the lower-order oligomers transformations early in the process, we were able to propose an improved model for the stefin B fibril formation. PMID:24013380

  13. Studies in the Mineral and Salt-Catalyzed Formation of RNA Oligomers

    NASA Astrophysics Data System (ADS)

    Miyakawa, Shin; Joshi, Prakash C.; Gaffey, Michael J.; Gonzalez-Toril, Elena; Hyland, Callen; Ross, Teresa; Rybij, Kristin; Ferris, James P.

    2006-08-01

    Activated mononucleotides oligomerize in the presence of montmorillonite clay to form RNA oligomers. In the present study, effects of salts, temperature and pH on the clay-catalyzed synthesis of RNA oligomers were investigated. This reaction is favored by relatively high concentration of salts, such as 1 M NaCl. It was shown that the presence of divalent cations was not required for this reaction. High concentrations of NH4 + and HCO3 - and 0.01 M HPO4 2- inhibit the reaction. The yields of RNA oligomers decreased as the temperature was raised from 4 ^∘C to 50 ^∘C. A5' ppA was the major product at pH's below 6. The catalytic activity of a variety of minerals and three meteorites were investigated but none of them except galena catalyzed the oligomerization. ATP was generated from ADP but it was due to the presence of HEPES buffer and not due to the minerals. Meteorites catalyzed the hydrolysis of the pyrophosphate bonds of ATP. The results suggest that oligomers of RNA could have formed in pH 7-9 solutions of alkali metal salts in the presence of montmorillonite clay.

  14. Alzheimer's disease-type neuronal tau hyperphosphorylation induced by Aβ oligomers

    PubMed Central

    De Felice, Fernanda G.; Wu, Diana; Lambert, Mary P.; Fernandez, Sara J.; Velasco, Pauline T.; Lacor, Pascale N.; Bigio, Eileen H.; Jerecic, Jasna; Acton, Paul J.; Shughrue, Paul J.; Chen-Dodson, Elizabeth; Kinney, Gene G.; Klein, William L.

    2008-01-01

    Alzheimer’s disease (AD) is characterized by presence of extracellular fibrillar Aβ in amyloid plaques, intraneuronal neurofibrillary tangles consisting of aggregated hyperphosphorylated tau and elevated brain levels of soluble Aβ oligomers (ADDLs). A major question is how these disparate facets of AD pathology are mechanistically related. Here we show that, independent of the presence of fibrils, ADDLs stimulate tau phosphorylation in mature cultures of hippocampal neurons and in neuroblastoma cells at epitopes characteristically hyperphosphorylated in AD. A monoclonal antibody that targets ADDLs blocked their attachment to synaptic binding sites and prevented tau hyperphosphorylation. Tau phosphorylation was blocked by the Src family tyrosine kinase inhibitor, 4-amino-5-(4-chlorophenyl)-7(t-butyl)pyrazol(3,4-D)pyramide (PP1), and by the phosphatidylinositol-3-kinase inhibitor LY294002. Significantly, tau hyperphosphorylation was also induced by a soluble aqueous extract containing Aβ oligomers from AD brains, but not by an extract from non-AD brains. Aβ oligomers have been increasingly implicated as the main neurotoxins in AD, and the current results provide a unifying mechanism in which oligomer activity is directly linked to tau hyperphosphorylation in AD pathology. PMID:17403556

  15. Enhanced Volatile Organic Compounds emissions and organic aerosol mass increase the oligomer content of atmospheric aerosols.

    PubMed

    Kourtchev, Ivan; Giorio, Chiara; Manninen, Antti; Wilson, Eoin; Mahon, Brendan; Aalto, Juho; Kajos, Maija; Venables, Dean; Ruuskanen, Taina; Levula, Janne; Loponen, Matti; Connors, Sarah; Harris, Neil; Zhao, Defeng; Kiendler-Scharr, Astrid; Mentel, Thomas; Rudich, Yinon; Hallquist, Mattias; Doussin, Jean-Francois; Maenhaut, Willy; Bäck, Jaana; Petäjä, Tuukka; Wenger, John; Kulmala, Markku; Kalberer, Markus

    2016-10-13

    Secondary organic aerosol (SOA) accounts for a dominant fraction of the submicron atmospheric particle mass, but knowledge of the formation, composition and climate effects of SOA is incomplete and limits our understanding of overall aerosol effects in the atmosphere. Organic oligomers were discovered as dominant components in SOA over a decade ago in laboratory experiments and have since been proposed to play a dominant role in many aerosol processes. However, it remains unclear whether oligomers are relevant under ambient atmospheric conditions because they are often not clearly observed in field samples. Here we resolve this long-standing discrepancy by showing that elevated SOA mass is one of the key drivers of oligomer formation in the ambient atmosphere and laboratory experiments. We show for the first time that a specific organic compound class in aerosols, oligomers, is strongly correlated with cloud condensation nuclei (CCN) activities of SOA particles. These findings might have important implications for future climate scenarios where increased temperatures cause higher biogenic volatile organic compound (VOC) emissions, which in turn lead to higher SOA mass formation and significant changes in SOA composition. Such processes would need to be considered in climate models for a realistic representation of future aerosol-climate-biosphere feedbacks.

  16. Allosteric modulation in monomers and oligomers of a G protein-coupled receptor

    PubMed Central

    Shivnaraine, Rabindra V; Kelly, Brendan; Sankar, Krishana S; Redka, Dar'ya S; Han, Yi Rang; Huang, Fei; Elmslie, Gwendolynne; Pinto, Daniel; Li, Yuchong; Rocheleau, Jonathan V; Gradinaru, Claudiu C; Ellis, John; Wells, James W

    2016-01-01

    The M2 muscarinic receptor is the prototypic model of allostery in GPCRs, yet the molecular and the supramolecular determinants of such effects are unknown. Monomers and oligomers of the M2 muscarinic receptor therefore have been compared to identify those allosteric properties that are gained in oligomers. Allosteric interactions were monitored by means of a FRET-based sensor of conformation at the allosteric site and in pharmacological assays involving mutants engineered to preclude intramolecular effects. Electrostatic, steric, and conformational determinants of allostery at the atomic level were examined in molecular dynamics simulations. Allosteric effects in monomers were exclusively negative and derived primarily from intramolecular electrostatic repulsion between the allosteric and orthosteric ligands. Allosteric effects in oligomers could be positive or negative, depending upon the allosteric-orthosteric pair, and they arose from interactions within and between the constituent protomers. The complex behavior of oligomers is characteristic of muscarinic receptors in myocardial preparations. DOI: http://dx.doi.org/10.7554/eLife.11685.001 PMID:27151542

  17. Use of Doubly Charged Precursors to Validate Dissociation Mechanisms of Singly Charged Poly(Dimethylsiloxane) Oligomers

    NASA Astrophysics Data System (ADS)

    Fouquet, Thierry; Toniazzo, Valérie; Ruch, David; Charles, Laurence

    2013-07-01

    Collision-induced dissociation of doubly charged poly(dimethylsiloxane) (PDMS) molecules was investigated to provide experimental evidence for fragmentation reactions proposed to occur upon activation of singly charged oligomers. This study focuses on two PDMS species holding trimethylsilyl or methoxy end-groups and cationized with ammonium. In both cases, introduction of the additional charge did not induce significant differences in dissociation behavior, and the use of doubly charged precursors enabled the occurrence of charge-separation reactions, allowing molecules always eliminated as neutrals upon activation of singly charged oligomers to be detected as cationized species. In the case of trimethylsilyl-terminated oligomers, random location of the adducted charge combined with rapid consecutive reactions proposed to occur from singly charged precursors could be validated based on MS/MS data of doubly charged oligomers. In the case of methoxy-terminated PDMS, favored interaction of the adducted ammonium with both end-groups, proposed to rationalize the dissociation behavior of singly charged molecules, was also supported by MS/MS data obtained for molecules adducted with two ammonium cations.

  18. Stabilizing Off-pathway Oligomers by Polyphenol Nanoassemblies for IAPP Aggregation Inhibition

    NASA Astrophysics Data System (ADS)

    Nedumpully-Govindan, Praveen; Kakinen, Aleksandr; Pilkington, Emily H.; Davis, Thomas P.; Chun Ke, Pu; Ding, Feng

    2016-01-01

    Experimental studies have shown that many naturally occurring polyphenols have inhibitory effect on the aggregation of several proteins. Here, we use discrete molecular dynamics (DMD) simulations and high-throughput dynamic light scattering (DLS) experiments to study the anti-aggregation effects of two polyphenols, curcumin and resveratrol, on the aggregation of islet amyloid polypeptide (IAPP or amylin). Our DMD simulations suggest that the aggregation inhibition is caused by stabilization of small molecular weight IAPP off-pathway oligomers by the polyphenols. Our analysis indicates that IAPP-polyphenol hydrogen bonds and π-π stacking combined with hydrophobic interactions are responsible for the stabilization of oligomers. The presence of small oligomers is confirmed with DLS measurements in which nanometer-sized oligomers are found to be stable for up to 7.5 hours, the time frame within which IAPP aggregates in the absence of polyphenols. Our study offers a general anti-aggregation mechanism for polyphenols, and further provides a computational framework for the future design of anti-amyloid aggregation therapeutics.

  19. Chemical evolution. XXII - The hydantoins released on hydrolysis of HCN oligomers

    NASA Technical Reports Server (NTRS)

    Ferris, J. P.; Wos, J. D.; Lobo, A. P.

    1974-01-01

    The isolation of three hydantoins from HCN oligomers is described. One of these hydantoins, 5-carboxymethylidine hydantoin (5-CMH), rearranges to pyrimidine orotic acid in basic solution. The isolation of 5-CMH suggests the possibility that pyrimidines were formed directly from HCN on the primitive earth.

  20. WASP-1, a canonical Wnt signaling potentiator, rescues hippocampal synaptic impairments induced by Aβ oligomers.

    PubMed

    Vargas, Jessica Y; Ahumada, Juan; Arrázola, Macarena S; Fuenzalida, Marco; Inestrosa, Nibaldo C

    2015-02-01

    Amyloid-β (Aβ) oligomers are a key factor in Alzheimer's disease (AD)-associated synaptic dysfunction. Aβ oligomers block the induction of hippocampal long-term potentiation (LTP) in rodents. The activation of Wnt signaling prevents Aβ oligomer-induced neurotoxic effects. The compound WASP-1 (Wnt-activating small molecule potentiator-1), has been described as a synergist of the ligand Wnt-3a, enhancing the activation of Wnt/β-catenin signaling. Herein, we report that WASP-1 administration successfully rescued Aβ-induced synaptic impairments both in vitro and in vivo. The activation of canonical Wnt/β-catenin signaling by WASP-1 increased synaptic transmission and rescued hippocampal LTP impairments induced by Aβ oligomers. Additionally, intra-hippocampal administration of WASP-1 to the double transgenic APPswe/PS1dE9 mouse model of AD prevented synaptic protein loss and reduced tau phosphorylation levels. Moreover, we found that WASP-1 blocked Aβ aggregation in vitro and reduced pathological tau phosphorylation in vivo. These results indicate that targeting canonical Wnt signaling with WASP-1 could have value for treating AD.

  1. Enhanced Volatile Organic Compounds emissions and organic aerosol mass increase the oligomer content of atmospheric aerosols

    NASA Astrophysics Data System (ADS)

    Kourtchev, Ivan; Giorio, Chiara; Manninen, Antti; Wilson, Eoin; Mahon, Brendan; Aalto, Juho; Kajos, Maija; Venables, Dean; Ruuskanen, Taina; Levula, Janne; Loponen, Matti; Connors, Sarah; Harris, Neil; Zhao, Defeng; Kiendler-Scharr, Astrid; Mentel, Thomas; Rudich, Yinon; Hallquist, Mattias; Doussin, Jean-Francois; Maenhaut, Willy; Bäck, Jaana; Petäjä, Tuukka; Wenger, John; Kulmala, Markku; Kalberer, Markus

    2016-10-01

    Secondary organic aerosol (SOA) accounts for a dominant fraction of the submicron atmospheric particle mass, but knowledge of the formation, composition and climate effects of SOA is incomplete and limits our understanding of overall aerosol effects in the atmosphere. Organic oligomers were discovered as dominant components in SOA over a decade ago in laboratory experiments and have since been proposed to play a dominant role in many aerosol processes. However, it remains unclear whether oligomers are relevant under ambient atmospheric conditions because they are often not clearly observed in field samples. Here we resolve this long-standing discrepancy by showing that elevated SOA mass is one of the key drivers of oligomer formation in the ambient atmosphere and laboratory experiments. We show for the first time that a specific organic compound class in aerosols, oligomers, is strongly correlated with cloud condensation nuclei (CCN) activities of SOA particles. These findings might have important implications for future climate scenarios where increased temperatures cause higher biogenic volatile organic compound (VOC) emissions, which in turn lead to higher SOA mass formation and significant changes in SOA composition. Such processes would need to be considered in climate models for a realistic representation of future aerosol-climate-biosphere feedbacks.

  2. Student-Driven Design of Peptide Mimetics: Microwave-Assisted Synthesis of Peptoid Oligomers

    ERIC Educational Resources Information Center

    Pohl, Nicola L. B.; Kirshenbaum, Kent; Yoo, Barney; Schulz, Nathan; Zea, Corbin J.; Streff, Jennifer M.; Schwarz, Kimberly L.

    2011-01-01

    An experiment for the undergraduate organic laboratory is described in which peptide mimetic oligomers called "peptoids" are built stepwise on a solid-phase resin. Students employ two modern strategies to facilitate rapid multistep syntheses: solid-phase techniques to obviate the need for intermediate purifications and microwave irradiation to…

  3. Rapid Multistep Synthesis of a Bioactive Peptidomimetic Oligomer for the Undergraduate Laboratory

    ERIC Educational Resources Information Center

    Utku, Yeliz; Rohatgi, Abhinav; Yoo, Barney; Kirshenbaum, Kent; Zuckermann, Ronald N.; Pohl, Nicola L.

    2010-01-01

    Peptidomimetic compounds are increasingly important in drug-discovery applications. We introduce the synthesis of an N-substituted glycine oligomer, a bioactive "peptoid" trimer. The six-step protocol is conducted on solid-phase resin, enabling the synthesis to be performed by undergraduate organic chemistry students. This synthesis lab was…

  4. Synthesis and Properties of Bis(aniline, methyl)siloxy-octaphenylsilsesquioxane Modified Thermosetting Polyimide Oligomers

    DTIC Science & Technology

    2011-08-19

    Conference Paper 3. DATES COVERED (From - To) 4. TITLE AND SUBTITLE 5a. CONTRACT NUMBER Synthesis and Properties of Bis( aniline , methyl)siloxy...SYNTHESIS AND PROPERTIES OF BIS( ANILINE , METHYL)SILOXY-OCTAPHENYLSILSESQUIOXANE MODIFIED THERMOSETTING POLYIMIDE OLIGOMERS Gregory R. Yandek1...oxydiphenylene aniline (Kapton™) reduced its moisture uptake by 83% concurrently improving mechanical properties.4 The objective of this work is to

  5. Stabilizing Off-pathway Oligomers by Polyphenol Nanoassemblies for IAPP Aggregation Inhibition

    PubMed Central

    Nedumpully-Govindan, Praveen; Kakinen, Aleksandr; Pilkington, Emily H.; Davis, Thomas P.; Chun Ke, Pu; Ding, Feng

    2016-01-01

    Experimental studies have shown that many naturally occurring polyphenols have inhibitory effect on the aggregation of several proteins. Here, we use discrete molecular dynamics (DMD) simulations and high-throughput dynamic light scattering (DLS) experiments to study the anti-aggregation effects of two polyphenols, curcumin and resveratrol, on the aggregation of islet amyloid polypeptide (IAPP or amylin). Our DMD simulations suggest that the aggregation inhibition is caused by stabilization of small molecular weight IAPP off-pathway oligomers by the polyphenols. Our analysis indicates that IAPP-polyphenol hydrogen bonds and π-π stacking combined with hydrophobic interactions are responsible for the stabilization of oligomers. The presence of small oligomers is confirmed with DLS measurements in which nanometer-sized oligomers are found to be stable for up to 7.5 hours, the time frame within which IAPP aggregates in the absence of polyphenols. Our study offers a general anti-aggregation mechanism for polyphenols, and further provides a computational framework for the future design of anti-amyloid aggregation therapeutics. PMID:26763863

  6. Optimization of the All-D Peptide D3 for Aβ Oligomer Elimination.

    PubMed

    Klein, Antonia Nicole; Ziehm, Tamar; Tusche, Markus; Buitenhuis, Johan; Bartnik, Dirk; Boeddrich, Annett; Wiglenda, Thomas; Wanker, Erich; Funke, Susanne Aileen; Brener, Oleksandr; Gremer, Lothar; Kutzsche, Janine; Willbold, Dieter

    2016-01-01

    The aggregation of amyloid-β (Aβ) is postulated to be the crucial event in Alzheimer's disease (AD). In particular, small neurotoxic Aβ oligomers are considered to be responsible for the development and progression of AD. Therefore, elimination of thesis oligomers represents a potential causal therapy of AD. Starting from the well-characterized d-enantiomeric peptide D3, we identified D3 derivatives that bind monomeric Aβ. The underlying hypothesis is that ligands bind monomeric Aβ and stabilize these species within the various equilibria with Aβ assemblies, leading ultimately to the elimination of Aβ oligomers. One of the hereby identified d-peptides, DB3, and a head-to-tail tandem of DB3, DB3DB3, were studied in detail. Both peptides were found to: (i) inhibit the formation of Thioflavin T-positive fibrils; (ii) bind to Aβ monomers with micromolar affinities; (iii) eliminate Aβ oligomers; (iv) reduce Aβ-induced cytotoxicity; and (v) disassemble preformed Aβ aggregates. The beneficial effects of DB3 were improved by DB3DB3, which showed highly enhanced efficacy. Our approach yielded Aβ monomer-stabilizing ligands that can be investigated as a suitable therapeutic strategy against AD.

  7. The Volumetric Diversity of Misfolded Prion Protein Oligomers Revealed by Pressure Dissociation*

    PubMed Central

    Torrent, Joan; Lange, Reinhard; Rezaei, Human

    2015-01-01

    Protein oligomerization has been associated with a wide range of diseases. High pressure approaches offer a powerful tool for deciphering the underlying molecular mechanisms by revealing volume changes associated with the misfolding and assembly reactions. We applied high pressure to induce conformational changes in three distinct β-sheet-rich oligomers of the prion protein PrP, a protein characterized by a variety of infectious quaternary structures that can propagate stably and faithfully and cause diseases with specific phenotypic traits. We show that pressure induces dissociation of the oligomers and leads to a lower volume monomeric PrP state that refolds into the native conformation after pressure release. By measuring the different pressure and temperature sensitivity of the tested PrP oligomers, we demonstrate significantly different void volumes in their quaternary structure. In addition, by focusing on the kinetic and energetic behavior of the pressure-induced dissociation of one specific PrP oligomer, we reveal a large negative activation volume and an increase in both apparent activation enthalpy and entropy. This suggests a transition state ensemble that is less structured and significantly more hydrated than the oligomeric state. Finally, we found that site-specific fluorescent labeling allows monitoring of the transient population of a kinetic intermediate in the dissociation reaction. Our results indicate that defects in atomic packing may deserve consideration as a new factor that influences differences between PrP assemblies and that could be relevant also for explaining the origin of prion strains. PMID:26126829

  8. Enhanced Volatile Organic Compounds emissions and organic aerosol mass increase the oligomer content of atmospheric aerosols

    PubMed Central

    Kourtchev, Ivan; Giorio, Chiara; Manninen, Antti; Wilson, Eoin; Mahon, Brendan; Aalto, Juho; Kajos, Maija; Venables, Dean; Ruuskanen, Taina; Levula, Janne; Loponen, Matti; Connors, Sarah; Harris, Neil; Zhao, Defeng; Kiendler-Scharr, Astrid; Mentel, Thomas; Rudich, Yinon; Hallquist, Mattias; Doussin, Jean-Francois; Maenhaut, Willy; Bäck, Jaana; Petäjä, Tuukka; Wenger, John; Kulmala, Markku; Kalberer, Markus

    2016-01-01

    Secondary organic aerosol (SOA) accounts for a dominant fraction of the submicron atmospheric particle mass, but knowledge of the formation, composition and climate effects of SOA is incomplete and limits our understanding of overall aerosol effects in the atmosphere. Organic oligomers were discovered as dominant components in SOA over a decade ago in laboratory experiments and have since been proposed to play a dominant role in many aerosol processes. However, it remains unclear whether oligomers are relevant under ambient atmospheric conditions because they are often not clearly observed in field samples. Here we resolve this long-standing discrepancy by showing that elevated SOA mass is one of the key drivers of oligomer formation in the ambient atmosphere and laboratory experiments. We show for the first time that a specific organic compound class in aerosols, oligomers, is strongly correlated with cloud condensation nuclei (CCN) activities of SOA particles. These findings might have important implications for future climate scenarios where increased temperatures cause higher biogenic volatile organic compound (VOC) emissions, which in turn lead to higher SOA mass formation and significant changes in SOA composition. Such processes would need to be considered in climate models for a realistic representation of future aerosol-climate-biosphere feedbacks. PMID:27733773

  9. Secondary Ion Mass Spectrometry of Zeolite Materials: Observation of Abundant Aluminosilicate Oligomers Using an Ion Trap

    SciTech Connect

    Groenewold, Gary Steven; Kessinger, Glen Frank; Scott, Jill Rennee; Gianotto, Anita Kay; Appelhans, Anthony David; Delmore, James Edward

    2000-12-01

    Oligomeric oxyanions were observed in the secondary ion mass spectra (SIMS) of zeolite materials. The oxyanions have the general composition AlmSinO2(m+n)H(m-1)- (m + n = 2 to 8) and are termed dehydrates. For a given mass, multiple elemental compositions are possible because (Al + H) is an isovalent and isobaric substitute for Si. Using 18 keV Ga+ as a projectile, oligomer abundances are low relative to the monomers. Oligomer abundance can be increased by using the polyatomic projectile ReO4- (~5 keV). Oligomer abundance can be further increased using an ion trap (IT-) SIMS; in this instrument, long ion lifetimes (tens of ms) and relatively high He pressure result in significant collisional stabilization and increased high-mass abundance. The dehydrates rapidly react with adventitious H2O present in the IT-SIMS to form mono-, di-, and trihydrates. The rapidity of the reaction and comparison to aluminum oxyanion hydration suggest that H2O adds to the aluminosilicate oxyanions in a dissociative fashion, forming covalently bound product ions. In addition to these findings, it was noted that production of abundant oligomeric aluminosilicates could be significantly increased by substituting the countercation (NH4+) with the larger alkali ions Rb+ and Cs+. This constitutes a useful tactic for generating large aluminosilicate oligomers for surface characterization and ion-molecule reactivity studies.

  10. DOPAL derived alpha-synuclein oligomers impair synaptic vesicles physiological function

    PubMed Central

    Plotegher, N.; Berti, G.; Ferrari, E.; Tessari, I.; Zanetti, M.; Lunelli, L.; Greggio, E.; Bisaglia, M.; Veronesi, M.; Girotto, S.; Dalla Serra, M.; Perego, C.; Casella, L.; Bubacco, L.

    2017-01-01

    Parkinson’s disease is a neurodegenerative disorder characterized by the death of dopaminergic neurons and by accumulation of alpha-synuclein (aS) aggregates in the surviving neurons. The dopamine catabolite 3,4-dihydroxyphenylacetaldehyde (DOPAL) is a highly reactive and toxic molecule that leads to aS oligomerization by covalent modifications to lysine residues. Here we show that DOPAL-induced aS oligomer formation in neurons is associated with damage of synaptic vesicles, and with alterations in the synaptic vesicles pools. To investigate the molecular mechanism that leads to synaptic impairment, we first aimed to characterize the biochemical and biophysical properties of the aS-DOPAL oligomers; heterogeneous ensembles of macromolecules able to permeabilise cholesterol-containing lipid membranes. aS-DOPAL oligomers can induce dopamine leak in an in vitro model of synaptic vesicles and in cellular models. The dopamine released, after conversion to DOPAL in the cytoplasm, could trigger a noxious cycle that further fuels the formation of aS-DOPAL oligomers, inducing neurodegeneration. PMID:28084443

  11. Synthesis of a new π-conjugated redox oligomer: Electrochemical and optical investigation

    NASA Astrophysics Data System (ADS)

    Blili, Saber; Zaâboub, Zouhour; Maaref, Hassen; Haj Said, Ayoub

    2017-01-01

    A new π-conjugated redox oligomer was prepared according a two-Step Synthesis. Firstly, an oligophenylene (OMPA) was obtained from the anodic oxidation of the (4-methoxyphenyl)acetonitrile. Then, the resulting material was chemically modified by the Knoevenagel condensation with the ferrocenecarboxaldehyde. This reaction led to a redox-conjugated oligomer the Fc-OMPA. The synthesized material was characterized using different spectroscopic techniques: NMR, FTIR, UV-vis and photoluminescence (PL) spectroscopy. The Fc-OMPA was used to modify a platinum electrode surface and the electrochemical response of the ferrocene redox-center was investigated by cyclic voltammetry. Moreover, the room temperature PL spectra of Fc-OMPA revealed that the ferrocene moiety, which acts as an electron donor, can effectively quench the oligomer luminescence. However, when ferrocene was oxidized to ferrocenium ion, the intramolecular charge transfer process was prevented which consequently enhanced the light emission. Thus, the oligomer light-emission can be, chemically or electrochemically tuned. The obtained results showed that the prepared material is a good candidate for the elaboration of electrochemical sensors and for the development of luminescent Redox-switchable devices.

  12. Structural Insights into Amyloid Oligomers of the Parkinson Disease-related Protein α-Synuclein*

    PubMed Central

    Gallea, J. Ignacio; Celej, M. Soledad

    2014-01-01

    The presence of intraneuronal deposits mainly formed by amyloid fibrils of the presynaptic protein α-synuclein (AS) is a hallmark of Parkinson disease. Currently, neurotoxicity is attributed to prefibrillar oligomeric species rather than the insoluble aggregates, although their mechanisms of toxicity remain elusive. Structural details of the supramolecular organization of AS oligomers are critically needed to decipher the structure-toxicity relationship underlying their pathogenicity. In this study, we employed site-specific fluorescence to get a deeper insight into the internal architecture of AS oligomeric intermediates. We demonstrate that AS oligomers are ordered assemblies possessing a well defined pattern of intermolecular contacts. Some of these contacts involve regions that form the β-sheet core in the fibrillar state, although their spatial arrangement may differ in the two aggregated forms. However, even though the two termini are excluded from the fibrillar core, they are engaged in a number of intermolecular interactions within the oligomer. Therefore, substantial structural remodeling of early oligomeric interactions is essential for fibril growth. The intermolecular contacts identified in AS oligomers can serve as targets for the rational design of anti-amyloid compounds directed at preventing oligomeric interactions/reorganizations. PMID:25143382

  13. Glycan arrays containing synthetic Clostridium difficile lipoteichoic acid oligomers as tools toward a carbohydrate vaccine.

    PubMed

    Martin, Christopher E; Broecker, Felix; Eller, Steffen; Oberli, Matthias A; Anish, Chakkumkal; Pereira, Claney L; Seeberger, Peter H

    2013-08-18

    Clostridium difficile is a leading cause of severe nosocomial infections. Cell-surface carbohydrate antigens are promising vaccine candidates. Here we report the first total synthesis of oligomers of the lipoteichoic acid antigen repeating unit. Synthetic glycan microarrays revealed anti-glycan antibodies in the blood of patients that help to define epitopes for vaccine development.

  14. Facile Synthesis of Highly Crystalline and Large Areal Hexagonal Boron Nitride from Borazine Oligomers

    NASA Astrophysics Data System (ADS)

    Park, Sungchan; Seo, Tae Hoon; Cho, Hyunjin; Min, Kyung Hyun; Lee, Dong Su; Won, Dong-Il; Kang, Sang Ook; Kim, Myung Jong

    2017-01-01

    A novel and facile synthetic method for h-BN films from borazine oligomer (B3N3H4)x precursors has been developed. This method only includes spin-coating of borazine oligomer onto nickel catalysts and a subsequent annealing step. Large areal and highly crystalline h-BN films were obtained. The stoichiometric B/N ratio of borazine oligomer precursor was preserved in the final h-BN product such that it was close to 1 as revealed by XPS. Catalytic effect of nickel for h-BN formation was clearly demonstrated by lowering crystallization temperature compared to the growth condition in the absence of catalyst. The graphene field effect transistor (GFET) characterization has proved the high quality synthesis of h-BN films, showing the shift of neutrality point and the increase of the mobility. This method can also provide functional h-BN coating on various surfaces by annealing Ni-coated borazine oligomer films and subsequent removal of Ni catalyst.

  15. High-Capacity Conductive Nanocellulose Paper Sheets for Electrochemically Controlled Extraction of DNA Oligomers

    PubMed Central

    Razaq, Aamir; Nyström, Gustav; Strømme, Maria; Mihranyan, Albert; Nyholm, Leif

    2011-01-01

    Highly porous polypyrrole (PPy)-nanocellulose paper sheets have been evaluated as inexpensive and disposable electrochemically controlled three-dimensional solid phase extraction materials. The composites, which had a total anion exchange capacity of about 1.1 mol kg−1, were used for extraction and subsequent release of negatively charged fluorophore tagged DNA oligomers via galvanostatic oxidation and reduction of a 30–50 nm conformal PPy layer on the cellulose substrate. The ion exchange capacity, which was, at least, two orders of magnitude higher than those previously reached in electrochemically controlled extraction, originated from the high surface area (i.e. 80 m2 g−1) of the porous composites and the thin PPy layer which ensured excellent access to the ion exchange material. This enabled the extractions to be carried out faster and with better control of the PPy charge than with previously employed approaches. Experiments in equimolar mixtures of (dT)6, (dT)20, and (dT)40 DNA oligomers showed that all oligomers could be extracted, and that the smallest oligomer was preferentially released with an efficiency of up to 40% during the reduction of the PPy layer. These results indicate that the present material is very promising for the development of inexpensive and efficient electrochemically controlled ion-exchange membranes for batch-wise extraction of biomolecules. PMID:22195031

  16. Synthesis of DNA mimics representing HypNA-pPNA hetero-oligomers.

    PubMed

    Efimov, Vladimir A; Chakhmakhcheva, Oksana G

    2005-01-01

    The methods for the synthesis and purification of negatively charged peptide nucleic acid (PNA)-relative deoxyribonucleic acid (DNA) mimics containing alternating residues of phosphono peptide nucleic acid (pPNA) monomers and PNA-like monomers on the base of trans-4-hydroxy-L-proline are described. Examples of the chimeric oligomers hybridization with complementary DNA and ribonucleic acid fragments are demonstrated.

  17. Facile Synthesis of Highly Crystalline and Large Areal Hexagonal Boron Nitride from Borazine Oligomers

    PubMed Central

    Park, Sungchan; Seo, Tae Hoon; Cho, Hyunjin; Min, Kyung Hyun; Lee, Dong Su; Won, Dong-Il; Kang, Sang Ook; Kim, Myung Jong

    2017-01-01

    A novel and facile synthetic method for h-BN films from borazine oligomer (B3N3H4)x precursors has been developed. This method only includes spin-coating of borazine oligomer onto nickel catalysts and a subsequent annealing step. Large areal and highly crystalline h-BN films were obtained. The stoichiometric B/N ratio of borazine oligomer precursor was preserved in the final h-BN product such that it was close to 1 as revealed by XPS. Catalytic effect of nickel for h-BN formation was clearly demonstrated by lowering crystallization temperature compared to the growth condition in the absence of catalyst. The graphene field effect transistor (GFET) characterization has proved the high quality synthesis of h-BN films, showing the shift of neutrality point and the increase of the mobility. This method can also provide functional h-BN coating on various surfaces by annealing Ni-coated borazine oligomer films and subsequent removal of Ni catalyst. PMID:28074854

  18. High-resolution NMR characterization of low abundance oligomers of amyloid-β without purification

    NASA Astrophysics Data System (ADS)

    Kotler, Samuel A.; Brender, Jeffrey R.; Vivekanandan, Subramanian; Suzuki, Yuta; Yamamoto, Kazutoshi; Monette, Martine; Krishnamoorthy, Janarthanan; Walsh, Patrick; Cauble, Meagan; Holl, Mark M. Banaszak; Marsh, E. Neil. G.; Ramamoorthy, Ayyalusamy

    2015-07-01

    Alzheimer’s disease is characterized by the misfolding and self-assembly of the amyloidogenic protein amyloid-β (Aβ). The aggregation of Aβ leads to diverse oligomeric states, each of which may be potential targets for intervention. Obtaining insight into Aβ oligomers at the atomic level has been a major challenge to most techniques. Here, we use magic angle spinning recoupling 1H-1H NMR experiments to overcome many of these limitations. Using 1H-1H dipolar couplings as a NMR spectral filter to remove both high and low molecular weight species, we provide atomic-level characterization of a non-fibrillar aggregation product of the Aβ1-40 peptide using non-frozen samples without isotopic labeling. Importantly, this spectral filter allows the detection of the specific oligomer signal without a separate purification procedure. In comparison to other solid-state NMR techniques, the experiment is extraordinarily selective and sensitive. A resolved 2D spectra could be acquired of a small population of oligomers (6 micrograms, 7% of the total) amongst a much larger population of monomers and fibers (93% of the total). By coupling real-time 1H-1H NMR experiments with other biophysical measurements, we show that a stable, primarily disordered Aβ1-40 oligomer 5-15 nm in diameter can form and coexist in parallel with the well-known cross-β-sheet fibrils.

  19. Oligomer formation during gas-phase ozonolysis of small alkenes and enol ethers: new evidence for the central role of the Criegee Intermediate as oligomer chain unit

    NASA Astrophysics Data System (ADS)

    Sadezky, A.; Winterhalter, R.; Kanawati, B.; Römpp, A.; Spengler, B.; Mellouki, A.; Le Bras, G.; Chaimbault, P.; Moortgat, G. K.

    2008-05-01

    An important fraction of secondary organic aerosol (SOA) formed by atmospheric oxidation of diverse volatile organic compounds (VOC) has recently been shown to consist of high-molecular weight oligomeric species. In our previous study (Sadezky et al., 2006), we reported the identification and characterization of oligomers as main constituents of SOA from gas-phase ozonolysis of small enol ethers. These oligomers contained repeated chain units of the same chemical composition as the main Criegee Intermediates (CI) formed during the ozonolysis reaction, which were CH2O2 (mass 46) for alkyl vinyl ethers (AVE) and C2H4O2 (mass 60) for ethyl propenyl ether (EPE). In the present work, we extend our previous study to another enol ether (ethyl butenyl ether EBE) and a variety of structurally related small alkenes (trans-3-hexene, trans-4-octene and 2,3-dimethyl-2-butene). Experiments have been carried out in a 570 l spherical glass reactor at atmospheric conditions in the absence of seed aerosol. SOA formation was measured by a scanning mobility particle sizer (SMPS). SOA filter samples were collected and chemically characterized off-line by ESI(+)/TOF MS and ESI(+)/TOF MS/MS, and elemental compositions were determined by ESI(+)/FTICR MS and ESI(+)/FTICR MS/MS. The results for all investigated unsaturated compounds are in excellent agreement with the observations of our previous study. Analysis of the collected SOA filter samples reveal the presence of oligomeric compounds in the mass range 200 to 800 u as major constituents. The repeated chain units of these oligomers are shown to systematically have the same chemical composition as the respective main Criegee Intermediate (CI) formed during ozonolysis of the unsaturated compounds, which is C3H6O2 (mass 74) for ethyl butenyl ether (EBE), trans-3-hexene, and 2,3-dimethyl-2-butene, and C4H8O2 (mass 88) for trans-4-octene. Analogous fragmentation pathways among the oligomers formed by gas-phase ozonolysis of the different

  20. Synthesis and characterization of aryl phosphine oxide containing thermoplastic polyimides and thermosetting polyimides with controlled reactivity

    NASA Astrophysics Data System (ADS)

    Zhuang, Hong

    1998-11-01

    Phosphorus containing monomers, bis(3-aminophenyl)methyl phosphine oxide (m-DAMPO) and bis(3-aminophenyl)phenyl phosphine oxide (m-DAPPO), were synthesized and incorporated into a thermoplastic poly(arylene ether imide) based upon 2,2sp'-bis (4-(3,4-dicarboxyphenoxy)phenyl) propane dianhydride and 1,3-phenylene diamine, in order to study their influence on flame resistance and other properties. DAMPO or DAPPO were quantitatively incorporated in concentrations of 25, 50, 75 and 100 mole percent, using the "one pot" ester-acid method. The number average molecular weights of the prepared materials were controlled to 20,000g/mol by off-setting the stoichiometry and endcapping with phthalic anhydride. This strategy enabled one to distinguish the effects of the phosphine oxide incorporation from the influence of molecular weight. The resulting copolymers demonstrated a significant increase in char yield as a function of the phosphine oxide content, thus suggesting improved fire resistance. Glass transition temperatures similar to the control were determined by DSC analysis. Analysis of the mechanical behavior of the DAMPO system at room temperature showed that tensile strength and elongation at failure values were comparable to the control system, while the DAPPO containing copolymers were surprisingly brittle. The influence of the reactive endgroup on the synthesis, cure behavior and network properties of thermosetting polyetherimides was investigated. Reactive phenylacetylene, acetylene and maleimide terminated poly(ether imide) oligomers were prepared and characterized. Optimal reaction conditions were established to produce fully endcapped oligomers with imidized structures and controlled molecular weight. The phenylacetylene endcapped system was synthesized by a conventional ester-acid method. The acetylene endcapped system was prepared via modified ester-acid method and the maleimide endcapped system was fabricated utilizing an amic-acid route. It was determined

  1. Novel chemo-enzymatic oligomers of cinnamic acids as direct and indirect inhibitors of coagulation proteinases.

    PubMed

    Monien, Bernhard H; Henry, Brian L; Raghuraman, Arjun; Hindle, Michael; Desai, Umesh R

    2006-12-01

    Thrombin and factor Xa, two important procoagulant enzymes, have been prime targets for regulation of clotting through the direct and indirect mechanism of inhibition. Our efforts on exploiting the indirect mechanism led us to study a carboxylic acid-based scaffold, which displayed major acceleration in the inhibition of these enzymes [J. Med. Chem.2005, 48, 1269, 5360]. This work advances the study to chemo-enzymatically prepared oligomers of 4-hydroxycinnamic acids, DHPs, which display interesting anticoagulant properties. Oligomers, ranging in size from tetramers to pentadecamers, were prepared through peroxidase-catalyzed oxidative coupling of caffeic, ferulic, and sinapic acids, and sulfated using triethylamine-sulfur trioxide complex. Chromatographic, spectroscopic, and elemental studies suggest that the DHPs are heterogeneous, polydisperse preparations composed of inter-monomer linkages similar to those found in natural lignins. Measurement of activated thromboplastin and prothrombin time indicates that both the sulfated and unsulfated derivatives of the DHPs display anticoagulant activity, which is dramatically higher than that of the reference polyacrylic acids. More interestingly, this activity approaches that of low-molecular-weight heparin with the sulfated derivative showing approximately 2- to 3-fold greater potency than the unsulfated parent. Studies on the inhibition of factor Xa and thrombin indicate that the oligomers exert their anticoagulant effect through both direct and indirect inhibition mechanisms. This dual inhibition property of 4-hydroxycinnamic acid-based DHP oligomers is the first example in inhibitors of coagulation. This work puts forward a novel, non-heparin structure, which may be exploited for the design of potent, dual action inhibitors of coagulation through combinatorial virtual screening on a library of DHP oligomers.

  2. PrPSc-Specific Antibodies with the Ability to Immunodetect Prion Oligomers

    PubMed Central

    Tayebi, Mourad; Jones, Daryl Rhys; Taylor, William Alexander; Stileman, Benjamin Frederick; Chapman, Charlotte; Zhao, Deming; David, Monique

    2011-01-01

    The development of antibodies with binding capacity towards soluble oligomeric forms of PrPSc recognised in the aggregation process in early stage of the disease would be of paramount importance in diagnosing prion diseases before extensive neuropathology has ensued. As blood transfusion appears to be efficient in the transmission of the infectious prion agent, there is an urgent need to develop reagents that would specifically recognize oligomeric forms of the abnormally folded prion protein, PrPSc. To that end, we show that anti-PrP monoclonal antibodies (called PRIOC mAbs) derived from mice immunised with native PrP-coated microbeads are able to immunodetect oligomers/multimers of PrPSc. Oligomer-specific immunoreactivity displayed by these PRIOC mAbs was demonstrated as large aggregates of immunoreactive deposits in prion-permissive neuroblastoma cell lines but not in equivalent non-infected or prn-p0/0 cell lines. In contrast, an anti-monomer PrP antibody displayed diffuse immunoreactivity restricted to the cell membrane. Furthermore, our PRIOC mAbs did not display any binding with monomeric recombinant and cellular prion proteins but strongly detected PrPSc oligomers as shown by a newly developed sensitive and specific ELISA. Finally, PrioC antibodies were also able to bind soluble oligomers formed of Aβ and α-synuclein. These findings demonstrate the potential use of anti-prion antibodies that bind PrPSc oligomers, recognised in early stage of the disease, for the diagnosis of prion diseases in blood and other body fluids. PMID:21625515

  3. Postsynaptic Receptors for Amyloid-β Oligomers as Mediators of Neuronal Damage in Alzheimer's Disease.

    PubMed

    Dinamarca, Margarita C; Ríos, Juvenal A; Inestrosa, Nibaldo C

    2012-01-01

    The neurotoxic effect of amyloid-β peptide (Aβ) over the central synapses has been described and is reflected in the decrease of some postsynaptic excitatory proteins, the alteration in the number and morphology of the dendritic spines, and a decrease in long-term potentiation. Many studies has been carried out to identify the putative Aβ receptors in neurons, and is still no clear why the Aβ oligomers only affect the excitatory synapses. Aβ oligomers bind to neurite and preferentially to the postsynaptic region, where the postsynaptic protein-95 (PSD-95) is present in the glutamatergic synapse, and interacts directly with the N-methyl-D-aspartate receptor (NMDAR) and neuroligin (NL). NL is a postsynaptic protein which binds to the presynaptic protein, neurexin to form a heterophilic adhesion complex, the disruption of this interaction affects the integrity of the synaptic contact. Structurally, NL has an extracellular domain homolog to acetylcholinesterase, the first synaptic protein that was found to interact with Aβ. In the present review we will document the interaction between Aβ and the extracellular domain of NL-1 at the excitatory synapse, as well as the interaction with other postsynaptic components, including the glutamatergic receptors (NMDA and mGluR5), the prion protein, the neurotrophin receptor, and the α7-nicotinic acetylcholine receptor. We conclude that several Aβ oligomers receptors exist at the excitatory synapse, which could be the responsible for the neurotoxic effect described for the Aβ oligomers. The characterization of the interaction between Aβ receptors and Aβ oligomers could help to understand the source of the neurologic damage observed in the brain of the Alzheimer's disease patients.

  4. Chitosan oligomers as potential and safe absorption enhancers for improving the pulmonary absorption of interferon-alpha in rats.

    PubMed

    Yamada, Keigo; Odomi, Masaaki; Okada, Naoki; Fujita, Takuya; Yamamoto, Akira

    2005-11-01

    Effects of chitosan oligomers on pulmonary absorption of interferon-alpha (IFN) were examined by means of an in vivo pulmonary absorption experiment. Chitosan oligomers used in this study were chitosan dimer, tetramer, hexamer, and water-soluble (WS) chitosan. A significant increase in serum IFN concentrations was observed after intratracheal administration of IFN with these oligomers. Of these chitosan oligomers, 0.5% w/v chitosan hexamer appeared to be more effective in enhancing the pulmonary absorption of IFN than other oligomers at the same concentration, and the AUC value of IFN with chitosan hexamer increased 2.6-fold as compared with the control. On the other hand, chitosan polymers, which have relatively high molecular weights (22-96 kDa), were not effective in enhancing the pulmonary absorption of IFN due to their low solubility in water. Additionally, the effect of different concentrations (0.1%-1% w/v) of chitosan hexamer on the pulmonary absorption of IFN was studied. Of these different concentrations of chitosan hexamers, the highest AUC value of IFN was obtained in the presence of 0.5% w/v chitosan hexamer. Furthermore, chitosan oligomers did not cause any membrane damage to the rat pulmonary tissues, as determined by leakage of protein and lactate dehydrogenase (LDH) in bronchoalveolar lavage (BAL) fluid. Therefore, these findings indicated that the use of chitosan oligomers would be a promising approach for improving of the pulmonary absorption of biologically active peptides including IFN.

  5. Direct observation of single amyloid-β(1-40) oligomers on live cells: binding and growth at physiological concentrations.

    PubMed

    Johnson, Robin D; Schauerte, Joseph A; Wisser, Kathleen C; Gafni, Ari; Steel, Duncan G

    2011-01-01

    Understanding how amyloid-β peptide interacts with living cells on a molecular level is critical to development of targeted treatments for Alzheimer's disease. Evidence that oligomeric Aβ interacts with neuronal cell membranes has been provided, but the mechanism by which membrane binding occurs and the exact stoichiometry of the neurotoxic aggregates remain elusive. Physiologically relevant experimentation is hindered by the high Aβ concentrations required for most biochemical analyses, the metastable nature of Aβ aggregates, and the complex variety of Aβ species present under physiological conditions. Here we use single molecule microscopy to overcome these challenges, presenting direct optical evidence that small Aβ(1-40) oligomers bind to living neuroblastoma cells at physiological Aβ concentrations. Single particle fluorescence intensity measurements indicate that cell-bound Aβ species range in size from monomers to hexamers and greater, with the majority of bound oligomers falling in the dimer-to-tetramer range. Furthermore, while low-molecular weight oligomeric species do form in solution, the membrane-bound oligomer size distribution is shifted towards larger aggregates, indicating either that bound Aβ oligomers can rapidly increase in size or that these oligomers cluster at specific sites on the membrane. Calcium indicator studies demonstrate that small oligomer binding at physiological concentrations induces only mild, sporadic calcium leakage. These findings support the hypothesis that small oligomers are the primary Aβ species that interact with neurons at physiological concentrations.

  6. Acute amnestic encephalopathy in amyloid-β oligomer-injected mice is due to their widespread diffusion in vivo.

    PubMed

    Epelbaum, Stéphane; Youssef, Ihsen; Lacor, Pascale N; Chaurand, Pierre; Duplus, Eric; Brugg, Bernard; Duyckaerts, Charles; Delatour, Benoît

    2015-06-01

    Amyloid-β (Aβ) oligomers are the suspected culprit as initiators of Alzheimer's disease (AD). However, their diffusion in the brain remains unknown. Here, we studied Aβ oligomers' dissemination and evaluated their in vivo toxicity. Wild-type mice were injected with 50 pmol of synthetic Aβ oligomers (of different size) in the hippocampus. Oligomers diffused largely in the brain as soon as 1 hour and up to 7 days after injection. A transient encephalopathy with memory impairment was induced by this unique injection. The immunoreactivity of the postsynaptic marker PSD95 was diffusely decreased. Similar results (both on memory and PSD95 immunoreactivity) were obtained with delipidated and high molecular weight oligomers (>50 kDa) but not with smaller assemblies. Tau hyperphosphorylation was observed in the oligomer-injected brains. Finally, fos immunostaining was increased in Aβ-derived diffusible ligands-injected mice, suggesting neuronal hyperactivity. Rapid and widespread diffusion of Aβ oligomers was demonstrated in vivo and associated with decreased synaptic markers and memory deficits which gives new insight to the pathogenicity of Aβ.

  7. Protective spin-labeled fluorenes maintain amyloid beta peptide in small oligomers and limit transitions in secondary structure

    PubMed Central

    Altman, Robin; Ly, Sonny; Hilt, Silvia; Petrlova, Jitka; Maezawa, Izumi; Kálai, Tamás; Hideg, Kálmán; Jin, Lee-Way; Laurence, Ted A.; Voss, John C.

    2015-01-01

    Alzheimer’s disease is characterized by the presence of extracellular plaques comprised of amyloid beta (Aβ) peptides. Soluble oligomers of the Aβ peptide underlie a cascade of neuronal loss and dysfunction associated with Alzheimer’s disease. Single particle analyses of Aβ oligomers in solution by fluorescence correlation spectroscopy (FCS) were used to provide real-time descriptions of how spin-labeled fluorenes (SLFs; bi-functional small molecules that block the toxicity of Aβ) prevent and disrupt oligomeric assemblies of Aβ in solution. Furthermore, the circular dichroism (CD) spectrum of untreated Aβ shows a continuous, progressive change over a 24-hour period, while the spectrum of Aβ treated with SLF remains relatively constant following initial incubation. These findings suggest the conformation of Aβ within the oligomer provides a complementary determinant of Aβ toxicity in addition to oligomer growth and size. Although SLF does not produce a dominant state of secondary structure in Aβ, it does induce a net reduction in beta secondary content compared to untreated samples of Aβ. The FCS results, combined with electron paramagnetic resonance spectroscopy and CD spectroscopy, demonstrate SLFs can inhibit the growth of Aβ oligomers and disrupt existing oligomers, while retaining Aβ as a population of smaller, yet largely disordered oligomers. PMID:26374940

  8. Matrix-assisted laser desorption/ionization mass spectrometry of discrete mass poly(butylene glutarate) oligomers.

    PubMed

    Williams, John B; Chapman, Toby M; Hercules, David M

    2003-07-01

    The mass dependency of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) response has been studied using equimolar mixtures of synthetic discrete mass poly(butylene glutarate) (PBG) oligomers of known structure having degrees of polymerization of 8, 16, 32, and 64. Mass discrimination observed was attributed to choice of matrix and detector saturation caused by higher laser intensity and inclusion of matrix ions in the MALDI spectra. Optimization of sample preparation and instrumental parameters provided uniform response over the mass ranged spanned by these four oligomers. The oligomer mixture was shown to serve as a model of more complex polymer distributions in the mass range 780-6000 Da, and application of the discrete mass oligomers as internal and calibration standards was demonstrated. Inclusion of PBG discrete mass oligomers as an internal standard in a quasi-equimolar mixture with polydispersed poly(butylene adipate) (PBA) indicated that some diminution of response occurred during the analysis of this mixture of materials. Reasons for differences in the corrected molecular weight averages of the polydispersed PBA obtained from measurements using MALDI and GPC were studied using individual discrete mass oligomers as calibration standards for GPC. The data indicated that differences in hydrodynamic volumes of PBG oligomers and PEG standards at similar masses resulted in an overestimation by GPC of the molecular weight averages of the PBA distribution.

  9. Protective spin-labeled fluorenes maintain amyloid beta peptide in small oligomers and limit transitions in secondary structure

    SciTech Connect

    Altman, Robin; Ly, Sonny; Hilt, Silvia; Petrlova, Jitka; Maezawa, Izumi; Kálai, Tamás; Hideg, Kálmán; Jin, Lee-Way; Laurence, Ted A.; Voss, John C.

    2015-12-01

    Alzheimer’s disease is characterized by the presence of extracellular plaques comprised of amyloid beta (Aβ) peptides. Soluble oligomers of the Aβ peptide underlie a cascade of neuronal loss and dysfunction associated with Alzheimer's disease. Single particle analyses of Aβ oligomers in solution by fluorescence correlation spectroscopy (FCS) were used to provide real-time descriptions of how spin-labeled fluorenes (SLFs; bi-functional small molecules that block the toxicity of Aβ) prevent and disrupt oligomeric assemblies of Aβ in solution. The FCS results, combined with electron paramagnetic resonance spectroscopy and circular dichroism spectroscopy, demonstrate SLFs can inhibit the growth of Aβ oligomers and disrupt existing oligomers while retaining Aβ in a largely disordered state. Furthermore, while the ability of SLF to block Aβ toxicity correlates with a reduction in oligomer size, our results suggest the conformation of Aβ within the oligomer determines the toxicity of the species. Attenuation of Aβ toxicity, which has been associated primarily with the soluble oligomeric form, can be achieved through redistribution of the peptides into smaller oligomers and arrest of the fractional increase in beta secondary structure.

  10. Antigenic implications of human immunodeficiency virus type 1 envelope quaternary structure: oligomer-specific and -sensitive monoclonal antibodies.

    PubMed Central

    Broder, C C; Earl, P L; Long, D; Abedon, S T; Moss, B; Doms, R W

    1994-01-01

    A majority of monoclonal antibodies (mAbs) raised against soluble oligomeric human immunodeficiency virus type 1 isolate IIIB (HIV-1IIIB) envelope (env) glycoprotein reacted with conformational epitopes within the gp120 or gp41 subunits. Of 35 mAbs directed against gp41, 21 preferentially reacted with oligomeric env. A subset of these mAbs reacted only with env oligomers (oligomer-specific mAbs). In contrast, only 1 of 27 mAbs directed against the gp120 subunit reacted more strongly with env oligomers than with monomers, and none were oligomer-specific. However, 50% of anti-gp120 mAbs preferentially recognized monomeric env, suggesting that some epitopes in gp120 are partially masked or altered by intersubunit contacts in the native env oligomer. Two mAbs to oligomer-dependent epitopes in gp41 neutralized HIV-1IIIB and HIV-1SF2, and binding of these mAbs to env was blocked by preincubation with HIV-1-positive human serum. Thus, immunization with soluble, oligomeric env elicits antibodies to conserved, conformational epitopes including a newly defined class of neutralizing antibodies that bind to oligomer-specific epitopes in gp41, and may also minimize the production of antibodies that preferentially react with monomeric env protein. Images PMID:7972127

  11. Effects of secreted oligomers of amyloid β-protein on hippocampal synaptic plasticity: a potent role for trimers

    PubMed Central

    Townsend, Matthew; Shankar, Ganesh M; Mehta, Tapan; Walsh, Dominic M; Selkoe, Dennis J

    2006-01-01

    The accumulation of amyloid β-protein (Aβ) in brain regions serving memory and cognition is a central pathogenic feature of Alzheimer's disease (AD). We have shown that small soluble oligomers of human Aβ that are naturally secreted by cultured cells inhibit hippocampal long-term potentiation (LTP) in vitro and in vivo and transiently impair the recall of a complex learned behaviour in rats. These results support the hypothesis that diffusible oligomers of Aβ initiate a synaptic dysfunction that may be an early event in AD. We now report detailed electrophysiological analyses that define conditions under which acute application of soluble Aβ inhibits hippocampal synaptic plasticity in wild-type mice. To ascertain which Aβ assemblies contribute to the impairment of LTP, we fractionated oligomers by size-exclusion chromatography and found that Aβ trimers fully inhibit LTP, whereas dimers and tetramers have an intermediate potency. Natural Aβ oligomers are sensitive to heat denaturation, primarily inhibit the induction phase of LTP, and cause a sustained impairment of LTP even after extensive washout. We observed no effects of Aβ oligomers on presynaptic vesicle release. LTP in juvenile mice is resistant to the effects of Aβ oligomers, as is brain-derived-neurotrophic-factor-induced LTP in adult hippocampus. We conclude that specific assemblies, particularly timers, of naturally secreted Aβ oligomers are potent and selective inhibitors of certain forms of hippocampal LTP. PMID:16469784

  12. The load of amyloid-β oligomers is decreased in the cerebrospinal fluid of Alzheimer's disease patients.

    PubMed

    Sancesario, Giulia M; Cencioni, Maria T; Esposito, Zaira; Borsellino, Giovanna; Nuccetelli, Marzia; Martorana, Alessandro; Battistini, Luca; Sorge, Roberto; Spalletta, Gianfranco; Ferrazzoli, Davide; Bernardi, Giorgio; Bernardini, Sergio; Sancesario, Giuseppe

    2012-01-01

    Amyloid-β (Aβ) oligomers are heterogeneous and instable compounds of variable molecular weight. Flow cytometry and fluorescence resonance energy transfer (FRET)-based methods allow the simultaneous detection of Aβ oligomers with low and high molecular weight in their native form. We evaluated whether an estimate of different species of Aβ oligomers in the cerebrospinal fluid (CSF) with or without dilution with RIPA buffer could be more useful in the diagnosis of Alzheimer's disease (AD) than the measurement of Aβ42 monomers, total tau (t-tau), and phosphorylated tau (p-tau). Increased t-tau (p < 0.01) and p-tau (p < 0.01), and decreased Aβ42 (p < 0.01), were detected in the CSF of patients with AD (n = 46), compared to patients with other dementia (OD) (n = 35) or with other neurological disorders (OND) (n = 56). In native CSF (n = 137), the levels of Aβ oligomers were lower (p < 0.05) in AD than in OD and OND patients; in addition, the ratio Aβ oligomers/p-tau was lower in AD than in OD (p < 0.01) and OND (p < 0.05) patients, yielding a sensitivity of 75% and a specificity of 64%. However, in CSF diluted with RIPA (n = 30), Aβ oligomers appeared higher (p < 0.05) in AD than in OND patients, suggesting they become partially disaggregated and more easily detectable after RIPA. In conclusion, FRET analysis in native CSF is essential to correctly determine the composition of Aβ oligomers. In this experimental setting, the simultaneous estimate of low and high molecular weight Aβ oligomers is as useful as the other biomarkers in the diagnosis of AD. The low amount of Aβ oligomers detected in native CSF of AD may be inversely related to their levels in the brain, as occurs for Aβ monomers, representing a biomarker for the amyloid pathogenic cascade.

  13. Nonenzymatic synthesis of RNA and DNA oligomers on hexitol nucleic acid templates: the importance of the A structure

    NASA Technical Reports Server (NTRS)

    Kozlov, I. A.; Politis, P. K.; Van Aerschot, A.; Busson, R.; Herdewijn, P.; Orgel, L. E.; Bada, J. L. (Principal Investigator); Dolan, M. (Principal Investigator)

    1999-01-01

    Hexitol nucleic acid (HNA) is an analogue of DNA containing the standard nucleoside bases, but with a phosphorylated 1,5-anhydrohexitol backbone. HNA oligomers form duplexes having the nucleic acid A structure with complementary DNA or RNA oligomers. The HNA decacytidylate oligomer is an efficient template for the oligomerization of the 5'-phosphoroimidazolides of guanosine or deoxyguanosine. Comparison of the oligomerization efficiencies on HNA, RNA, and DNA decacytidylate templates under various conditions suggests strongly that only nucleic acid double helices with the A structure support efficient template-directed synthesis when 5'-phosphoroimidazolides of nucleosides are used as substrates.

  14. Purified high molecular weight synthetic Aβ(1-42) and biological Aβ oligomers are equipotent in rapidly inducing MTT formazan exocytosis.

    PubMed

    Weidner, Adam M; Housley, Molly; Murphy, M Paul; Levine, Harry

    2011-06-15

    Synthetic soluble Aβ oligomers are often used as a surrogate for biologic material in a number of model systems. We compared the activity of Aβ oligomers (synthetic and cell culture media derived) on the human SH-SY5Y neuroblastoma and C2C12 mouse myoblast cell lines in a novel, modified MTT assay. Separating oligomers from monomeric peptide by size exclusion chromatography produced effects at peptide concentrations approaching physiologic levels (10-100 nM). Purified oligomers, but not monomers or fibrils, elicited an increase of a detergent-insoluble form of MTT formazan within 2h as opposed to a control toxin (H(2)O(2)). This effect was comparable for biological and synthetic peptide in both cell types. Monomeric Aβ attenuated the effect of soluble oligomers. This study suggests that the activities of biological and synthetic oligomers are indistinguishable during early stages of Aβ oligomer-cell interaction.

  15. Oligomer formation during gas-phase ozonolysis of small alkenes and enol ethers: new evidence for the central role of the Criegee Intermediate as oligomer chain unit

    NASA Astrophysics Data System (ADS)

    Sadezky, A.; Winterhalter, R.; Kanawati, B.; Römpp, A.; Spengler, B.; Mellouki, A.; Le Bras, G.; Chaimbault, P.; Moortgat, G. K.

    2007-10-01

    An important fraction of secondary organic aerosol (SOA) formed by atmospheric oxidation of diverse volatile organic compounds (VOC) has recently been shown to consist of high-molecular weight oligomeric species. In our previous study (Sadezky et al., 2006), we reported the identification and characterization of oligomers as main constituents of SOA from gas-phase ozonolysis of small enol ethers. These oligomers contained repeated chain units of the same chemical composition as the main Criegee Intermediates (CI) formed during the ozonolysis reaction, which were CH2O2 (mass 46) for alkyl vinyl ethers (AVE) and C2H4O2 (mass 60) for ethyl propenyl ether (EPE). In the present work, we extend our previous study (Sadezky et al., 2006) to another enol ether (ethyl butenyl ether EBE) and a variety of structurally related small alkenes (trans-3-hexene, trans-4-octene and 2,3-dimethyl-2-butene). Experiments have been carried out in a 570 l spherical glass reactor at atmospheric conditions in the absence of seed aerosol. SOA formation was measured by a scanning mobility particle sizer (SMPS). SOA filter samples were collected and chemically characterized off-line by ESI(+)/MS-TOF and ESI(+)/MS/MS-TOF, and elemental compositions were confirmed by ESI(+)/MS/MS-FTICR. The results for all investigated unsaturated compounds are in excellent agreement with the observations of our previous study (Sadezky et al., 2006). Analysis of the collected SOA filter samples reveal the presence of oligomeric compounds in the mass range 200 to 800 u as major constituents. The repeated chain units of these oligomers are shown to systematically have the same chemical composition as the respective main Criegee Intermediate (CI) formed during ozonolysis of the unsaturated compounds, which is C3H6O2 (mass 74) for ethyl butenyl ether (EBE), trans-3-hexene, and 2,3-dimethyl-2-butene, and C4H8O2 (mass 88) for trans-4-octene. Analogous fragmentation pathways among the oligomers formed by gas

  16. Distinct molecular structures and hydrogen bond patterns of α,α-diethyl-substituted cyclic imide, lactam, and acetamide derivatives in the crystalline phase

    NASA Astrophysics Data System (ADS)

    Krivoshein, Arcadius V.; Ordonez, Carlos; Khrustalev, Victor N.; Timofeeva, Tatiana V.

    2016-10-01

    α,α-Dialkyl- and α-alkyl-α-aryl-substituted cyclic imides, lactams, and acetamides show promising anticonvulsant, anxiolytic, and anesthetic activities. While a number of crystal structures of various α-substituted cyclic imides, lactams, and acetamides were reported, no in-depth comparison of crystal structures and solid-state properties of structurally matched compounds have been carried out so far. In this paper, we report molecular structure and intermolecular interactions of three α,α-diethyl-substituted compounds - 3,3-diethylpyrrolidine-2,5-dione, 3,3-diethylpyrrolidin-2-one, and 2,2-diethylacetamide - in the crystalline phase, as studied using single-crystal X-ray diffraction and IR spectroscopy. We found considerable differences in the patterns of H-bonding and packing of the molecules in crystals. These differences correlate with the compounds' melting points and are of significance to physical pharmacy and formulation development of neuroactive drugs.

  17. Comparison of the anodic behavior of aluminum current collectors in imide-based ionic liquids and consequences on the stability of high voltage supercapacitors

    NASA Astrophysics Data System (ADS)

    Kühnel, Ruben-Simon; Balducci, Andrea

    2014-03-01

    In this work, the influence of two common ionic liquid (IL) anions on the anodic stability of Al current collectors was studied. Namely, the Al corrosion/passivation process in N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14TFSI) is compared to the one in N-butyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide (PYR14FSI). It is shown, that Al slowly corrodes in PYR14FSI, while it is much better passivated in PYR14TFSI, although the ionic liquids were prepared in the same way. Float tests were carried out to illustrate the consequences of these different anodic stabilities of Al on the cycling stability of supercapacitors. Interestingly, when the chloride content of PYR14FSI was <1 ppm, Al electrodes were also pretty stable in this IL, and a similar cycling stability during float tests than for PYR14TFSI could be obtained.

  18. Physical and electrochemical properties of N-alkyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide ionic liquids: PY13FSI and PY14FSI.

    PubMed

    Zhou, Qian; Henderson, Wesley A; Appetecchi, Giovanni B; Montanino, Maria; Passerini, Stefano

    2008-10-30

    Two ionic liquids based upon N-alkyl-N-methylpyrrolidinium cations (PY(1R)(+)) (R=3 for propyl or 4 for butyl) and the bis(fluorosulfonyl)imide (FSI(-)), N(SO2F)2(-), anion have been extensively characterized. The ionic conductivity and viscosity of these materials are found to be among the highest and lowest, respectively, reported for aprotic ionic liquids. Both ionic liquids crystallize readily on cooling and undergo several solid-solid phase transitions on heating prior to melting. PY13FSI and PY14FSI are found to melt at -9 and -18 degrees C, respectively. The thermal stability of PY13FSI and PY14FSI is notably lower than for the analogous salts with the bis(trifluoromethanesulfonyl)imide (TFSI(-)), N(SO2CF3)2(-), anion. Both ionic liquids have a relatively wide electrochemical stability window of approximately 5 V.

  19. Amyloid β oligomers induce interleukin-1β production in primary microglia in a cathepsin B- and reactive oxygen species-dependent manner

    SciTech Connect

    Taneo, Jun; Adachi, Takumi; Yoshida, Aiko; Takayasu, Kunio; Takahara, Kazuhiko; Inaba, Kayo

    2015-03-13

    Amyloid β (Aβ) peptide, a causative agent of Alzheimer's disease, forms two types of aggregates: oligomers and fibrils. These aggregates induce inflammatory responses, such as interleukin-1β (IL-1β) production by microglia, which are macrophage-like cells located in the brain. In this study, we examined the effect of the two forms of Aβ aggregates on IL-1β production in mouse primary microglia. We prepared Aβ oligomer and fibril from Aβ (1–42) peptide in vitro. We analyzed the characteristics of these oligomers and fibrils by electrophoresis and atomic force microscopy. Interestingly, Aβ oligomers but not Aβ monomers or fibrils induced robust IL-1β production in the presence of lipopolysaccharide. Moreover, Aβ oligomers induced endo/phagolysosome rupture, which released cathepsin B into the cytoplasm. Aβ oligomer-induced IL-1β production was inhibited not only by the cathepsin B inhibitor CA-074-Me but also by the reactive oxygen species (ROS) inhibitor N-acetylcysteine. Random chemical crosslinking abolished the ability of the oligomers to induce IL-1β. Thus, multimerization and fibrillization causes Aβ oligomers to lose the ability to induce IL-1β. These results indicate that Aβ oligomers, but not fibrils, induce IL-1β production in primary microglia in a cathepsin B- and ROS-dependent manner. - Highlights: • We prepared amyloid β (Aβ) fibrils with minimum contamination of Aβ oligomers. • Primary microglia (MG) produced IL-1β in response to Aβ oligomers, but not fibrils. • Only Aβ oligomers induced leakage of cathepsin B from endo/phagolysosomes. • IL-1β production in response to Aβ oligomers depended on both cathepsin B and ROS. • Crosslinking reduced the ability of the Aβ oligomers to induce IL-1β from MG.

  20. Activity Coefficients at Infinite Dilution of Organic Compounds in Trihexyl(tetradecyl)phophonium Bis(trifluoromethylsulfonyl)imide Using Inverse Gas Chromatography

    SciTech Connect

    Revelli, Anne-Laure; Sprunger, Laura; Gibbs, Jennifer; Acree, William; Baker, Gary A; Mutelet, Fabrice

    2009-01-01

    Activity coefficients at infinite dilution of organic compounds in the ionic liquid (IL) trihexyl(tetradecyl) phosphonium bis(trifluoromethylsulfonyl)imide were determined using inverse gas chromatography at three temperatures, T ) (302.45, 322.35, and 342.45) K. Linear free energy relationship (LFER) correlations have been obtained for describing the gas-to-IL and water-to-IL partition coefficients.