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Sample records for crosslinks enable highly

  1. Highly Efficient Perovskite Nanocrystal Light-Emitting Diodes Enabled by a Universal Crosslinking Method.

    PubMed

    Li, Guangru; Rivarola, Florencia Wisnivesky Rocca; Davis, Nathaniel J L K; Bai, Sai; Jellicoe, Tom C; de la Peña, Francisco; Hou, Shaocong; Ducati, Caterina; Gao, Feng; Friend, Richard H; Greenham, Neil C; Tan, Zhi-Kuang

    2016-05-01

    The preparation of highly efficient perovskite nanocrystal light-emitting diodes is shown. A new trimethylaluminum vapor-based crosslinking method to render the nanocrystal films insoluble is applied. The resulting near-complete nanocrystal film coverage, coupled with the natural confinement of injected charges within the perovskite crystals, facilitates electron-hole capture and give rise to a remarkable electroluminescence yield of 5.7%.

  2. Highly Efficient Perovskite Nanocrystal Light-Emitting Diodes Enabled by a Universal Crosslinking Method.

    PubMed

    Li, Guangru; Rivarola, Florencia Wisnivesky Rocca; Davis, Nathaniel J L K; Bai, Sai; Jellicoe, Tom C; de la Peña, Francisco; Hou, Shaocong; Ducati, Caterina; Gao, Feng; Friend, Richard H; Greenham, Neil C; Tan, Zhi-Kuang

    2016-05-01

    The preparation of highly efficient perovskite nanocrystal light-emitting diodes is shown. A new trimethylaluminum vapor-based crosslinking method to render the nanocrystal films insoluble is applied. The resulting near-complete nanocrystal film coverage, coupled with the natural confinement of injected charges within the perovskite crystals, facilitates electron-hole capture and give rise to a remarkable electroluminescence yield of 5.7%. PMID:26990965

  3. Differentially photo-crosslinked polymers enable self-assembling microfluidics

    PubMed Central

    Jamal, Mustapha; Zarafshar, Aasiyeh M.; Gracias, David H.

    2012-01-01

    An important feature of naturally self-assembled systems such as leaves and tissues is that they are curved and have embedded fluidic channels that enable the transport of nutrients to, or removal of waste from, specific three-dimensional (3D) regions. Here, we report the self-assembly of photopatterned polymers, and consequently microfluidic devices, into curved geometries. We discovered that differentially photo-crosslinked SU-8 films spontaneously and reversibly curved upon film de-solvation and re-solvation. Photolithographic patterning of the SU-8 films enabled the self-assembly of cylinders, cubes, and bidirectionally folded sheets. We integrated polydimethylsiloxane (PDMS) microfluidic channels with these SU-8 films to self-assemble curved microfluidic networks. PMID:22068594

  4. Characterization of the crosslinking reaction in high performance phenolic resins

    NASA Astrophysics Data System (ADS)

    Patel, Jigneshkumar; Zou, Guo Xiang; Hsu, Shaw Ling; university of massachusetts/Polymer science; Engineering Team

    In this study, a combination of thermal analysis, infrared spectroscopy (near and mid) in conjunction with low field NMR, was used to characterize the crosslinking reaction involving phenol formaldehyde resin and a crosslinking agent, Hexamethylenetetramine (HMTA). The strong hydrogen bonds in the resin and the completely crystalline HMTA (Tm = 280 °C) severely hamper the crosslinking process. Yet the addition of a small amount of plasticizer can induce a highly efficient crosslinking reaction to achieve the desired mechanical properties needed in a number of high performance organic-inorganic composites. The infrared spectroscopy clarifies the dissolution process of the crystalline crosslinker and the specific interactions needed to achieve miscibility of the reactants. The thermal analysis enabled us to follow the changing mobility of the system as a function of temperature. The low field NMR with the T1 inverse recovery technique allowed us to monitor the crosslinking process directly. For the first time, it is now possible to identify the functionality of the plasticizer and correlate the crosslinked structure achieved to the macroscopic performance needed for high performance organic-inorganic composites.

  5. Highly cross-linked nanoporous polymers

    DOEpatents

    Steckle, Jr., Warren P.; Apen, Paul G.; Mitchell, Michael A.

    1997-01-01

    Condensation polymerization followed by a supercritical extraction step can be used to obtain highly cross-linked nanoporous polymers with high surface area, controlled pore sizes and rigid structural integrity. The invention polymers are useful for applications requiring separation membranes.

  6. Highly cross-linked nanoporous polymers

    DOEpatents

    Steckle, Jr., Warren P.; Apen, Paul G.; Mitchell, Michael A.

    1998-01-01

    Condensation polymerization followed by a supercritical extraction step can be used to obtain highly cross-linked nanoporous polymers with high surface area, controlled pore sizes and rigid structural integrity. The invention polymers are useful for applications requiring separation membranes.

  7. Grafting functional antioxidants on highly crosslinked polyethylene

    NASA Astrophysics Data System (ADS)

    Al-Malaika, S.; Riasat, S.; Lewucha, C.

    2016-05-01

    The problem of interference of antioxidants, such as hindered phenols, with peroxide-initiated crosslinking of polyethylene was addressed through the use of functional (reactive) graftable antioxidants (g-AO). Reactive derivatives of hindered phenol and hindered amine antioxidants were synthesised, characterised and used to investigate their grafting reactions in high density polyethylene; both non-crosslinked (PE) and highly peroxide-crosslinked (PEXa). Assessment of the extent of in-situ grafting of the antioxidants, their retention after exhaustive solvent extraction in PE and PEXa, and the stabilising performance of the grafted antioxidants (g-AO) in the polymer were examined and benchmarked against conventionally stabilised crosslinked & non-crosslinked polyethylene. It was shown that the functional antioxidants graft to a high extent in PEXa, and that the level of interference of the g-AOs with the polymer crosslinking process was minimal compared to that of conventional antioxidants which bear the same antioxidant function. The much higher level of retention of the g-AOs in PEXa after exhaustive solvent extraction, compared to that of the corresponding conventional antioxidants, accounts for their superior long-term thermal stabilising performance under severe extractive conditions.

  8. Highly cross-linked nanoporous polymers

    DOEpatents

    Steckle, W.P. Jr.; Apen, P.G.; Mitchell, M.A.

    1998-01-20

    Condensation polymerization followed by a supercritical extraction step can be used to obtain highly cross-linked nanoporous polymers with high surface area, controlled pore sizes and rigid structural integrity. The invention polymers are useful for applications requiring separation membranes. 1 fig.

  9. Wear of highly crosslinked polyethylene acetabular components

    PubMed Central

    Callary, Stuart A; Solomon, Lucian B; Holubowycz, Oksana T; Campbell, David G; Munn, Zachary; Howie, Donald W

    2015-01-01

    Background and purpose Wear rates of highly crosslinked polyethylene (XLPE) acetabular components have varied considerably between different published studies. This variation is in part due to the different techniques used to measure wear and to the errors inherent in measuring the relatively low amounts of wear in XLPE bearings. We undertook a scoping review of studies that have examined the in vivo wear of XLPE acetabular components using the most sensitive method available, radiostereometric analysis (RSA). Methods A systematic search of the PubMed, Scopus, and Cochrane databases was performed to identify published studies in which RSA was used to measure wear of XLPE components in primary total hip arthroplasty (THA). Results 18 publications examined 12 primary THA cohorts, comprising only 260 THAs at 2–10 years of follow-up. The mean or median proximal wear rate reported ranged from 0.00 to 0.06 mm/year. However, differences in the manner in which wear was determined made it difficult to compare some studies. Furthermore, differences in RSA methodology between studies, such as the use of supine or standing radiographs and the use of beaded or unbeaded reference segments, may limit future meta-analyses examining the effect of patient and implant variables on wear rates. Interpretation This scoping review confirmed the low wear rates of XLPE in THA, as measured by RSA. We make recommendations to enhance the standardization of reporting of RSA wear results, which will facilitate early identification of poorly performing implants and enable a better understanding of the effects of surgical and patient factors on wear. PMID:25301435

  10. Microrheology of highly crosslinked microtubule networks is dominated by force-induced crosslinker unbinding

    NASA Astrophysics Data System (ADS)

    Valentine, Megan; Yang, Yali; Bai, Mo; Klug, William; Levine, Alex

    2013-03-01

    We determine the viscoelastic responses of reconstituted networks of microtubules that have been strongly bonded by labile crosslinkers using a magnetic tweezers device to apply localized forces. At short time scales, the networks respond nonlinearly to applied force, with stiffening at small forces, followed by a reduction in the stiffening response at high forces, which we attribute to the force-induced unbinding of crosslinks. At long time scales, force-induced bond unbinding leads to local network rearrangement and significant bead creep. Interestingly, for rigidly crosslinked networks, the material retains its elastic modulus even under conditions of significant plastic flow, suggesting that crosslinker breakage is balanced by the formation of new bonds. To better understand this effect, we developed a finite element model of such a stiff filament network with crosslinkers obeying force-dependent Bell model unbinding dynamics. The coexistence of dissipation, due to bond breakage, and the elastic recovery of the network is possible because each filament has many crosslinkers. Recovery can occur as long as a sufficient number of the original crosslinkers are preserved under the loading period. When these remaining original crosslinkers are broken, plastic flow results.

  11. Crosslink density, oxidation and chain scission in retrieved, highly cross-linked UHMWPE tibial bearings.

    PubMed

    Reinitz, Steven D; Currier, Barbara H; Levine, Rayna A; Van Citters, Douglas W

    2014-05-01

    Irradiated, thermally stabilized, highly cross-linked UHMWPE bearings have demonstrated superior wear performance and improved in vitro oxidation resistance compared with terminally gamma-sterilized bearings, yet retrieval analysis reveals unanticipated in vivo oxidation in these materials despite fewer or no measurable free radicals. There has been little evidence to date that the oxidation mechanism in thermally stabilized materials is the same as that in conventional materials, and so it is unknown whether oxidation in these materials is leading to chain scission and a degradation of mechanical properties, molecular weight, and crosslink density. The aim of this study was to determine whether measured in vivo oxidation in retrieved, highly cross-linked tibial bearings corresponds with a decreasing crosslink density. Analysis of three tibial bearing materials revealed that crosslink density decreased following in vivo duration, and that the change in crosslink density was strongly correlated with oxidation. The results suggest that oxidation in highly cross-linked materials is causing chain scissions that may, in time, impact the material properties. If in vivo oxidation continues over longer durations, there is potential for a clinically significant degradation of mechanical properties.

  12. Microrheology of highly crosslinked microtubule networks is dominated by force-induced crosslinker unbinding

    PubMed Central

    Yang, Yali; Bai, Mo; Klug, William S.; Levine, Alex J.

    2012-01-01

    We determine the time- and force-dependent viscoelastic responses of reconstituted networks of microtubules that have been strongly crosslinked by biotin-streptavidin bonds. To measure the microscale viscoelasticity of such networks, we use a magnetic tweezers device to apply localized forces. At short time scales, the networks respond nonlinearly to applied force, with stiffening at small forces, followed by a reduction in the stiffening response at high forces, which we attribute to the force-induced unbinding of crosslinks. At long time scales, force-induced bond unbinding leads to local network rearrangement and significant bead creep. Interestingly, the network retains its elastic modulus even under conditions of significant plastic flow, suggesting that crosslinker breakage is balanced by the formation of new bonds. To better understand this effect, we developed a finite element model of such a stiff filament network with labile crosslinkers obeying force-dependent Bell model unbinding dynamics. The coexistence of dissipation, due to bond breakage, and the elastic recovery of the network is possible because each filament has many crosslinkers. Recovery can occur as long as a sufficient number of the original crosslinkers are preserved under the loading period. When these remaining original crosslinkers are broken, plastic flow results. PMID:23577042

  13. Highly crosslinked silicon polymers for gas chromatography columns

    NASA Technical Reports Server (NTRS)

    Shen, Thomas C. (Inventor)

    1994-01-01

    A new highly crosslinked silicone polymer particle for gas chromatography application and a process for synthesizing such copolymer are described. The new copolymer comprises vinyltriethoxysilane and octadecyltrichlorosilane. The copolymer has a high degree of crosslinking and a cool balance of polar to nonpolar sites in the porous silicon polymer assuring fast separation of compounds of variable polarity.

  14. Simulation of interfacial fracture in highly crosslinked adhesives

    SciTech Connect

    STEVENS,MARK J.

    2000-05-22

    The fracture of highly-crosslinked networks is investigated by molecular dynamics simulations. The network is modeled as a bead-spring polymer network between two solid surfaces. The network is dynamically formed by crosslinking an equilibrated liquid mixture. Tensile pull fracture is simulated as a function of the number of interracial bonds. The sequence of molecular structural deformations that lead to failure are determined, and the connectivity is found to strongly control the stress-strain response and failure modes. The failure strain is related to the minimal paths in the network that connect the two solid surfaces. The failure stress is a fraction of the ideal stress required to fracture all the interracial bonds, and is linearly proportional to the number of interracial bonds. By allowing only a single bond between a crosslinker and the surface, interracial failure always occurs. Allowing up to half of the crosslinker's bonds to occur with the surface, cohesive failure can occur.

  15. Unified wear model for highly crosslinked ultra-high molecular weight polyethylenes (UHMWPE).

    PubMed

    Muratoglu, O K; Bragdon, C R; O'Connor, D O; Jasty, M; Harris, W H; Gul, R; McGarry, F

    1999-08-01

    Crosslinking has been shown to improve the wear resistance of ultra-high molecular weight polyethylene in both in vitro and clinical in vivo studies. The molecular mechanisms and material properties that are responsible for this marked improvement in wear resistance are still not well understood. In fact, following crosslinking a number of mechanical properties of UHMWPE are decreased including toughness, modulus, ultimate tensile strength, yield strength, and hardness. In general, these changes would be expected to constitute a precursor for lower wear resistance, presenting a paradox in that wear resistance increases with crosslinking. In order to understand better and to analyze this paradoxical behaviour of crosslinked UHMWPE, we investigated the wear behavior of (i) radiation-crosslinked GUR 1050 resin, (ii) peroxide-crosslinked GUR 1050 resin and (iii) peroxide-crosslinked Himont 1900 resin using a bi-directional pin-on-disk (POD) machine. Wear behavior was analyzed as a function of crystallinity, ultimate tensile strength (UTS), yield strength (YS), and molecular weight between crosslinks (Mc). The crosslink density increased with increasing radiation dose level and initial peroxide content. The UTS, YS, and crystallinity decreased with increasing crosslink density. While these variations followed the same trend, the absolute changes as a function of crosslink density were different for the three types of crosslinked UHMWPE studied. There was no unified correlation for the wear behavior of the three types of crosslinked UHMWPE with the crystallinity, UTS and YS. However, the POD wear rate showed the identical linear dependence on Mc with all three types of crosslinked UHMWPEs studied. Therefore, we have strong evidence to propose that Mc or crosslink density is a fundamental material property that governs the lubricated adhesive and abrasive wear mechanisms of crosslinked UHMWPEs, overriding the possible effects of other material properties such as UTS, YS

  16. Enabling High Efficiency Ethanol Engines

    SciTech Connect

    Szybist, J.; Confer, K.

    2011-03-01

    Delphi Automotive Systems and ORNL established this CRADA to explore the potential to improve the energy efficiency of spark-ignited engines operating on ethanol-gasoline blends. By taking advantage of the fuel properties of ethanol, such as high compression ratio and high latent heat of vaporization, it is possible to increase efficiency with ethanol blends. Increasing the efficiency with ethanol-containing blends aims to remove a market barrier of reduced fuel economy with E85 fuel blends, which is currently about 30% lower than with petroleum-derived gasoline. The same or higher engine efficiency is achieved with E85, and the reduction in fuel economy is due to the lower energy density of E85. By making ethanol-blends more efficient, the fuel economy gap between gasoline and E85 can be reduced. In the partnership between Delphi and ORNL, each organization brought a unique and complementary set of skills to the project. Delphi has extensive knowledge and experience in powertrain components and subsystems as well as overcoming real-world implementation barriers. ORNL has extensive knowledge and expertise in non-traditional fuels and improving engine system efficiency for the next generation of internal combustion engines. Partnering to combine these knowledge bases was essential towards making progress to reducing the fuel economy gap between gasoline and E85. ORNL and Delphi maintained strong collaboration throughout the project. Meetings were held regularly, usually on a bi-weekly basis, with additional reports, presentations, and meetings as necessary to maintain progress. Delphi provided substantial hardware support to the project by providing components for the single-cylinder engine experiments, engineering support for hardware modifications, guidance for operational strategies on engine research, and hardware support by providing a flexible multi-cylinder engine to be used for optimizing engine efficiency with ethanol-containing fuels.

  17. Vitamin E diffused, highly crosslinked UHMWPE: a review

    PubMed Central

    Muratoglu, Orhun K.

    2010-01-01

    Highly crosslinked UHMWPE has become the bearing surface of choice in total hip arthroplasty. First generation crosslinked UHMWPEs, clinically introduced in the 1990s, show significant improvements compared to gamma sterilised, conventional UHMWPE in decreasing wear and osteolysis. These crosslinked UHMWPEs were thermally treated (annealed or melted) after irradiation to improve their oxidation resistance. While annealing resulted in the retention of some oxidation potential, post-irradiation melted UHMWPEs had reduced fatigue strength due to the crystallinity loss during melting. Thus, the stabilisation of radiation crosslinked UHMWPEs by the diffusion of the antioxidant vitamin E was developed to obtain oxidation resistance with improved fatigue strength by avoiding post-irradiation melting. A two-step process was developed to incorporate vitamin E into irradiated UHMWPE by diffusion to obtain a uniform concentration profile. Against accelerated and real-time aging in vitro, this material showed superior oxidation resistance to UHMWPEs with residual free radicals. The fatigue strength was improved compared to irradiated and melted UHMWPEs crosslinked using the same irradiation dose. Several adverse testing schemes simulating impingement showed satisfactory behaviour. Peri-prosthetic tissue reaction to vitamin E was evaluated in rabbits and any effects of vitamin E on device fixation were evaluated in a canine model, both of which showed no detrimental effects of the inclusion of vitamin E in crosslinked UHMWPE. Irradiated, vitamin E-diffused, and gamma sterilised UHMWPEs have been in clinical use in hips since 2007 and in knees since 2008. The clinical outcome of this material will be apparent from the results of prospective, randomised clinical studies. PMID:21120476

  18. Single-molecule FRET and crosslinking studies in structural biology enabled by noncanonical amino acids.

    PubMed

    Tyagi, Swati; Lemke, Edward A

    2015-06-01

    Contemporary structural biology research promises more than just static snap-shots of molecular machineries. This goal is not just facilitated by combining different structural biology techniques, but also by new tools from the field of protein and genetic engineering, as well as from chemistry. Genetic encoding of noncanonical amino acids (ncAAs) through codon-suppression technology provides an excellent opportunity to probe biomolecules using different structural biology methods. In this article, we review the applications of ncAA incorporation into proteins for determining structural information through various techniques with the main focus on crosslinking mass spectrometry and single-molecule FRET-based techniques. Furthermore, advances and limitations of the incorporation of multiple ncAAs are discussed, with respect to design of an ideal host organism for modern and integrative structural biology research.

  19. High temperature well treating with crosslinked gelled solutions

    SciTech Connect

    Ely, J.; Tinsley, J.

    1980-07-01

    A description is given of a method of treating a well formation existing at a temperature in the range of from about 120/sup 0/F to about 350/sup 0/F with a temporary blocking agent comprising the steps of: preparing a temporary blocking agent composition which forms a highly viscious crosslinked gel at the temperature of said well formation, said composition being comprised of water, a gelling agent present in the range of from about 1 to about 13 parts by weight per 100 parts by weight of said water and selected from the group consisting of water soluble polysaccharides having a molecular weight of at least about 100,000, said water soluble polysaccharides crosslinked with a compound selected from the group consisting of dialdehydes having the general formula: OHC(CH/sub 2/)/sub n/CHO, wherein n is an integer within the range of 0 to about 3, 2-hydroxyadipaldehyde, diemthylol urea, water soluble urea formaldehyde resins, water soluble melamine formaldehyde resins, and mixtures thereof, water soluble polyacrylamides and mixtures thereof, and hexamethyoxymethylmelamine present in the range of from about 0.05 to aboiut 5 parts by weight per 100 parts by weight of said water; and introducing said composition into said well formation whereby said composition is heated to a temperature in the range of from about 120/sup 0/F to about 350/sup 0/F and formed into a highly viscious crosslinked gel in said formation.

  20. Autoclavable highly cross-linked polyurethane networks in ophthalmology.

    PubMed

    Bruin, P; Meeuwsen, E A; van Andel, M V; Worst, J G; Pennings, A J

    1993-11-01

    Highly cross-linked aliphatic polyurethane networks have been prepared by the bulk step reaction of low molecular weight polyols and hexamethylenediisocyanate (HDI). These polyurethane networks are optically transparent, colourless and autoclavable amorphous glassy thermosets, which are suited for use in ophthalmic applications such as intraocular lenses and keratoprostheses. The properties of these glassy polyurethanes, obtained from the reaction of the low molecular weight polyols triisopropanolamine (TIPA) or tetrakis (2-hydroxypropyl)ethylenediamine (Quadrol) and HDI in stoichiometric proportions, have been investigated in more detail. The glassy Quadrol/HDI-based polyurethane exhibits a reduction in ultimate glass transition temperature from 85 to 48 degrees C by uptake of 1% of water, and good ultimate mechanical properties (tensile strength 80-85 MPa, elongation at break ca 15%, modulus ca 1.5 GPa). IR spectra of these hydrophobic polyurethane networks revealed the absence of an isocyanate absorption, indicating that all isocyanates, apparently, had reacted during the cross-linking reaction. The biocompatibility could be increased by grafting tethered polyacrylamide chains onto the surface during network formation. These transparent cross-linked polyurethanes did not transmit UV light up to 400 nm, by incorporation of a small amount of the UV absorbing chromophore Coumarin 102, and could be sterilized simply by autoclaving. They were implanted in rabbit eyes, either in the form of small circular disks or in the form of a keratoprosthesis (artificial cornea). It was shown that the material was well tolerated by the rabbit eyes. Serious opacification of the cornea, a direct result of an adverse reaction to the implant, was never seen. Even 1 yr after implantation of a polyurethane keratoprosthesis the eye was still 'quiet'. PMID:7508760

  1. Tunable high performance cross-linked alkaline anion exchange membranes for fuel cell applications.

    PubMed

    Robertson, Nicholas J; Kostalik, Henry A; Clark, Timothy J; Mutolo, Paul F; Abruña, Héctor D; Coates, Geoffrey W

    2010-03-17

    Fuel cells are energy conversion devices that show great potential in numerous applications ranging from automobiles to portable electronics. However, further development of fuel cell components is necessary for them to become commercially viable. One component critical to their performance is the polymer electrolyte membrane, which is an ion conductive medium separating the two electrodes. While proton conducting membranes are well established (e.g., Nafion), hydroxide conducting membranes (alkaline anion exchange membranes, AAEMs) have been relatively unexplored by comparison. Operating under alkaline conditions offers significant efficiency benefits, especially for the oxygen reduction reaction; therefore, effective AAEMs could significantly advance fuel cell technologies. Here we demonstrate the use of ring-opening metathesis polymerization to generate new cross-linked membrane materials exhibiting high hydroxide ion conductivity and good mechanical properties. Cross-linking allows for increased ion incorporation, which, in turn supports high conductivities. This facile synthetic approach enables the preparation of cross-linked materials with the potential to meet the demands of hydrogen-powered fuel cells as well as direct methanol fuel cells. PMID:20178312

  2. Tunable High Performance Cross-Linked Alkaline Anion Exchange Membranes for Fuel Cell Applications

    SciTech Connect

    Robertson, Nicholas J.; Kostalik, IV, Henry A.; Clark, Timothy J.; Mutolo, Paul F.; Abruña, Héctor D.; Coates, Geoffrey W.

    2010-02-23

    Fuel cells are energy conversion devices that show great potential in numerous applications ranging from automobiles to portable electronics. However, further development of fuel cell components is necessary for them to become commercially viable. One component critical to their performance is the polymer electrolyte membrane, which is an ion conductive medium separating the two electrodes. While proton conducting membranes are well established (e.g., Nafion), hydroxide conducting membranes (alkaline anion exchange membranes, AAEMs) have been relatively unexplored by comparison. Operating under alkaline conditions offers significant efficiency benefits, especially for the oxygen reduction reaction; therefore, effective AAEMs could significantly advance fuel cell technologies. Here we demonstrate the use of ring-opening metathesis polymerization to generate new cross-linked membrane materials exhibiting high hydroxide ion conductivity and good mechanical properties. Cross-linking allows for increased ion incorporation, which, in turn supports high conductivities. This facile synthetic approach enables the preparation of cross-linked materials with the potential to meet the demands of hydrogen-powered fuel cells as well as direct methanol fuel cells.

  3. Reversible bond formation enables the replication and amplification of a crosslinking salen complex as an orthogonal base pair

    NASA Astrophysics Data System (ADS)

    Kaul, Corinna; Müller, Markus; Wagner, Mirko; Schneider, Sabine; Carell, Thomas

    2011-10-01

    The universal genetic code relies on two hydrogen-bonded Watson-Crick base pairs that can form 64 triplet codons. This places a limit on the number of amino acids that can be encoded, which has motivated efforts to create synthetic base pairs that are orthogonal to the natural ones. An additional base pair would result in another 61 triplet codons. Artificial organic base pairs have been described in enzymatic incorporation studies, and inorganic T-Hg-T and C-Ag-C base pairs have been reported to form in primer extension studies. Here, we demonstrate a metal base pair that is fully orthogonal and can be replicated, and can even be amplified by polymerase chain reaction in the presence of the canonical pairs dA:dT and dG:dC. Crystal structures of a dS-Cu-dS base pair inside a polymerase show that reversible chemistry is possible directly inside the polymerase, which enables the efficient copying of the inorganic crosslink. The results open up the possibility of replicating and amplifying artificial inorganic DNA nanostructures by extending the genetic alphabet.

  4. High temperature concrete composites containing organosiloxane crosslinked copolymers

    DOEpatents

    Zeldin, Arkady; Carciello, Neal; Kukacka, Lawrence; Fontana, Jack

    1980-01-01

    This invention relates to high temperature polymer concrete composites comprising about 10-30% by weight of a liquid monomer mixture consisting essentially of an organosiloxane polymer crosslinked with an olefinically unsaturated monomer selected from the group consisting of styrene, methyl methacrylate, trimethylolpropane trimethacrylate, triallyl cyanurate, n-phenylmalimide, divinyl benzene and mixtures theroef; and about 70-90% by weight of an inert inorganic filler system containing silica sand and preferably a member selected from the group consisting of portland cement, Fe.sub.2 O.sub.3, carbon black and mixtures thereof; and optionally a free radical initiator such as di-tert-butyl peroxide, azobisisobutyronitrile, benzoyl peroxide, lauryl peroxide and other organic peroxides to initiate crosspolymerization of the monomer mixture in the presence of the inorganic filler.

  5. High temperature concrete composites containing organosiloxane crosslinked copolymers

    DOEpatents

    Zeldin, A.; Carciello, N.; Kukacka, L.; Fontana, J.

    High temperature polymer concrete composites comprising about 10 to 30% by weight of a liquid monomer mixture is described. It consists essentially of an organosiloxane polymer crosslinked with an olefinically unsaturated monomer selected from the group consisting of styrene, methyl methacrylate, trimethylolpropane trimethacrylate, triallyl cyanurate, n-phenylmalimide, divinyl benzene and mixtures thereof. About 70 to 90% by weight of an inert inorganic filler system containing silica sand and portland cement, Fe/sub 2/O/sub 3/, carbon black or mixtures thereof. Optionally a free radical initiator such as di-tert-butyl peroxide, azobisisobyutyronitrile, benzoyl peroxide, lauryl peroxide and other organic peroxides are used to initiate crosspolymerization of the monomer mixture in the presence of the inorganic filler.

  6. A highly reversible room-temperature lithium metal battery based on crosslinked hairy nanoparticles

    NASA Astrophysics Data System (ADS)

    Choudhury, Snehashis; Mangal, Rahul; Agrawal, Akanksha; Archer, Lynden A.

    2015-12-01

    Rough electrodeposition, uncontrolled parasitic side-reactions with electrolytes and dendrite-induced short-circuits have hindered development of advanced energy storage technologies based on metallic lithium, sodium and aluminium electrodes. Solid polymer electrolytes and nanoparticle-polymer composites have shown promise as candidates to suppress lithium dendrite growth, but the challenge of simultaneously maintaining high mechanical strength and high ionic conductivity at room temperature has so far been unmet in these materials. Here we report a facile and scalable method of fabricating tough, freestanding membranes that combine the best attributes of solid polymers, nanocomposites and gel-polymer electrolytes. Hairy nanoparticles are employed as multifunctional nodes for polymer crosslinking, which produces mechanically robust membranes that are exceptionally effective in inhibiting dendrite growth in a lithium metal battery. The membranes are also reported to enable stable cycling of lithium batteries paired with conventional intercalating cathodes. Our findings appear to provide an important step towards room-temperature dendrite-free batteries.

  7. A highly reversible room-temperature lithium metal battery based on crosslinked hairy nanoparticles.

    PubMed

    Choudhury, Snehashis; Mangal, Rahul; Agrawal, Akanksha; Archer, Lynden A

    2015-12-04

    Rough electrodeposition, uncontrolled parasitic side-reactions with electrolytes and dendrite-induced short-circuits have hindered development of advanced energy storage technologies based on metallic lithium, sodium and aluminium electrodes. Solid polymer electrolytes and nanoparticle-polymer composites have shown promise as candidates to suppress lithium dendrite growth, but the challenge of simultaneously maintaining high mechanical strength and high ionic conductivity at room temperature has so far been unmet in these materials. Here we report a facile and scalable method of fabricating tough, freestanding membranes that combine the best attributes of solid polymers, nanocomposites and gel-polymer electrolytes. Hairy nanoparticles are employed as multifunctional nodes for polymer crosslinking, which produces mechanically robust membranes that are exceptionally effective in inhibiting dendrite growth in a lithium metal battery. The membranes are also reported to enable stable cycling of lithium batteries paired with conventional intercalating cathodes. Our findings appear to provide an important step towards room-temperature dendrite-free batteries.

  8. Water and polymer dynamics in highly crosslinked polyamide membranes

    NASA Astrophysics Data System (ADS)

    Frieberg, Bradley; Chan, Edwin; Tyagi, Madhu; Stafford, Christopher; Soles, Christopher

    Highly crosslinked polyamides for reverse osmosis are the state-of-the-art active material in membranes for desalination. The thin film composite membrane structure that is used commercially has been empirically designed to selectively allow the passage of water molecules and minimize the passage of solutes such as salt. However, due to the large roughness and variability of the polyamide layer, there is a limited understanding of the structure-property relationship for these materials as well as the transport mechanism. To better understand the water transport mechanism we measure the water and polymer dynamics of polyamide membranes using quasi-elastic neutron scattering (QENS). By hydrating the membrane with deuterated water, we are able to isolate the dynamics of the hydrogenated membrane on the pico- and nanosecond time scales. By subsequently hydrating the membranes with hydrogenated water, the QENS measurements on the same times scales reveal information about both the translational and rotational dynamics of water confined within the polyamide membrane. Further understanding of the water diffusion mechanism will establish design rules in which the performance of future membrane materials can be improved.

  9. Metal Chelating Crosslinkers Form Nanogels with High Chelation Stability.

    PubMed

    Lux, Jacques; Chan, Minnie; Elst, Luce Vander; Schopf, Eric; Mahmoud, Enas; Laurent, Sophie; Almutairi, Adah

    2013-12-14

    We present a series of hydrogel nanoparticles (nanogels) incorporating either acyclic or cyclic metal chelates as crosslinkers. These crosslinkers are used to formulate polyacrylamide-based nanogels (diameter 50 to 85 nm) yielding contrast agents with enhanced relaxivities (up to 6-fold greater than Dotarem®), because this nanogel structure slows the chelator's tumbling frequency and allows fast water exchange. Importantly, these nanogels also stabilize Gd(3+) within the chelator thermodynamically and kinetically against metal displacement through transmetallation, which should reduce toxicity associated with release of free Gd(3+). This chelation stability suggests that the chelate crosslinker strategy may prove useful for other applications of metal-chelating nanoparticles in medicine, including other imaging modalities and radiotherapy.

  10. Metal Chelating Crosslinkers Form Nanogels with High Chelation Stability

    PubMed Central

    Elst, Luce Vander; Schopf, Eric; Mahmoud, Enas; Laurent, Sophie; Almutairi, Adah

    2013-01-01

    We present a series of hydrogel nanoparticles (nanogels) incorporating either acyclic or cyclic metal chelates as crosslinkers. These crosslinkers are used to formulate polyacrylamide-based nanogels (diameter 50 to 85 nm) yielding contrast agents with enhanced relaxivities (up to 6-fold greater than Dotarem®), because this nanogel structure slows the chelator's tumbling frequency and allows fast water exchange. Importantly, these nanogels also stabilize Gd3+ within the chelator thermodynamically and kinetically against metal displacement through transmetallation, which should reduce toxicity associated with release of free Gd3+. This chelation stability suggests that the chelate crosslinker strategy may prove useful for other applications of metal-chelating nanoparticles in medicine, including other imaging modalities and radiotherapy. PMID:24505553

  11. Metal Chelating Crosslinkers Form Nanogels with High Chelation Stability.

    PubMed

    Lux, Jacques; Chan, Minnie; Elst, Luce Vander; Schopf, Eric; Mahmoud, Enas; Laurent, Sophie; Almutairi, Adah

    2013-12-14

    We present a series of hydrogel nanoparticles (nanogels) incorporating either acyclic or cyclic metal chelates as crosslinkers. These crosslinkers are used to formulate polyacrylamide-based nanogels (diameter 50 to 85 nm) yielding contrast agents with enhanced relaxivities (up to 6-fold greater than Dotarem®), because this nanogel structure slows the chelator's tumbling frequency and allows fast water exchange. Importantly, these nanogels also stabilize Gd(3+) within the chelator thermodynamically and kinetically against metal displacement through transmetallation, which should reduce toxicity associated with release of free Gd(3+). This chelation stability suggests that the chelate crosslinker strategy may prove useful for other applications of metal-chelating nanoparticles in medicine, including other imaging modalities and radiotherapy. PMID:24505553

  12. Characterization of radiation-crosslinked, high-density polyethylene for thermal energy storage applications. [Electron beams

    SciTech Connect

    Whitaker, R.B.; Craven, S.M.; Etter, D.E.; Jendrek, E.F.

    1981-01-01

    This study is directed toward characterization of the crosslinked, form-stable high-density polyethylene (HDPE) pellets produced by electron beam radiation crosslinking, and the effects of crosslinking on crystallinity and heat of fusion. Methods used include differential scanning calorimetry (DSC), Fourier Transform Infrared Spectroscopy (FTIR), and x-ray diffraction measurements. DSC measurements of the heats of fusion (..delta..H/sub f/) of the radiation-crosslinked HDPE showed that while a substantial decrease in ..delta..H/sub f/ occurred after the first melting cycle, slow cooling on recrystallization of the pellets could restore the ..delta..H/sub f/ value to greater than or equal to 95% of that of the uncrosslinked HDPE up to 9.0 Mrad dosage exposure. The form stability of the 9.0-Mrad HDPE was very good even after 500 melt-freeze cycles in ethylene glycol. However, some further decline in ..delta..H/sub f/ was noted and more extensive thermal cycling tests would be required to verify this. X-ray diffraction measurements showed little or no difference in crystallinity among the various radiation-crosslinked HDPE's and the uncrosslinked control HDPE. This indicates the crosslinking occurs primarily in the amorphous regions of the polyethylene. FTIR spectroscopy was used to estimate the relative amounts of crosslinking occurring with the varying radiation dosages, and the uniformity of crosslinking throughout the pellets. The relative amount of crosslinking was based on the ratio of the 965 cm/sup -1/ absorption band to the 909 cm/sup -1/ band. This ratio did increase with increasing radiation dosage: from 1.9 for the crosslinked HDPE dosed with 9.0 Mrad, to 5.3 for that dosed with 18.0 Mrad. Also, the amount of crosslinking from the outside to the center of the pellets was found to be uniform, which would assist in maintaining long-term form stability in the pellets.

  13. Physical properties of pectin-high amylose starch mixtures cross-linked with sodium trimetaphosphate.

    PubMed

    Carbinatto, Fernanda M; de Castro, Ana Dóris; Cury, Beatriz S F; Magalhães, Alviclér; Evangelista, Raul C

    2012-02-28

    Pectin-high amylose starch mixtures (1:4; 1:1; 4:1) were cross-linked at different degrees and characterized by rheological, thermal, X-ray diffraction and NMR analyses. For comparison, samples without cross-linker addition were also prepared and characterized. Although all samples behaved as gels, the results evidenced that the phosphorylation reaction promotes the network strengthening, resulting in covalent gels (highest critical stress, G' and recovery %). Likewise, cross-linked samples presented the highest thermal stability. However, alkaline treatment without cross-linker allowed a structural reorganization of samples, as they also behaved as covalent gels, but weaker than those gels from cross-linked samples, and presented higher thermal stability than the physical mixtures. X-ray diffractograms also evidenced the occurrence of physical and chemical modifications due to the cross-linking process and indicated that samples without cross-linker underwent some structural reorganization, resulting in a decrease of crystallinity. The chemical shift of resonance signals corroborates the occurrence of structural modifications by both alkaline treatment and cross-linking reaction. PMID:22178896

  14. Polymorphism of highly cross-linked F-actin networks: Probing multiple length scales

    NASA Astrophysics Data System (ADS)

    Nguyen, Lam T.; Hirst, Linda S.

    2011-03-01

    The assembly properties of F-actin filaments in the presence of different biological cross-linker concentrations and types have been investigated using a combined approach of fluorescence confocal microscopy and coarse-grained molecular dynamics simulation. In particular for highly cross-linked regimes, new network morphologies are observed. Complex network formation and the details of the resulting structure are strongly dependent on the ratio of cross-linkers to actin monomers and cross-linker shape but only weakly dependent on overall actin concentration and filament length. The work presented here may help to provide some fundamental understanding of how excessive cross-linkers interact with the actin filament solution, creating different structures in the cell under high cross-linker concentrations. F-actin is not only of biological importance but also, as an example of a semiflexible polymer, has attracted significant interest in its physical behavior. In combination with different cross-linkers semiflexible filaments may provide new routes to bio-materials development and act as the inspiration for new hierarchical network-based materials.

  15. Cross-linking high-k fluoropolymer gate dielectrics enhances the charge mobility in rubrene field effect transistors

    NASA Astrophysics Data System (ADS)

    Adhikari, Jwala; Gadinski, Matthew; Wang, Qing; Gomez, Enrique

    2015-03-01

    Polymer dielectrics are promising materials where the chemical flexibility enables gate insulators with desired properties. For example, polar groups can be introduced to enhance the dielectric constant, although fluctuations in chain conformations at the semiconductor-dielectric interface can introduce energetic disorder and limit charge mobilities in thin-film transistors. Here, we demonstrate a photopatternable high-K fluoropolymer, poly(vinylidene fluoride-bromotrifluoroethylene) P(VDF-BTFE), with a dielectric constant between 8 and 11. The bromotrifluoroethylene moiety enables photo-crosslinking and stabilization of gate insulator films while also significantly enhancing the population of trans torsional conformations of the chains. Using rubrene single crystals as the active layer, charge mobilities exceeding 10 cm2/Vs are achieved in thin film transistors with cross-linked P(VDF-BTFE) gate dielectrics. We hypothesize that crosslinking reduces energetic disorder at the dielectric-semiconductor interface by suppressing segmental motion and controlling chain conformations of P(VDF-BTFE), thereby leading to approximately a three-fold enhancement in the charge mobility of rubrene thin-film transistors over devices incorporating uncross-linked dielectrics or silicon oxide. Center for Flexible Electronic, Penn State; The Dow Chemical Company.

  16. In Vivo Oxidative Stability Changes of Highly Cross-Linked Polyethylene Bearings: An Ex Vivo Investigation.

    PubMed

    Rowell, Shannon L; Reyes, Christopher R; Malchau, Henrik; Muratoglu, Orhun K

    2015-10-01

    The development of highly cross-linked UHMWPEs focused on stabilizing radiation-induced free radicals as the sole precursor to oxidative degradation. However, secondary in vivo oxidation mechanisms have been discovered. After a preliminary post-operative analysis, we subjected highly cross-linked retrievals with 1-4 years in vivo durations and never-implanted controls to accelerated aging to predict the extent to which their oxidative stability was compromised in vivo. Lipid absorption, oxidation, and hydroperoxides were measured using infrared spectroscopy. Gravimetric swelling was used to measure cross-link density. After aging, all retrievals, except vitamin E-stabilized components, regardless of initial lipid levels or oxidation, showed significant oxidative degradation, demonstrated by subsurface oxidative peaks, increased hydroperoxides and decreased cross-link density, compared to their post-operative material properties and never-implanted counterparts, confirming oxidative stability changes.

  17. No adverse effects of submelt-annealed highly crosslinked polyethylene in cemented cups

    PubMed Central

    2012-01-01

    Background and purpose Highly crosslinked polyethylene (PE) is in standard use worldwide. Differences in the crosslinking procedure may affect the clinical performance. Experimenatal data from retrieved cups have shown free radicals and excessive wear of annealed highly crosslinked PE. We have previously reported low wear and good clinical performance after 6 years with this implant, and now report on the 10-year results. Patients and methods In 8 patients, we measured wear of annealed highly crosslinked PE prospectively with radiostereometry after 10 years. Activity was assessed by UCLA activity score and a specifically designed activity score. Conventional radiographs were evaluated for osteolysis and clinical outcome by the Harris hip score (HHS). Results The mean (95% CI) proximal head penetration for highly crosslinked PE after 10 years was 0.07 (–0.015 to 0.153) mm, and the 3D wear was 0.2 (0.026 to 0.36) mm. Without creep, proximal head penetration was 0.02 (–0.026 to 0.066) mm and for 3D penetration was 0.016 (–0.47 to 0.08) mm. This represents an annual proximal wear of less than 2 µm. All cups were clinically and radiographically stable but showed a tendency of increased rotation after 5 years. Interpretation Wear for annealed highly crosslinked PE is extremely low up to 10 years. Free radicals do not affect mechanical performance or lead to clinically adverse effects. Creep stops after the first 6 months after implantation. Highly crosslinked PE is a true competitor of hard-on-hard bearings. PMID:22248172

  18. Quantum dot enabled high color gamut LCDs

    NASA Astrophysics Data System (ADS)

    Chen, Jian; Kan, Shihai; Lee, Ernie; Gensler, Steve; Hartlove, Jason

    2015-03-01

    Quantum dots are a new generation of phosphor material that have high photon conversion efficiency, narrow spectral line-widths and can be continuously tuned in their emission wavelengths. Since 2013, quantum dots have been adopted by the consumer electronics industry into LCDs to significantly increase their color performance. Compared to the OLED solution, quantum dot LCDs have higher energy efficiency, larger color gamut, longer lifetime, and are offered at a fraction of the cost of OLED panels. In this paper, we demonstrate that quantum-dot based LCDs can achieve more than 90% coverage of the ultra-wide color gamut, Rec. 2020, which is the new color standard for UHDTV.

  19. Friedel–Crafts Crosslinked Highly Sulfonated Polyether Ether Ketone (SPEEK) Membranes for a Vanadium/Air Redox Flow Battery

    PubMed Central

    Merle, Géraldine; Ioana, Filipoi Carmen; Demco, Dan Eugen; Saakes, Michel; Hosseiny, Seyed Schwan

    2014-01-01

    Highly conductive and low vanadium permeable crosslinked sulfonated poly(ether ether ketone) (cSPEEK) membranes were prepared by electrophilic aromatic substitution for a Vanadium/Air Redox Flow Battery (Vanadium/Air-RFB) application. Membranes were synthesized from ethanol solution and crosslinked under different temperatures with 1,4-benzenedimethanol and ZnCl2 via the Friedel–Crafts crosslinking route. The crosslinking mechanism under different temperatures indicated two crosslinking pathways: (a) crosslinking on the sulfonic acid groups; and (b) crosslinking on the backbone. It was observed that membranes crosslinked at a temperature of 150 °C lead to low proton conductive membranes, whereas an increase in crosslinking temperature and time would lead to high proton conductive membranes. High temperature crosslinking also resulted in an increase in anisotropy and water diffusion. Furthermore, the membranes were investigated for a Vanadium/Air Redox Flow Battery application. Membranes crosslinked at 200 °C for 30 min with a molar ratio between 2:1 (mol repeat unit:mol benzenedimethanol) showed a proton conductivity of 27.9 mS/cm and a 100 times lower VO2+ crossover compared to Nafion. PMID:24957118

  20. Friedel-Crafts Crosslinked Highly Sulfonated Polyether Ether Ketone (SPEEK) Membranes for a Vanadium/Air Redox Flow Battery.

    PubMed

    Merle, Géraldine; Ioana, Filipoi Carmen; Demco, Dan Eugen; Saakes, Michel; Hosseiny, Seyed Schwan

    2013-12-30

    Highly conductive and low vanadium permeable crosslinked sulfonated poly(ether ether ketone) (cSPEEK) membranes were prepared by electrophilic aromatic substitution for a Vanadium/Air Redox Flow Battery (Vanadium/Air-RFB) application. Membranes were synthesized from ethanol solution and crosslinked under different temperatures with 1,4-benzenedimethanol and ZnCl2 via the Friedel-Crafts crosslinking route. The crosslinking mechanism under different temperatures indicated two crosslinking pathways: (a) crosslinking on the sulfonic acid groups; and (b) crosslinking on the backbone. It was observed that membranes crosslinked at a temperature of 150 °C lead to low proton conductive membranes, whereas an increase in crosslinking temperature and time would lead to high proton conductive membranes. High temperature crosslinking also resulted in an increase in anisotropy and water diffusion. Furthermore, the membranes were investigated for a Vanadium/Air Redox Flow Battery application. Membranes crosslinked at 200 °C for 30 min with a molar ratio between 2:1 (mol repeat unit:mol benzenedimethanol) showed a proton conductivity of 27.9 mS/cm and a 100 times lower VO2+ crossover compared to Nafion.

  1. A highly reversible room-temperature lithium metal battery based on crosslinked hairy nanoparticles

    PubMed Central

    Choudhury, Snehashis; Mangal, Rahul; Agrawal, Akanksha; Archer, Lynden A.

    2015-01-01

    Rough electrodeposition, uncontrolled parasitic side-reactions with electrolytes and dendrite-induced short-circuits have hindered development of advanced energy storage technologies based on metallic lithium, sodium and aluminium electrodes. Solid polymer electrolytes and nanoparticle-polymer composites have shown promise as candidates to suppress lithium dendrite growth, but the challenge of simultaneously maintaining high mechanical strength and high ionic conductivity at room temperature has so far been unmet in these materials. Here we report a facile and scalable method of fabricating tough, freestanding membranes that combine the best attributes of solid polymers, nanocomposites and gel-polymer electrolytes. Hairy nanoparticles are employed as multifunctional nodes for polymer crosslinking, which produces mechanically robust membranes that are exceptionally effective in inhibiting dendrite growth in a lithium metal battery. The membranes are also reported to enable stable cycling of lithium batteries paired with conventional intercalating cathodes. Our findings appear to provide an important step towards room-temperature dendrite-free batteries. PMID:26634644

  2. Comparison of Wear and Oxidation in Retrieved Conventional and Highly Cross-Linked UHMWPE Tibial Inserts.

    PubMed

    Currier, Barbara H; Currier, John H; Franklin, Katherine J; Mayor, Michael B; Reinitz, Steven D; Van Citters, Douglas W

    2015-12-01

    Two groups of retrieved tibial inserts from one manufacturer's knee system were analyzed to evaluate the effect of a highly cross-linked bearing surface on wear and in vivo oxidation. The two groups ((1) conventional gamma-inert sterilized and (2) highly cross-linked, coupled with the same rough (Ra=0.25) Ti-6Al-4V tray) were matched with statistically similar in vivo duration and patient variables. The retrieved inserts were analyzed for ketone oxidation and wear in the form of dimensional change. The difference in oxidation rate between highly cross-linked and conventional gamma-inert sterilized inserts did not reach statistical significance. Observations suggest that the majority of wear can be accounted for by the backside interface with the rough Ti-6Al-4V tray; however, wear measured by thickness-change rate was statistically indistinguishable between the two bearing materials.

  3. Fatigue crack propagation resistance of virgin and highly crosslinked, thermally treated ultra-high molecular weight polyethylene.

    PubMed

    Gencur, Sara J; Rimnac, Clare M; Kurtz, Steven M

    2006-03-01

    To prolong the life of total joint replacements, highly crosslinked ultra-high molecular weight polyethylenes (UHMWPEs) have been introduced to improve the wear resistance of the articulating surfaces. However, there are concerns regarding the loss of ductility and potential loss in fatigue crack propagation (FCP) resistance. The objective of this study was to evaluate the effects of gamma radiation-induced crosslinking with two different post-irradiation thermal treatments on the FCP resistance of UHMWPE. Two highly crosslinked and one virgin UHMWPE treatment groups (ram-extruded, orthopedic grade, GUR 1050) were examined. For the two highly crosslinked treatment groups, UHMWPE rods were exposed to 100 kGy and then underwent post-irradiation thermal processing either above the melt temperature or below the melt temperature (2 h-150 degrees C, 110 degrees C). Compact tension specimens were cyclically loaded to failure and the fatigue crack growth rate, da/dN, vs. cyclic stress intensity factor, DeltaK, behavior was determined and compared between groups. Scanning electron microscopy was used to examine fracture surface characteristics. Crosslinking was found to decrease the ability of UHMWPE to resist crack inception and propagation under cyclic loading. The findings also suggested that annealing as a post-irradiation treatment may be somewhat less detrimental to FCP resistance of UHMWPE than remelting. Scanning electron microscopy examination of the fracture surfaces demonstrated that the virgin treatment group failed in a more ductile manner than the two highly crosslinked treatment groups.

  4. Durability of highly cross-linked polyethylene in total hip and total knee arthroplasty.

    PubMed

    Dion, Neil T; Bragdon, Charles; Muratoglu, Orhun; Freiberg, Andrew A

    2015-07-01

    This article reviews the history of the development of highly cross-linked polyethylene and provides an in-depth review of the clinical results regarding the durability of highly cross-linked polyethylene (HXLPE) used in total hip arthroplasty (THA) and total knee arthroplasty (TKA). The use of polyethylene as a bearing surface has contributed to the success of THA and TKA; however, polyethylene wear and osteolysis can lead to failure. Ongoing clinical and retrieval studies are required to analyze outcomes at longer-term follow-up.

  5. Durability of highly cross-linked polyethylene in total hip and total knee arthroplasty.

    PubMed

    Dion, Neil T; Bragdon, Charles; Muratoglu, Orhun; Freiberg, Andrew A

    2015-07-01

    This article reviews the history of the development of highly cross-linked polyethylene and provides an in-depth review of the clinical results regarding the durability of highly cross-linked polyethylene (HXLPE) used in total hip arthroplasty (THA) and total knee arthroplasty (TKA). The use of polyethylene as a bearing surface has contributed to the success of THA and TKA; however, polyethylene wear and osteolysis can lead to failure. Ongoing clinical and retrieval studies are required to analyze outcomes at longer-term follow-up. PMID:26043046

  6. Vitamin E-diffused highly cross-linked UHMWPE particles induce less osteolysis compared to highly cross-linked virgin UHMWPE particles in vivo.

    PubMed

    Bichara, David A; Malchau, Erik; Sillesen, Nanna H; Cakmak, Selami; Nielsen, G Petur; Muratoglu, Orhun K

    2014-09-01

    Recent in vitro findings suggest that UHMWPE wear particles containing vitamin E (VE) may have reduced biologic activity and decreased osteolytic potential. We hypothesized that particles from VE-stabilized, radiation cross-linked UHMWPE would cause less osteolysis in a murine calvarial bone model when compared to virgin gamma irradiated cross-linked UHMWPE. Groups received equal amount of particulate debris overlaying the calvarium for 10 days. Calvarial bone was examined using high resolution micro-CT and histomorphometric analyses. There was a statistically significant difference between virgin (12.2%±8%) and VE-UHMWPE (3%±1.4%) groups in regards to bone resorption (P=0.005) and inflammatory fibrous tissue overlaying the calvaria (0.48 vs. 0.20, P<0.0001). These results suggest that VE-UHMWPE particles have reduced osteolytic potential in vivo when compared to virgin UHMWPE.

  7. Cross-linked block copolymer templated assembly of nanoparticle arrays with high density and position selectivity

    NASA Astrophysics Data System (ADS)

    Liu, Zhicheng; Chang, Tongxin; Huang, Haiying; Bai, Lu

    2016-10-01

    Patterning ordered nanoparticle arrays is crucial for the fascinating collective properties of nanoparticles. Block copolymer template provides us a platform for the simple and efficient assembly of nanoparticle arrays. In this work, cylinder-forming poly(styrene-block-2-vinylpyridine) thin film was firstly plasma-etched to expose poly(2-vinylpyridine) cylinders. Then the templates were cross-linked by small molecules so as to access gold nanoparticle arrays with both high density and excellent position selectivity. The cross-linking process significantly restrains the unfavorable surface reconstruction of the thin film. It is demonstrated that the quality of the nanoparticle array was affected by the degree of the cross-linking and the immersion time in nanoparticle solution. The highly ordered gold nanoparticle arrays are promising in several fields such as optics and surface enhanced Raman scattering (SERS).

  8. Dynamic Heterogeneity in Highly Cross-linked Epoxy in the Vicinity of Glass Transition

    NASA Astrophysics Data System (ADS)

    Lin, Po-Han; Khare, Rajesh

    2010-03-01

    Cross-linked epoxy has been widely used in aerospace and electronics industries. The highly cross-linked nature of these systems leads to different chain dynamics as compared to the linear polymeric systems. In this work, we have used molecular dynamics (MD) simulations to study the dynamic heterogeneity in cross-linked epoxy near the glass transition temperature. Well-relaxed atomistic models of cross-linked epoxy were first created by employing the simulated annealing polymerization approach. The specific epoxy system studied consisted of diglycidyl ether of bisphenol-A (DGEBA) as the epoxy monomer and trimethylene glycol di-p-aminobenzoate (TMAB) as the cross-linker. The glass transition temperature of these model structures was determined from MD simulation by monitoring their volume-temperature behaviour in a stepwise cooling run. The chain dynamics of these systems were characterized by their local translational and orientational mobility. Furthermore, dynamic heterogeneity was studied by analyzing the spatial distribution of the mobile and immobile atoms in the system near the glass transition temperature.

  9. Tensile and tribological properties of high-crystallinity radiation crosslinked UHMWPE

    SciTech Connect

    Bistolfi, Alessandro; Turell, Mary Beth; Lee, Ying-Lung; Bellare, Anuj

    2009-09-02

    Osteolysis due to particulate wear debris associated with ultrahigh molecular weight polyethylene (UHMWPE) components of total joint replacement prostheses has been a major factor determining their in vivo lifetime. In recent years, radiation crosslinking has been employed to decrease wear rates in PE components, especially in acetabular cups of total hip replacement prostheses. A drawback of radiation crosslinking is that it leads to a crosslinked PE (or XPE) with lower mechanical properties compared with uncrosslinked PE. In contrast, high-crystallinity PEs are known to have several mechanical properties higher than conventional PE. In this study, we hypothesized that increasing the crystallinity of radiation crosslinked and remelted XPE would result in an increase in tensile properties without compromising wear resistance. High-pressure crystallization was performed on PE and XPE and analyzed for the resulting morphological alterations using differential scanning calorimeter, low voltage scanning electron microscopy, and ultrasmall angle X-ray scattering. Uniaxial tensile tests showed that high-pressure crystallization increased the tensile modulus and yield stress in both PE and XPE, decreased the ultimate strain and ultimate stress in PE but had no significant effect on ultimate strain or ultimate stress in XPE. Multidirectional wear tests demonstrated that high-pressure crystallization decreased the wear resistance of PE but had no effect on the wear resistance of XPE. In conclusion, this study shows that high-pressure crystallization can be effectively used to increase the crystallinity and modulus of XPE without compromising its superior wear resistance compared with PE.

  10. Comparison between decrosslinking of crosslinked high and low density polyethylenes via ultrasonically aided extrusion

    NASA Astrophysics Data System (ADS)

    Isayev, Avraam I.; Huang, Keyuan

    2016-03-01

    Among various crosslinked plastics, recycling of crosslinked polyethylenes is of a great importance due to the presence of a three-dimensional network. To solve this problem, novel environmentally friendly technologies for decrosslinking of the crosslinked polymers are developed based on ultrasonically assisted single (SSE) and twin screw (TSE) extruders. In particular, decrosslinking of peroxide crosslinked high-density polyethylene (XHDPE) and low-density polyethylene (XLDPE) by means of an ultrasonic SSE and TSE is investigated. Barrel pressure, die pressure and ultrasonic power consumption during extrusion are recorded. Swelling, rheological, thermal analysis and tensile tests are used to elucidate the structure-property relationships of decrosslinked XHDPE and XLDPE. The frequency dependencies of the storage and loss moduli, complex viscosity and tangent loss of XHDPE, XLDPE and their decrosslinked networks are described by the post critical gel model with its parameters correlated with gel fraction and crosslink density. The dynamic, thermal and tensile properties of the decrosslinked XHDPE and XLDPE are greatly affected by the type of preferential bond breakage. It was found that the decrosslinking of XLDPE is more difficult than that of XHDPE. An analysis based on the Horikx function reveals a highly preferential breakage of crosslinks during decrosslinking of XHDPE. In contrast to decrosslinking of XHDPE, the presence of long-chain branching in XLDPE is found to lead to the breakage of its main chains during decrosslinking. An improvement and a reduction in mechanical properties of decrosslinked XHDPE and XLDPE are, respectively, observed in comparison with those of virgin XHDPE and XLDPE.

  11. Probabilistic cross-link analysis and experiment planning for high-throughput elucidation of protein structure.

    PubMed

    Ye, Xiaoduan; O'Neil, Patrick K; Foster, Adrienne N; Gajda, Michal J; Kosinski, Jan; Kurowski, Michal A; Bujnicki, Janusz M; Friedman, Alan M; Bailey-Kellogg, Chris

    2004-12-01

    Emerging high-throughput techniques for the characterization of protein and protein-complex structures yield noisy data with sparse information content, placing a significant burden on computation to properly interpret the experimental data. One such technique uses cross-linking (chemical or by cysteine oxidation) to confirm or select among proposed structural models (e.g., from fold recognition, ab initio prediction, or docking) by testing the consistency between cross-linking data and model geometry. This paper develops a probabilistic framework for analyzing the information content in cross-linking experiments, accounting for anticipated experimental error. This framework supports a mechanism for planning experiments to optimize the information gained. We evaluate potential experiment plans using explicit trade-offs among key properties of practical importance: discriminability, coverage, balance, ambiguity, and cost. We devise a greedy algorithm that considers those properties and, from a large number of combinatorial possibilities, rapidly selects sets of experiments expected to discriminate pairs of models efficiently. In an application to residue-specific chemical cross-linking, we demonstrate the ability of our approach to plan experiments effectively involving combinations of cross-linkers and introduced mutations. We also describe an experiment plan for the bacteriophage lambda Tfa chaperone protein in which we plan dicysteine mutants for discriminating threading models by disulfide formation. Preliminary results from a subset of the planned experiments are consistent and demonstrate the practicality of planning. Our methods provide the experimenter with a valuable tool (available from the authors) for understanding and optimizing cross-linking experiments. PMID:15557270

  12. EFFECT OF CROSSLINK DENSITY ON THE HIGH PRESSURE CRYSTALLIZATION OF UHMWPE

    PubMed Central

    Oral, Ebru; Beckos, Christine Godleski; Ghali, Bassem W.; Lozynsky, Andrew J.; Muratoglu, Orhun K.

    2010-01-01

    Ultrahigh molecular weight polyethylene (UHMWPE) is a bearing surface material for total joint implants. It is radiation cross-linked for high wear resistance and is melted or treated with vitamin E for oxidative stability. We investigated high pressure crystallization (HPC) of irradiated UHMWPE as an alternative method to improve the mechanical strength while stabilizing the residual free radicals from radiation crosslinking. HPC of uncross-linked UHMWPE has resulted in the formation of extended chain crystals and increased crystallinity, leading to improved strength. We hypothesized that increased cross-link density would hinder crystallization during HPC due to decreased chain mobility. Therefore, we investigated the crystalline structure and tensile mechanical properties of high pressure crystallized 25-, 65- and 100-kGy irradiated UHMWPE. We also determined free radical content and wear. The strength of 25- and 65-kGy irradiated UHMWPEs was improved by HPC with increased crystallinity and crystal size. 100-kGy irradiated UHMWPE did not show improved strength, supporting our hypothesis that decreased chain mobility would hinder crystal formation and strength improvement. None of the HPC irradiated UHMWPEs contained detectable free radicals and their wear properties were maintained, suggesting oxidative and mechanical stability in the long term. Therefore, HPC can be used effectively for imparting oxidative stability while strength improvement can be achieved for irradiated UHMWPE with low to moderate crosslink density. PMID:19213055

  13. THE EFFECTS OF HIGH DOSE IRRADIATION ON THE CROSS-LINKING OF VITAMIN E-BLENDED ULTRAHIGH MOLECULAR WEIGHT POLYETHYLENE

    PubMed Central

    Oral, Ebru; Beckos, Christine Godleski; Malhi, Arnaz S.; Muratoglu, Orhun K.

    2008-01-01

    Vitamin E-stabilized, highly cross-linked ultrahigh molecular weight polyethylene (UHMWPE) is a promising oxidation and wear resistant UHMWPE with improved mechanical strength in comparison with the first generation, irradiated and melted UHMWPE. One approach of incorporating vitamin E in UHMWPE is through blending of vitamin E in UHMWPE powder followed by consolidation and radiation crosslinking. However radiation crosslinking efficiency of UHMWPE decreases in the presence of vitamin E. Therefore an optimum vitamin E concentration and radiation dose level needs to be determined to achieve a cross-link density comparable to 100-kGy irradiated and melted UHMWPE, which has shown excellent wear properties in vivo. We investigated the cross-link density and mechanical properties of vitamin E-blended UHMWPEs as a function of vitamin E concentration in the blend and gamma irradiation doses up to 200 kGy. We found that 0.3 wt% vitamin E-blended UHMWPE could not be cross-linked above a cross-link density achieved at a radiation dose of 65 kGy for virgin UHMWPE and 1.0 wt% vitamin E-blended UHMWPE could not be cross-linked above a cross-link density achieved at a radiation dose of 25 kGy for virgin UHMWPE even when the former were irradiated to a radiation dose of 200 kGy. In addition, higher plasticity at vitamin E concentrations at and above 0.3 wt% indicated that increased chain scissioning may be prevalent. Since the wear resistance of this irradiated UHMWPE would be expected to be low, vitamin E concentrations equal to or above 0.3 wt% are not recommended for subsequent irradiation to achieve a wear resistant cross-linked UHMWPE. The long–term oxidative stability of irradiated blends with low vitamin E concentrations has yet to be studied to determine an optimum between cross-link density and long-term oxidative stability. PMID:18514813

  14. Highly stable pyridinium-functionalized cross-linked anion exchange membranes for all vanadium redox flow batteries

    NASA Astrophysics Data System (ADS)

    Zeng, L.; Zhao, T. S.; Wei, L.; Zeng, Y. K.; Zhang, Z. H.

    2016-11-01

    It has recently been demonstrated that the use of anion exchange membranes (AEMs) in vanadium redox flow batteries (VRFBs) can reduce the migration of vanadium ions through the membrane due to the Donnan exclusion effect among the positively charged functional groups and vanadium ions. However, AEMs are plagued by low chemical stability in harsh chemical environments. Here we propose and fabricate a pyridinium-functionalized cross-linked AEM for VRFBs. The pyridinium-functionalized bromomethylated poly (2,6-dimethyl-1,4-phenylene oxide) exhibits a superior chemical stability as a result of the strengthened internal cross-linking networks and the chemical inertness of the polymer backbone. Therefore, the membrane exhibits littler decay in a harsh environment for 20 days during the course of an ex situ immersion test. A cycling test also demonstrates that the VRFB assembled with the membrane enable to retain 80% of the initial discharge capacity over 537 cycles with a capacity decay rate of 0.037% cycle-1. Meanwhile, the membrane also shows a low vanadium permeability and a reasonably high conductivity in supporting electrolytes. Hence, all the measurements and performance tests reported in this work suggest that the membrane is a promising AEM for redox flow batteries to achieve excellent cycling stability and superior cell performance.

  15. Minimum 10-Year Wear Analysis of Highly Cross-Linked Polyethylene in Cementless Total Hip Arthroplasty.

    PubMed

    So, Kazutaka; Goto, Koji; Kuroda, Yutaka; Matsuda, Shuichi

    2015-12-01

    Fifty-four patients (64 hips) underwent cementless total hip arthroplasty between 2000 and 2003 with a 22-mm zirconia ceramic bearing on highly cross-linked polyethylene, and were evaluated with a mean 11.9-year postoperative follow-up (range, 10-14 years). Linear wear was measured on the anteroposterior radiograph of the hip. No evidence of osteolysis and loosening was found on the final radiograph in any of the cases, and the steady-state linear wear rate was 0.017±0.018 mm/year. No significant correlation was found between the linear wear rate and age, body weight, cup inclination angle, or polyethylene thickness. Highly cross-linked polyethylene showed excellent wear resistance for >10 years when used in combination with 22-mm zirconia heads.

  16. Borate cross-linked graphene oxide-chitosan as robust and high gas barrier films

    NASA Astrophysics Data System (ADS)

    Yan, Ning; Capezzuto, Filomena; Lavorgna, Marino; Buonocore, Giovanna G.; Tescione, Fabiana; Xia, Hesheng; Ambrosio, Luigi

    2016-05-01

    Chitosan (CS) is one of the most promising polymers due to its biocompatibility, biodegradability, and natural abundance. However, its poor mechanical and barrier properties make it difficult to satisfy a wide range of applications. Herein, borate ions, originating from the hydrolysis of sodium tetraborate decahydrate (borax), have been used to crosslink chitosan and graphene oxide (GO) nanocomposites. Chitosan films consisting of 1.0 wt% boron and 1.0 wt% GO exhibit a significant improvement in both the toughness and oxygen barrier properties compared to pristine chitosan. In particular the tensile strength of the samples after thermal treatment increases by ~160% compared to pristine chitosan, whereas their oxygen permeability reduces by ~90%. This is ascribed to the chemical crosslinking between chitosan and GO nanoplatelets through borate ions, as well as the formation of a layered morphology with graphene nanoplatelets oriented parallel to the sample surface. The exceptional robust and high gas barrier film has promising application in the packaging industry. The borate-crosslinking chemistry represents the potential strategy for improving properties of other polymer nanocomposites.Chitosan (CS) is one of the most promising polymers due to its biocompatibility, biodegradability, and natural abundance. However, its poor mechanical and barrier properties make it difficult to satisfy a wide range of applications. Herein, borate ions, originating from the hydrolysis of sodium tetraborate decahydrate (borax), have been used to crosslink chitosan and graphene oxide (GO) nanocomposites. Chitosan films consisting of 1.0 wt% boron and 1.0 wt% GO exhibit a significant improvement in both the toughness and oxygen barrier properties compared to pristine chitosan. In particular the tensile strength of the samples after thermal treatment increases by ~160% compared to pristine chitosan, whereas their oxygen permeability reduces by ~90%. This is ascribed to the chemical

  17. Comparative wear tests of ultra-high molecular weight polyethylene and cross-linked polyethylene.

    PubMed

    Harsha, A P; Joyce, Tom J

    2013-05-01

    Wear particle-induced osteolysis is a major concern in hip implant failure. Therefore, recent research work has focussed on wear-resistant materials, one of the most important of which is cross-linked polyethylene. In view of this, the objective of this study was to compare the in vitro wear performance of cross-linked polyethylene to traditional ultra-high molecular weight polyethylene. In order to mimic appropriate in vivo conditions, a novel high-capacity wear tester called a circularly translating pin-on-disc was used. The results of this in vitro study demonstrated that the wear rate for cross-linked polyethylene was about 80% lower than that of conventional ultra-high molecular weight polyethylene. This difference closely matches in vivo results reported in the literature for total hip replacements that use the two biopolymers. The in vitro results were also verified against ASTM F732-00 (standard test method for wear testing of polymeric materials for use in total joint prostheses). The 50-station circularly translating pin-on-disc proved to be a reliable device for in vitro wear studies of orthopaedic biopolymers.

  18. Enablement, Constraint, and "The 7 Habits of Highly Effective People."

    ERIC Educational Resources Information Center

    Carlone, David

    2001-01-01

    Uses interviews to examine how the self-help book "The 7 Habits of Highly Effective People" shapes the identity of organization members who read and use the book. Suggests that such people are simultaneously enabled and constrained as they confront tensions between individualism and community, competition and cooperation, and domination and…

  19. Wear measurement of highly cross-linked UHMWPE using a 7Be tracer implantation technique.

    PubMed

    Wimmer, Markus A; Laurent, Michel P; Dwiwedi, Yasha; Gallardo, Luis A; Chipps, Kelly A; Blackmon, Jeffery C; Kozub, Raymond L; Bardayan, Daniel W; Gross, Carl J; Stracener, Daniel W; Smith, Michael S; Nesaraja, Caroline D; Erikson, Luke; Patel, Nidhi; Rehm, Karl E; Ahmad, Irshad; Greene, John P; Greife, Uwe

    2013-04-01

    The very low wear rates achieved with the current highly cross-linked ultrahigh molecular weight polyethylenes (UHMWPE) used in joint prostheses have proven to be difficult to measure accurately by gravimetry. Tracer methods are therefore being explored. The purpose of this study was to perform a proof-of-concept experiment on the use of the radioactive tracer beryllium-7 ((7)Be) for the determination of in vitro wear in a highly cross-linked orthopedic UHMWPE. Three cross-linked and four conventional UHMWPE pins made from compression-molded GUR 1050, were activated with 10(9) to 10(10) (7)Be nuclei using a new implantation setup that produced a homogenous distribution of implanted nuclei up to 8.5 μm below the surface. The pins were tested for wear in a six-station pin-on-flat apparatus for up to 7.1 million cycles (178 km). A Germanium gamma detector was employed to determine activity loss of the UHMWPE pins at preset intervals during the wear test. The wear of the cross-linked UHMWPE pins was readily detected and estimated to be 17 ± 3 μg per million cycles. The conventional-to-cross-linked ratio of the wear rates was 13.1 ± 0.8, in the expected range for these materials. Oxidative degradation damage from implantation was negligible; however, a weak dependence of wear on implantation dose was observed limiting the number of radioactive tracer atoms that can be introduced. Future applications of this tracer technology may include the analysis of location-specific wear, such as loss of material in the post or backside of a tibial insert.

  20. Preparation and characterization of free films of high amylose/pectin mixtures cross-linked with sodium trimetaphosphate.

    PubMed

    Prezotti, Fabíola Garavello; Meneguin, Andréia Bagliotti; Evangelista, Raul Cesar; Cury, Beatriz Stringhetti Ferreira

    2012-11-01

    High amylose and pectin were mixed at 1:1 mass ratio and cross-linked with sodium trimetaphosphate (STMP) in alkaline medium. Films were prepared from aqueous dispersions of these cross-linked polymer blend at three different concentrations (3, 4 and 5%), by solvent casting method. Characterization of the films included thickness, surface morphology, water uptake, water vapor permeability (WVP), tensile strength measurements and enzymatic digestion. The cross-linking allowed to obtain films with improved mechanical properties and reduced WVP. The high resistance to enzymatic digestion exhibited by these films represents a promising approach to their application in the development of colon drug delivery systems. PMID:22251099

  1. Crosslinked polymeric ionic liquids as solid-phase microextraction sorbent coatings for high performance liquid chromatography.

    PubMed

    Yu, Honglian; Merib, Josias; Anderson, Jared L

    2016-03-18

    Neat crosslinked polymeric ionic liquid (PIL) sorbent coatings for solid-phase microextraction (SPME) compatible with high-performance liquid chromatography (HPLC) are reported for the first time. Six structurally different PILs were crosslinked to nitinol supports and applied for the determination of select pharmaceutical drugs, phenolics, and insecticides. Sampling conditions including sample solution pH, extraction time, desorption solvent, desorption time, and desorption solvent volume were optimized using design of experiment (DOE). The developed PIL sorbent coatings were stable when performing extractions under acidic pH and remained intact in various organic desorption solvents (i.e., methanol, acetonitrile, acetone). The PIL-based sorbent coating polymerized from the IL monomer 1-vinyl-3-(10-hydroxydecyl) imidazolium chloride [VC10OHIM][Cl] and IL crosslinker 1,12-di(3-vinylbenzylimidazolium) dodecane dichloride [(VBIM)2C12] 2[Cl] exhibited superior extraction performance compared to the other studied PILs. The extraction efficiency of pharmaceutical drugs and phenolics increased when the film thickness of the PIL-based sorbent coating was increased while many insecticides were largely unaffected. Satisfactory analytical performance was obtained with limits of detection (LODs) ranging from 0.2 to 2 μg L(-1) for the target analytes. The accuracy of the analytical method was examined by studying the relative recovery of analytes in real water samples, including tap water and lake water, with recoveries varying from 50.2% to 115.9% and from 48.8% to 116.6%, respectively. PMID:26896916

  2. Liquid immersion thermal crosslinking of 3D polymer nanopatterns for direct carbonisation with high structural integrity

    PubMed Central

    Kang, Da-Young; Kim, Cheolho; Park, Gyurim; Moon, Jun Hyuk

    2015-01-01

    The direct pyrolytic carbonisation of polymer patterns has attracted interest for its use in obtaining carbon materials. In the case of carbonisation of nanopatterned polymers, the polymer flow and subsequent pattern change may occur in order to relieve their high surface energies. Here, we demonstrated that liquid immersion thermal crosslinking of polymer nanopatterns effectively enhanced the thermal resistance and maintained the structure integrity during the heat treatment. We employed the liquid immersion thermal crosslinking for 3D porous SU8 photoresist nanopatterns and successfully converted them to carbon nanopatterns while maintaining their porous features. The thermal crosslinking reaction and carbonisation of SU8 nanopatterns were characterised. The micro-crystallinity of the SU8-derived carbon nanopatterns was also characterised. The liquid immersion heat treatment can be extended to the carbonisation of various polymer or photoresist nanopatterns and also provide a facile way to control the surface energy of polymer nanopatterns for various purposes, for example, to block copolymer or surfactant self-assemblies. PMID:26677949

  3. Liquid immersion thermal crosslinking of 3D polymer nanopatterns for direct carbonisation with high structural integrity

    NASA Astrophysics Data System (ADS)

    Kang, Da-Young; Kim, Cheolho; Park, Gyurim; Moon, Jun Hyuk

    2015-12-01

    The direct pyrolytic carbonisation of polymer patterns has attracted interest for its use in obtaining carbon materials. In the case of carbonisation of nanopatterned polymers, the polymer flow and subsequent pattern change may occur in order to relieve their high surface energies. Here, we demonstrated that liquid immersion thermal crosslinking of polymer nanopatterns effectively enhanced the thermal resistance and maintained the structure integrity during the heat treatment. We employed the liquid immersion thermal crosslinking for 3D porous SU8 photoresist nanopatterns and successfully converted them to carbon nanopatterns while maintaining their porous features. The thermal crosslinking reaction and carbonisation of SU8 nanopatterns were characterised. The micro-crystallinity of the SU8-derived carbon nanopatterns was also characterised. The liquid immersion heat treatment can be extended to the carbonisation of various polymer or photoresist nanopatterns and also provide a facile way to control the surface energy of polymer nanopatterns for various purposes, for example, to block copolymer or surfactant self-assemblies.

  4. Borate cross-linked graphene oxide-chitosan as robust and high gas barrier films.

    PubMed

    Yan, Ning; Capezzuto, Filomena; Lavorgna, Marino; Buonocore, Giovanna G; Tescione, Fabiana; Xia, Hesheng; Ambrosio, Luigi

    2016-05-19

    Chitosan (CS) is one of the most promising polymers due to its biocompatibility, biodegradability, and natural abundance. However, its poor mechanical and barrier properties make it difficult to satisfy a wide range of applications. Herein, borate ions, originating from the hydrolysis of sodium tetraborate decahydrate (borax), have been used to crosslink chitosan and graphene oxide (GO) nanocomposites. Chitosan films consisting of 1.0 wt% boron and 1.0 wt% GO exhibit a significant improvement in both the toughness and oxygen barrier properties compared to pristine chitosan. In particular the tensile strength of the samples after thermal treatment increases by ∼160% compared to pristine chitosan, whereas their oxygen permeability reduces by ∼90%. This is ascribed to the chemical crosslinking between chitosan and GO nanoplatelets through borate ions, as well as the formation of a layered morphology with graphene nanoplatelets oriented parallel to the sample surface. The exceptional robust and high gas barrier film has promising application in the packaging industry. The borate-crosslinking chemistry represents the potential strategy for improving properties of other polymer nanocomposites. PMID:27168418

  5. Crosslinked polymeric ionic liquids as solid-phase microextraction sorbent coatings for high performance liquid chromatography.

    PubMed

    Yu, Honglian; Merib, Josias; Anderson, Jared L

    2016-03-18

    Neat crosslinked polymeric ionic liquid (PIL) sorbent coatings for solid-phase microextraction (SPME) compatible with high-performance liquid chromatography (HPLC) are reported for the first time. Six structurally different PILs were crosslinked to nitinol supports and applied for the determination of select pharmaceutical drugs, phenolics, and insecticides. Sampling conditions including sample solution pH, extraction time, desorption solvent, desorption time, and desorption solvent volume were optimized using design of experiment (DOE). The developed PIL sorbent coatings were stable when performing extractions under acidic pH and remained intact in various organic desorption solvents (i.e., methanol, acetonitrile, acetone). The PIL-based sorbent coating polymerized from the IL monomer 1-vinyl-3-(10-hydroxydecyl) imidazolium chloride [VC10OHIM][Cl] and IL crosslinker 1,12-di(3-vinylbenzylimidazolium) dodecane dichloride [(VBIM)2C12] 2[Cl] exhibited superior extraction performance compared to the other studied PILs. The extraction efficiency of pharmaceutical drugs and phenolics increased when the film thickness of the PIL-based sorbent coating was increased while many insecticides were largely unaffected. Satisfactory analytical performance was obtained with limits of detection (LODs) ranging from 0.2 to 2 μg L(-1) for the target analytes. The accuracy of the analytical method was examined by studying the relative recovery of analytes in real water samples, including tap water and lake water, with recoveries varying from 50.2% to 115.9% and from 48.8% to 116.6%, respectively.

  6. Using high-performance networks to enable computational aerosciences applications

    NASA Technical Reports Server (NTRS)

    Johnson, Marjory J.

    1992-01-01

    One component of the U.S. Federal High Performance Computing and Communications Program (HPCCP) is the establishment of a gigabit network to provide a communications infrastructure for researchers across the nation. This gigabit network will provide new services and capabilities, in addition to increased bandwidth, to enable future applications. An understanding of these applications is necessary to guide the development of the gigabit network and other high-performance networks of the future. In this paper we focus on computational aerosciences applications run remotely using the Numerical Aerodynamic Simulation (NAS) facility located at NASA Ames Research Center. We characterize these applications in terms of network-related parameters and relate user experiences that reveal limitations imposed by the current wide-area networking infrastructure. Then we investigate how the development of a nationwide gigabit network would enable users of the NAS facility to work in new, more productive ways.

  7. High-periodicity nanostructures on a thermally cross-linkable copolymer

    NASA Astrophysics Data System (ADS)

    Strobel, Alexander; Tröger, David; Proschwitz, Steffi; Hildebrand, Dirk; Schondelmaier, Daniel; Limberg, Felix R. P.; Krüger, Hartmut

    2016-10-01

    This paper presents a low-cost and high-throughput process for nanoscale imprinting of a novel thermally cross-linkable polymer via laser interference lithography. This technique was applied to produce the highly periodic nanometer structures such as lines and dots. The negative of this master pattern was imprinted in the solvent-cast polymer resist via hot-embossing nanoimprint lithography. Using polydimethylsiloxane stamps, it is possible to replicate the original pattern on the resist. The interference lithography process and the master structures are discussed. Lines and dots are hot-embossed applying different holding pressures, achieving a period of 630 nm.

  8. Refined AFC-Enabled High-Lift System Integration Study

    NASA Technical Reports Server (NTRS)

    Hartwich, Peter M.; Shmilovich, Arvin; Lacy, Douglas S.; Dickey, Eric D.; Scalafani, Anthony J.; Sundaram, P.; Yadlin, Yoram

    2016-01-01

    A prior trade study established the effectiveness of using Active Flow Control (AFC) for reducing the mechanical complexities associated with a modern high-lift system without sacrificing aerodynamic performance at low-speed flight conditions representative of takeoff and landing. The current technical report expands on this prior work in two ways: (1) a refined conventional high-lift system based on the NASA Common Research Model (CRM) is presented that is more representative of modern commercial transport aircraft in terms of stall characteristics and maximum Lift/Drag (L/D) ratios at takeoff and landing-approach flight conditions; and (2) the design trade space for AFC-enabled high-lift systems is expanded to explore a wider range of options for improving their efficiency. The refined conventional high-lift CRM (HL-CRM) concept features leading edge slats and slotted trailing edge flaps with Fowler motion. For the current AFC-enhanced high lift system trade study, the refined conventional high-lift system is simplified by substituting simply-hinged trailing edge flaps for the slotted single-element flaps with Fowler motion. The high-lift performance of these two high-lift CRM variants is established using Computational Fluid Dynamics (CFD) solutions to the Reynolds-Averaged Navier-Stokes (RANS) equations. These CFD assessments identify the high-lift performance that needs to be recovered through AFC to have the CRM variant with the lighter and mechanically simpler high-lift system match the performance of the conventional high-lift system. In parallel to the conventional high-lift concept development, parametric studies using CFD guided the development of an effective and efficient AFC-enabled simplified high-lift system. This included parametric trailing edge flap geometry studies addressing the effects of flap chord length and flap deflection. As for the AFC implementation, scaling effects (i.e., wind-tunnel versus full-scale flight conditions) are addressed

  9. A novel crosslinking strategy for preparing poly(vinyl alcohol)-based proton-conducting membranes with high sulfonation

    NASA Astrophysics Data System (ADS)

    Tsai, Chun-En; Lin, Chi-Wen; Hwang, Bing-Joe

    This study synthesizes poly(vinyl alcohol) (PVA)-based polymer electrolyte membranes by a two-step crosslinking process involving esterization and acetal ring formation reactions. This work also uses sulfosuccinic acid (SSA) as the first crosslinking agent to form an inter-crosslinked structure and a promoting sulfonating agent. Glutaraldehyde (GA) as the second crosslinking agent, reacts with the spare OH group of PVA and forms, not only a dense structure at the outer membrane surface, but also a hydrophobic protective layer. Compared with membranes prepared by a traditional one-step crosslinking process, membranes prepared by the two-step crosslinking process exhibit excellent dissolution resistance in water. The membranes become water-insoluble even at a molar ratio of SO 3H/PVA-OH as high as 0.45. Moreover, the synthesized membranes also exhibit high proton conductivities and high methanol permeability resistance. The current study measures highest proton conductivity of 5.3 × 10 -2 S cm -1 at room temperature from one of the synthesized membranes, higher than that of the Nafion ® membrane. Methanol permeability of the synthesized membranes measures about 1 × 10 -7 cm 2 S -1, about one order of magnitude lower than that of the Nafion ® membrane.

  10. The sensitive and selective adsorption of aromatic compounds with highly crosslinked polymer nanoparticles.

    PubMed

    Liu, Shuqin; Chen, Darui; Zheng, Juan; Zeng, Lewei; Jiang, Jijun; Jiang, Ruifeng; Zhu, Fang; Shen, Yong; Wu, Dingcai; Ouyang, Gangfeng

    2015-10-28

    This study presents the preparation and characterization of a nanoscale Davankov-type hyper-crosslinked-polymer (HCP) as an adsorbent of benzene-ring-containing dyes and organic pollutants. HCP nanoparticles post-crosslinked from a poly(DVB-co-VBC) precursor were synthesized in this study, possessing ultrahigh surface area, hydrophobicity and stability. The as-synthesized Davankov-type HCP exhibited a rapid and selective adsorption ability towards the benzene-ring-containing dyes due to its highly conjugated structure. Besides, for the first time, the prepared HCP nanoparticles were adopted for the adsorption of nonpolar organic pollutants by means of solid-phase microextraction (SPME). Owing to its high hydrophobicity, diverse pore size distribution and highly conjugated structure, a 10 μm HCP coating exhibited excellent adsorption abilities towards benzene-ring-containing polycyclic aromatic hydrocarbons (PAHs) and benzene series compounds (benzene, toluene, ethylbenzene and o-xylene; abbreviated to BTEX) and to highly hydrophobic long-chain n-alkanes. Finally, the HCP-nanoparticles-coated SPME fiber was applied to the simultaneous analysis of five PAHs in environmental water samples and satisfactory recoveries were achieved. The findings could provide a new benchmark for the exploitation of superb HCPs as effective adsorbents for SPME or other adsorption applications.

  11. Does cyclic stress and accelerated ageing influence the wear behavior of highly crosslinked polyethylene?

    PubMed

    Affatato, Saverio; De Mattia, Jonathan Salvatore; Bracco, Pierangiola; Pavoni, Eleonora; Taddei, Paola

    2016-06-01

    First-generation (irradiated and remelted or annealed) and second-generation (irradiated and vitamin E blended or doped) highly crosslinked polyethylenes were introduced in the last decade to solve the problems of wear and osteolysis. In this study, the influence of the Vitamin-E addition on crosslinked polyethylene (XLPE_VE) was evaluated by comparing the in vitro wear behavior of crosslinked polyethylene (XLPE) versus Vitamin-E blended polyethylene XLPE and conventional ultra-high molecular weight polyethylene (STD_PE) acetabular cups, after accelerated ageing according to ASTM F2003-02 (70.0±0.1°C, pure oxygen at 5bar for 14 days). The test was performed using a hip joint simulator run for two millions cycles, under bovine calf serum as lubricant. Mass loss was found to decrease along the series XLPE_VE>STD_PE>XLPE, although no statistically significant differences were found between the mass losses of the three sets of cups. Micro-Raman spectroscopy was used to investigate at a molecular level the morphology changes induced by wear. The spectroscopic analyses showed that the accelerated ageing determined different wear mechanisms and molecular rearrangements during testing with regards to the changes in both the chain orientation and the distribution of the all-trans sequences within the orthorhombic, amorphous and third phases. The results of the present study showed that the addition of vitamin E was not effective to improve the gravimetric wear of PE after accelerated ageing. However, from a molecular point of view, the XLPE_VE acetabular cups tested after accelerated ageing appeared definitely less damaged than the STD_PE ones and comparable to XLPE samples. PMID:26970299

  12. Wear of PEEK-OPTIMA® and PEEK-OPTIMA®-Wear Performance articulating against highly cross-linked polyethylene.

    PubMed

    East, Rebecca H; Briscoe, Adam; Unsworth, Anthony

    2015-03-01

    The idea of all polymer artificial joints, particularly for the knee and finger, has been raised several times in the past 20 years. This is partly because of weight but also to reduce stress shielding in the bone when stiffer materials such as metals or ceramics are used. With this in mind, pin-on-plate studies of various polyetheretherketone preparations against highly cross-linked polyethylene were conducted to investigate the possibility of using such a combination in the design of a new generation of artificial joints. PEEK-OPTIMA(®) (no fibre) against highly cross-linked polyethylene gave very low wear factors of 0.0384 × 10(-6) mm(3)/N m for the polyetheretherketone pins and -0.025 × 10(-6) mm(3)/N m for the highly cross-linked polyethylene plates. The carbon-fibre-reinforced polyetheretherketone (PEEK-OPTIMA(®)-Wear Performance) also produced very low wear rates in the polyetheretherketone pins but produced very high wear in the highly cross-linked polyethylene, as might have been predicted since the carbon fibres are quite abrasive. When the fibres were predominantly tangential to the sliding plane, the mean wear factor was 0.052 × 10(-6) mm(3)/N m for the pins and 49.3 × 10(-6) mm(3)/N m for the highly cross-linked polyethylene plates; a half of that when the fibres ran axially in the pins (0.138 × 10(-6) mm(3)/N m for the pins and 97.5 × 10(-6) mm/ N m for the cross-linked polyethylene plates). PEEK-OPTIMA(®) against highly cross-linked polyethylene merits further investigation.

  13. Wear of PEEK-OPTIMA® and PEEK-OPTIMA®-Wear Performance articulating against highly cross-linked polyethylene.

    PubMed

    East, Rebecca H; Briscoe, Adam; Unsworth, Anthony

    2015-03-01

    The idea of all polymer artificial joints, particularly for the knee and finger, has been raised several times in the past 20 years. This is partly because of weight but also to reduce stress shielding in the bone when stiffer materials such as metals or ceramics are used. With this in mind, pin-on-plate studies of various polyetheretherketone preparations against highly cross-linked polyethylene were conducted to investigate the possibility of using such a combination in the design of a new generation of artificial joints. PEEK-OPTIMA(®) (no fibre) against highly cross-linked polyethylene gave very low wear factors of 0.0384 × 10(-6) mm(3)/N m for the polyetheretherketone pins and -0.025 × 10(-6) mm(3)/N m for the highly cross-linked polyethylene plates. The carbon-fibre-reinforced polyetheretherketone (PEEK-OPTIMA(®)-Wear Performance) also produced very low wear rates in the polyetheretherketone pins but produced very high wear in the highly cross-linked polyethylene, as might have been predicted since the carbon fibres are quite abrasive. When the fibres were predominantly tangential to the sliding plane, the mean wear factor was 0.052 × 10(-6) mm(3)/N m for the pins and 49.3 × 10(-6) mm(3)/N m for the highly cross-linked polyethylene plates; a half of that when the fibres ran axially in the pins (0.138 × 10(-6) mm(3)/N m for the pins and 97.5 × 10(-6) mm/ N m for the cross-linked polyethylene plates). PEEK-OPTIMA(®) against highly cross-linked polyethylene merits further investigation. PMID:25833994

  14. Comparative fatigue behavior and toughness of remelted and annealed highly crosslinked polyethylenes.

    PubMed

    Medel, Francisco J; Peña, P; Cegoñino, José; Gómez-Barrena, E; Puértolas, J A

    2007-11-01

    Highly cross-linked polyethylenes (HXLPEs) have been incorporated into the hip replacement armamentarium based on their improved wear resistance. However, two different methods of thermal treatment separate the orthopedic community as strategies to control potential long-term oxidation, and controversy remains with problems in the long-term use of acetabular liners (long-term oxidation, rim fracture after impingement, etc.). Meanwhile, the mechanical properties of HXLPEs that may alleviate these problems are still unclear. On the other hand, HXLPEs are scarcely used in knee replacements, as there exists concern about the probably reduced fatigue and fracture performances of these materials. Thus, our aim was to compare the effects of both thermal treatment regimes on mechanical properties and to associate these findings with the material microstructure. The fatigue behavior of annealed and remelted HXLPEs was characterized using short-term cyclic stress-strain, long-term fatigue, and fatigue crack propagation tests. On the other hand, impact tests, tensile experiments, and the J-integral multispecimen method allowed us to assess toughness. Microstructure features such as crosslink density, crystallinity percentage, and lamellar thickness were investigated by swelling measurements, differential scanning calorimetry, and transmission electron microscopy, respectively. This study confirms that annealing preserves mechanical properties better than remelting from both fatigue and fracture resistance points of view, and it remarks that a suitable selection of irradiation and stabilization conditions is needed to achieve optimal mechanical performances of ultra high molecular weight polyethylenes for each specific total joint replacement.

  15. Construction of monomer-free, highly crosslinked, water-compatible polymers.

    PubMed

    Dailing, E A; Lewis, S H; Barros, M D; Stansbury, J W

    2014-12-01

    Polymeric dental adhesives require the formation of densely crosslinked network structures to best ensure mechanical strength and durability in clinical service. Monomeric precursors to these materials typically consist of mixtures of hydrophilic and hydrophobic components that potentially undergo phase separation in the presence of low concentrations of water, which is detrimental to material performance and has motivated significant investigation into formulations that reduce this effect. We have investigated an approach to network formation based on nanogels that are dispersed in inert solvent and directly polymerized into crosslinked polymers. Monomers of various hydrophilic or hydrophobic characteristics were copolymerized into particulate nanogels bearing internal and external polymerizable functionality. Nanogel dispersions were stable at high concentrations in acetone or, with some exceptions, in water and produced networks with a wide range of mechanical properties. Networks formed rapidly upon light activation and reached high conversion with extremely low volumetric shrinkage. Prepolymerizing monomers into reactive nanostructures significantly changes how hydrophobic materials respond to water compared with networks obtained from polymerizations involving free monomer. The modulus of fully hydrated networks formed solely from nanogels was shown to equal or exceed the modulus in the dry state for networks based on nanogels containing a hydrophobic dimethacrylate and hydrophilic monomethacrylate, a result that was not observed in a hydroxyethyl methacrylate (HEMA) homopolymer or in networks formed from nanogels copolymerized with HEMA. These results highlight the unique approach to network development from nanoscale precursors and properties that have direct implications in functional dental materials. PMID:25248612

  16. Study the adsorption of sulfates by high cross-linked polystyrene divinylbenzene anion-exchange resin

    NASA Astrophysics Data System (ADS)

    Fathy, Mahmoud; Moghny, Th. Abdel; Awadallah, Ahmed E.; El-Bellihi, Abdel-Hameed A.-A.

    2014-11-01

    In response to rising concerns about the effect of sulfate on water quality, human health, and agriculture, many jurisdictions around the world are imposing tighter regulations for sulfate discharge. This is driving the need for environmental compliance in industries like mining, metal processing, pulp and paper, sewage treatment, and chemical manufacturing. The sulfate removal from synthetic water by high cross-linked polystyrene divinylbenzene resin was studied at batch experiments in this study. The effect of pH, contact time, sulfates concentration, and adsorbent dose on the sulfate sequestration was investigated. The optimum conditions were studied on Saline water as a case study. The results showed that with increasing of the absorbent amount; contact time, and pH improve the efficiency of sulfate removal. The maximum sulfates uptake was obtained in pH and contact time 3.0 and 120 min, respectively. Also, with increasing initial concentration of sulfates in water, the efficiency of sulfate removal decreased. The obtained results in this study were matched with Freundlich isotherm and pseudo-second-order kinetic. The maximum adsorption capacity (Qm) and constant rate were found 0.318 (mg/g) and 0.21 (mg/g.min), respectively. This study also showed that in the optimum conditions, the sulfate removal efficiency from Saline water by 0.1 mg/L sulfates was 65.64 %. Eventually, high cross-linked polystyrene divinylbenzene resin is recommended as a suitable and low cost absorbent to sulfate removal from aqueous solutions.

  17. Construction of Monomer-free, Highly Crosslinked, Water-compatible Polymers

    PubMed Central

    Dailing, E.A.; Lewis, S.H.; Barros, M.D.; Stansbury, J.W.

    2014-01-01

    Polymeric dental adhesives require the formation of densely crosslinked network structures to best ensure mechanical strength and durability in clinical service. Monomeric precursors to these materials typically consist of mixtures of hydrophilic and hydrophobic components that potentially undergo phase separation in the presence of low concentrations of water, which is detrimental to material performance and has motivated significant investigation into formulations that reduce this effect. We have investigated an approach to network formation based on nanogels that are dispersed in inert solvent and directly polymerized into crosslinked polymers. Monomers of various hydrophilic or hydrophobic characteristics were copolymerized into particulate nanogels bearing internal and external polymerizable functionality. Nanogel dispersions were stable at high concentrations in acetone or, with some exceptions, in water and produced networks with a wide range of mechanical properties. Networks formed rapidly upon light activation and reached high conversion with extremely low volumetric shrinkage. Prepolymerizing monomers into reactive nanostructures significantly changes how hydrophobic materials respond to water compared with networks obtained from polymerizations involving free monomer. The modulus of fully hydrated networks formed solely from nanogels was shown to equal or exceed the modulus in the dry state for networks based on nanogels containing a hydrophobic dimethacrylate and hydrophilic monomethacrylate, a result that was not observed in a hydroxyethyl methacrylate (HEMA) homopolymer or in networks formed from nanogels copolymerized with HEMA. These results highlight the unique approach to network development from nanoscale precursors and properties that have direct implications in functional dental materials. PMID:25248612

  18. Silica-Based, Hyper-Crosslinked Acid Stable Stationary Phases for High Performance Liquid Chromatography

    PubMed Central

    Zhang, Yu; Luo, Hao; Carr, Peter W.

    2011-01-01

    A new family of Hyper-Crosslinked (HC) phases has been recently introduced for use under very aggressive acid conditions including those encountered in ultra-fast, high temperature Two-Dimensional Liquid Chromatography (2DLC). This type of stationary phase showed significantly enhanced acid and thermal stability compared to the most acid stable, commercial RPLC phases. In addition, the use of “orthogonal” chemistry to make surface-confined polymer networks ensures good reproducibility and high efficiency. One of the most interesting features of the HC phases is the ability to derivatize the surface aromatic groups with various functional groups. This led to the development of a family of hyper-crosslinked phases possessing a wide variety of chromatographic selectivities by attaching hydrophobic (e.g. –C8), ionizable (e.g. -COOH, -SO3H), aromatic (e.g. –toluene) or polar (e.g. -OH) species to the aromatic polymer network. HC reversed phases with various degrees of hydrophobicity and mixed-mode HC phases with added strong and weak cation exchange sites have been synthesized, characterized and applied. These silica-based acid-stable HC phases, with their attractive chromatographic properties, should be very useful in the separations of bases or biological analytes in acidic media, especially at elevated temperatures. This work reviews the prior research on HC phases and introduces a novel HC phase made by alternative chemistry. PMID:21906745

  19. Graphene oxide-based benzimidazole-crosslinked networks for high-performance supercapacitors.

    PubMed

    Cui, Yi; Cheng, Qian-Yi; Wu, Haiping; Wei, Zhixiang; Han, Bao-Hang

    2013-09-21

    The synthesis of graphene oxide (GO)-based benzimidazole-crosslinked network (GOBIN) materials is presented. These materials are prepared by the covalent crosslinking of GO sheets using a condensation reaction between the carboxylic acid moieties on the GO surface and the o-aminophenyl end groups of 3,3'-diaminobenzidine (or 1,2,4,5-benzenetetraamine tetrahydrochloride). An efficient one-pot catalyst- and template-free synthesis was performed. The obtained porous GO-based materials possess a Brunauer-Emmett-Teller specific surface area ranging from 260 to 920 m(2) g(-1). Electrochemical testing indicates that the GOBIN materials display a specific capacitance up to 370 F g(-1) at a current density of 0.1 A g(-1) and about 90% of the original capacitance is retained after 5000 cycles at a current density of 3 A g(-1). Therefore, GOBIN materials can be employed as promising electrode materials for high-performance supercapacitors with outstanding cycling stability. Furthermore, owing to their significantly high specific surface area, these materials also show hydrogen uptake (up to 1.24 wt%, at 77 K and 1.0 bar) and carbon dioxide capture (up to 14.2 wt%, at 273 K and 1.0 bar) properties. As a result, these GO-based porous materials improve both the supercapacitor performance and gas sorption property, which demonstrate an excellent performance in the practical application of energy storage. PMID:23793833

  20. AFC-Enabled Simplified High-Lift System Integration Study

    NASA Technical Reports Server (NTRS)

    Hartwich, Peter M.; Dickey, Eric D.; Sclafani, Anthony J.; Camacho, Peter; Gonzales, Antonio B.; Lawson, Edward L.; Mairs, Ron Y.; Shmilovich, Arvin

    2014-01-01

    The primary objective of this trade study report is to explore the potential of using Active Flow Control (AFC) for achieving lighter and mechanically simpler high-lift systems for transonic commercial transport aircraft. This assessment was conducted in four steps. First, based on the Common Research Model (CRM) outer mold line (OML) definition, two high-lift concepts were developed. One concept, representative of current production-type commercial transonic transports, features leading edge slats and slotted trailing edge flaps with Fowler motion. The other CRM-based design relies on drooped leading edges and simply hinged trailing edge flaps for high-lift generation. The relative high-lift performance of these two high-lift CRM variants is established using Computational Fluid Dynamics (CFD) solutions to the Reynolds-Averaged Navier-Stokes (RANS) equations for steady flow. These CFD assessments identify the high-lift performance that needs to be recovered through AFC to have the CRM variant with the lighter and mechanically simpler high-lift system match the performance of the conventional high-lift system. Conceptual design integration studies for the AFC-enhanced high-lift systems were conducted with a NASA Environmentally Responsible Aircraft (ERA) reference configuration, the so-called ERA-0003 concept. These design trades identify AFC performance targets that need to be met to produce economically feasible ERA-0003-like concepts with lighter and mechanically simpler high-lift designs that match the performance of conventional high-lift systems. Finally, technical challenges are identified associated with the application of AFC-enabled highlift systems to modern transonic commercial transports for future technology maturation efforts.

  1. Oxidative degradation in highly cross-linked and conventional polyethylene after 2 years of real-time shelf aging.

    PubMed

    Willie, Bettina M; Bloebaum, Roy D; Ashrafi, Shadi; Dearden, Colette; Steffensen, Trina; Hofmann, Aaron A

    2006-04-01

    Previous studies have reported oxidative degradation of conventional polyethylene (PE) components during shelf aging, following radiation. However, no studies have yet reported data concerning the effect of real-time shelf aging in the manufacturer's packaging on the oxidative degradation of commercially available highly cross-linking PE components. The null hypothesis tested was that in either highly cross-linked or conventional PE acetabular components there would be no significant difference in the amount of oxidative degradation between time zero PE liners and PE liners that had been real-time shelf aged for 2 years in their respective packaging. The results of the study indicated that after 2 years of real-time shelf aging, negligible oxidative degradation occurred with minimal changes in oxidation index, density, and percent crystallinity in commercially available highly cross-linked and conventional PE acetabular liners. These data suggested that oxidative degradation was not a clinical issue in the highly cross-linked and conventional PE components examined after 2 years of real-time shelf aging. It is likely that current manufacturing and packaging technologies have limited the previous clinical concerns related to oxidative degradation during shelf aging of highly cross-linked and conventional PE components.

  2. Remelting of highly cross-linked polyethylene worn under laboratory conditions.

    PubMed

    Lazzarini, Adam M; Cottrell, Jocelyn M; Padgett, Douglas E; Wright, Timothy M

    2007-12-01

    It has been suggested that apparent wear damage in highly cross-linked polyethylene acetabular liners can be removed with subsequent remelting of retrieved liners. To test this hypothesis, we remelted liners that had been previously tested under controlled laboratory conditions and that had experienced nonzero wear rates and visible wear damage. Five liner groups were examined: three with a range of irradiation doses without heat treatment, and two irradiated to 100 kGys, one with remelting, and the other annealing. All groups had been worn in a hip simulator under impingement conditions that produced nonzero wear rates and loss of machining marks. Each liner was cut into quadrants that were graded for wear damage before and after posttest remelting. Cross-linked liners not previously heat-treated lost all prior damage and all machining marks. Remelted liners and three of six annealed liners experienced only a slight return of machining marks at the interface of the burnished area and the remaining intact machining marks. Our experiments represent a severe wear case but demonstrate removal of material from the surface through measurable wear prevents the return of identifiable machining marks despite remelting. PMID:18090470

  3. Coarse-Grained Molecular Dynamics Study of the Curing and Properties of Highly Cross-Linked Epoxy Polymers.

    PubMed

    Aramoon, Amin; Breitzman, Timothy D; Woodward, Christopher; El-Awady, Jaafar A

    2016-09-01

    In this work, a coarse-grained model is developed for highly cross-linked bisphenol A diglycidyl ether epoxy resin with diaminobutane hardener. In this model, all conformationally relevant coarse-grained degrees of freedom are accounted for by sampling over the free-energy surfaces of the atomic structures using quantum mechanical simulations. The interaction potentials between nonbonded coarse-grained particles are optimized to accurately predict the experimentally measured density and glass-transition temperature of the system. In addition, a new curing algorithm is also developed to model the creation of highly cross-linked epoxy networks. In this algorithm, to create a highly cross-linked network, the reactants are redistributed from regions with an excessive number of reactive molecules to regions with a lower number of reactants to increase the chances of cross-linking. This new algorithm also dynamically controls the rate of cross-linking at each local region to ensure uniformity of the resulting network. The curing simulation conducted using this algorithm is able to develop polymeric networks having a higher average degree of cross-linking, which is more uniform throughout the simulation cell as compared to that in the networks cured using other curing algorithms. The predicted gel point from the current curing algorithm is in the acceptable theoretical and experimental range of measured values. Also, the resulting cross-linked microstructure shows a volume shrinkage of 5%, which is close to the experimentally measured volume shrinkage of the cured epoxy. Finally, the thermal expansion coefficients of materials in the glassy and rubbery states show good agreement with the experimental values.

  4. Coarse-Grained Molecular Dynamics Study of the Curing and Properties of Highly Cross-Linked Epoxy Polymers.

    PubMed

    Aramoon, Amin; Breitzman, Timothy D; Woodward, Christopher; El-Awady, Jaafar A

    2016-09-01

    In this work, a coarse-grained model is developed for highly cross-linked bisphenol A diglycidyl ether epoxy resin with diaminobutane hardener. In this model, all conformationally relevant coarse-grained degrees of freedom are accounted for by sampling over the free-energy surfaces of the atomic structures using quantum mechanical simulations. The interaction potentials between nonbonded coarse-grained particles are optimized to accurately predict the experimentally measured density and glass-transition temperature of the system. In addition, a new curing algorithm is also developed to model the creation of highly cross-linked epoxy networks. In this algorithm, to create a highly cross-linked network, the reactants are redistributed from regions with an excessive number of reactive molecules to regions with a lower number of reactants to increase the chances of cross-linking. This new algorithm also dynamically controls the rate of cross-linking at each local region to ensure uniformity of the resulting network. The curing simulation conducted using this algorithm is able to develop polymeric networks having a higher average degree of cross-linking, which is more uniform throughout the simulation cell as compared to that in the networks cured using other curing algorithms. The predicted gel point from the current curing algorithm is in the acceptable theoretical and experimental range of measured values. Also, the resulting cross-linked microstructure shows a volume shrinkage of 5%, which is close to the experimentally measured volume shrinkage of the cured epoxy. Finally, the thermal expansion coefficients of materials in the glassy and rubbery states show good agreement with the experimental values. PMID:27504803

  5. Enabling High Efficiency Nanoplasmonics with Novel Nanoantenna Architectures

    PubMed Central

    Cohen, Moshik; Shavit, Reuven; Zalevsky, Zeev

    2015-01-01

    Surface plasmon polaritons (SPPs) are propagating excitations that arise from coupling of light with collective electron oscillations. Characterized by high field intensity and nanometric dimensions, SPPs fashion rapid expansion of interest from fundamental and applicative perspectives. However, high metallic losses at optical frequencies still make nanoplasmonics impractical when high absolute efficiency is paramount, with major challenge is efficient plasmon generation in deep nanoscale. Here we introduce the Plantenna, the first reported nanodevice with the potential of addressing these limitations utilizing novel plasmonic architecture. The Plantenna has simple 2D structure, ultracompact dimensions and is fabricated on Silicon chip for future CMOS integration. We design the Plantenna to feed channel (20 nm × 20 nm) nanoplasmonic waveguides, achieving 52% coupling efficiency with Plantenna dimensions of λ3/17,000. We theoretically and experimentally show that the Plantenna enormously outperforms dipole couplers, achieving 28 dB higher efficiency with broad polarization diversity and huge local field enhancement. Our findings confirm the Plantenna as enabling device for high efficiency plasmonic technologies such as quantum nanoplasmonics, molecular strong coupling and plasmon nanolasers. PMID:26620270

  6. Enabling High Efficiency Nanoplasmonics with Novel Nanoantenna Architectures.

    PubMed

    Cohen, Moshik; Shavit, Reuven; Zalevsky, Zeev

    2015-01-01

    Surface plasmon polaritons (SPPs) are propagating excitations that arise from coupling of light with collective electron oscillations. Characterized by high field intensity and nanometric dimensions, SPPs fashion rapid expansion of interest from fundamental and applicative perspectives. However, high metallic losses at optical frequencies still make nanoplasmonics impractical when high absolute efficiency is paramount, with major challenge is efficient plasmon generation in deep nanoscale. Here we introduce the Plantenna, the first reported nanodevice with the potential of addressing these limitations utilizing novel plasmonic architecture. The Plantenna has simple 2D structure, ultracompact dimensions and is fabricated on Silicon chip for future CMOS integration. We design the Plantenna to feed channel (20 nm × 20 nm) nanoplasmonic waveguides, achieving 52% coupling efficiency with Plantenna dimensions of λ(3)/17,000. We theoretically and experimentally show that the Plantenna enormously outperforms dipole couplers, achieving 28 dB higher efficiency with broad polarization diversity and huge local field enhancement. Our findings confirm the Plantenna as enabling device for high efficiency plasmonic technologies such as quantum nanoplasmonics, molecular strong coupling and plasmon nanolasers. PMID:26620270

  7. Ultra Low Density and Highly Crosslinked Biocompatible Shape Memory Polyurethane Foams

    PubMed Central

    Singhal, Pooja; Rodriguez, Jennifer N.; Small, Ward; Eagleston, Scott; Van de Water, Judy; Maitland, Duncan J.; Wilson, Thomas S.

    2012-01-01

    We report the development of highly chemically crosslinked, ultra low density (~0.015 g/cc) polyurethane shape memory foams synthesized from symmetrical, low molecular weight and branched hydroxyl monomers. Sharp single glass transitions (Tg) customizable in the functional range of 45–70 °C were achieved. Thermomechanical testing confirmed shape memory behavior with 97–98% shape recovery over repeated cycles, a glassy storage modulus of 200–300 kPa and recovery stresses of 5–15 kPa. Shape holding tests under constrained storage above the Tg showed stable shape memory. A high volume expansion of up to 70 times was seen on actuation of these foams from a fully compressed state. Low in-vitro cell activation induced by the foam compared to controls demonstrates low acute bio-reactivity. We believe these porous polymeric scaffolds constitute an important class of novel smart biomaterials with multiple potential applications. PMID:22570509

  8. The sensitive and selective adsorption of aromatic compounds with highly crosslinked polymer nanoparticles

    NASA Astrophysics Data System (ADS)

    Liu, Shuqin; Chen, Darui; Zheng, Juan; Zeng, Lewei; Jiang, Jijun; Jiang, Ruifeng; Zhu, Fang; Shen, Yong; Wu, Dingcai; Ouyang, Gangfeng

    2015-10-01

    This study presents the preparation and characterization of a nanoscale Davankov-type hyper-crosslinked-polymer (HCP) as an adsorbent of benzene-ring-containing dyes and organic pollutants. HCP nanoparticles post-crosslinked from a poly(DVB-co-VBC) precursor were synthesized in this study, possessing ultrahigh surface area, hydrophobicity and stability. The as-synthesized Davankov-type HCP exhibited a rapid and selective adsorption ability towards the benzene-ring-containing dyes due to its highly conjugated structure. Besides, for the first time, the prepared HCP nanoparticles were adopted for the adsorption of nonpolar organic pollutants by means of solid-phase microextraction (SPME). Owing to its high hydrophobicity, diverse pore size distribution and highly conjugated structure, a 10 μm HCP coating exhibited excellent adsorption abilities towards benzene-ring-containing polycyclic aromatic hydrocarbons (PAHs) and benzene series compounds (benzene, toluene, ethylbenzene and o-xylene; abbreviated to BTEX) and to highly hydrophobic long-chain n-alkanes. Finally, the HCP-nanoparticles-coated SPME fiber was applied to the simultaneous analysis of five PAHs in environmental water samples and satisfactory recoveries were achieved. The findings could provide a new benchmark for the exploitation of superb HCPs as effective adsorbents for SPME or other adsorption applications.This study presents the preparation and characterization of a nanoscale Davankov-type hyper-crosslinked-polymer (HCP) as an adsorbent of benzene-ring-containing dyes and organic pollutants. HCP nanoparticles post-crosslinked from a poly(DVB-co-VBC) precursor were synthesized in this study, possessing ultrahigh surface area, hydrophobicity and stability. The as-synthesized Davankov-type HCP exhibited a rapid and selective adsorption ability towards the benzene-ring-containing dyes due to its highly conjugated structure. Besides, for the first time, the prepared HCP nanoparticles were adopted for the

  9. A self-healable and highly stretchable supercapacitor based on a dual crosslinked polyelectrolyte

    NASA Astrophysics Data System (ADS)

    Huang, Yan; Zhong, Ming; Huang, Yang; Zhu, Minshen; Pei, Zengxia; Wang, Zifeng; Xue, Qi; Xie, Xuming; Zhi, Chunyi

    2015-12-01

    Superior self-healability and stretchability are critical elements for the practical wide-scale adoption of personalized electronics such as portable and wearable energy storage devices. However, the low healing efficiency of self-healable supercapacitors and the small strain of stretchable supercapacitors are fundamentally limited by conventional polyvinyl alcohol-based acidic electrolytes, which are intrinsically neither self-healable nor highly stretchable. Here we report an electrolyte comprising polyacrylic acid dual crosslinked by hydrogen bonding and vinyl hybrid silica nanoparticles, which displays all superior functions and provides a solution to the intrinsic self-healability and high stretchability problems of a supercapacitor. Supercapacitors with this electrolyte are non-autonomic self-healable, retaining the capacitance completely even after 20 cycles of breaking/healing. These supercapacitors are stretched up to 600% strain with enhanced performance using a designed facile electrode fabrication procedure.

  10. A self-healable and highly stretchable supercapacitor based on a dual crosslinked polyelectrolyte.

    PubMed

    Huang, Yan; Zhong, Ming; Huang, Yang; Zhu, Minshen; Pei, Zengxia; Wang, Zifeng; Xue, Qi; Xie, Xuming; Zhi, Chunyi

    2015-01-01

    Superior self-healability and stretchability are critical elements for the practical wide-scale adoption of personalized electronics such as portable and wearable energy storage devices. However, the low healing efficiency of self-healable supercapacitors and the small strain of stretchable supercapacitors are fundamentally limited by conventional polyvinyl alcohol-based acidic electrolytes, which are intrinsically neither self-healable nor highly stretchable. Here we report an electrolyte comprising polyacrylic acid dual crosslinked by hydrogen bonding and vinyl hybrid silica nanoparticles, which displays all superior functions and provides a solution to the intrinsic self-healability and high stretchability problems of a supercapacitor. Supercapacitors with this electrolyte are non-autonomic self-healable, retaining the capacitance completely even after 20 cycles of breaking/healing. These supercapacitors are stretched up to 600% strain with enhanced performance using a designed facile electrode fabrication procedure. PMID:26691661

  11. A self-healable and highly stretchable supercapacitor based on a dual crosslinked polyelectrolyte

    PubMed Central

    Huang, Yan; Zhong, Ming; Huang, Yang; Zhu, Minshen; Pei, Zengxia; Wang, Zifeng; Xue, Qi; Xie, Xuming; Zhi, Chunyi

    2015-01-01

    Superior self-healability and stretchability are critical elements for the practical wide-scale adoption of personalized electronics such as portable and wearable energy storage devices. However, the low healing efficiency of self-healable supercapacitors and the small strain of stretchable supercapacitors are fundamentally limited by conventional polyvinyl alcohol-based acidic electrolytes, which are intrinsically neither self-healable nor highly stretchable. Here we report an electrolyte comprising polyacrylic acid dual crosslinked by hydrogen bonding and vinyl hybrid silica nanoparticles, which displays all superior functions and provides a solution to the intrinsic self-healability and high stretchability problems of a supercapacitor. Supercapacitors with this electrolyte are non-autonomic self-healable, retaining the capacitance completely even after 20 cycles of breaking/healing. These supercapacitors are stretched up to 600% strain with enhanced performance using a designed facile electrode fabrication procedure. PMID:26691661

  12. Enabling propulsion materials for high-speed civil transport engines

    NASA Technical Reports Server (NTRS)

    Stephens, Joseph R.; Herbell, Thomas P.

    1992-01-01

    NASA Headquarters and LeRC have advocated an Enabling Propulsion Materials Program (EPM) to begin in FY-92. The High Speed Research Phase 1 program which began in FY-90 has focused on the environmental acceptability of a High Speed Civil Transport (HSCT). Studies by industry, including Boeing, McDonnell Douglas, GE Aircraft Engines, and Pratt & Whitney Aircraft, and in-house studies by NASA concluded that NO(x) emissions and airport noise reduction can only be economically achieved by revolutionary advancements in materials technologies. This is especially true of materials for the propulsion system where the combustor is the key to maintaining low emissions, and the exhaust nozzle is the key to reducing airport noise to an acceptable level. Both of these components will rely on high temperature composite materials that can withstand the conditions imposed by commercial aircraft operations. The proposed EPM program will operate in conjunction with the HSR Phase 1 Program and the planned HSR Phase 2 program slated to start in FY-93. Components and subcomponents developed from advanced materials will be evaluated in the HSR Phase 2 Program.

  13. Smart surface coating of drug nanoparticles with cross-linkable polyethylene glycol for bio-responsive and highly efficient drug delivery

    NASA Astrophysics Data System (ADS)

    Wei, Weijia; Zhang, Xiujuan; Chen, Xianfeng; Zhou, Mengjiao; Xu, Ruirui; Zhang, Xiaohong

    2016-04-01

    Many drug molecules can be directly used as nanomedicine without the requirement of any inorganic or organic carriers such as silica and liposome nanostructures. This new type of carrier-free drug nanoparticles (NPs) has great potential in clinical treatment because of its ultra-high drug loading capacity and biodegradability. For practical applications, it is essential for such nanomedicine to possess robust stability and minimal premature release of therapeutic molecules during circulation in the blood stream. To meet this requirement, herein, we develop GSH-responsive and crosslinkable amphiphilic polyethylene glycol (PEG) molecules to modify carrier-free drug NPs. These PEG molecules can be cross-linked on the surface of the NPs to endow them with greater stability and the cross-link is sensitive to intracellular environment for bio-responsive drug release. With this elegant design, our experimental results show that the liberation of DOX from DOX-cross-linked PEG NPs is dramatically slower than that from DOX-non-cross-linked PEG NPs, and the DOX release profile can be controlled by tuning the concentration of the reducing agent to break the cross-link between PEG molecules. More importantly, in vivo studies reveal that the DOX-cross-linked PEG NPs exhibit favorable blood circulation half-life (>4 h) and intense accumulation in tumor areas, enabling effective anti-cancer therapy. We expect this work will provide a powerful strategy for stabilizing carrier-free nanomedicines and pave the way to their successful clinical applications in the future.Many drug molecules can be directly used as nanomedicine without the requirement of any inorganic or organic carriers such as silica and liposome nanostructures. This new type of carrier-free drug nanoparticles (NPs) has great potential in clinical treatment because of its ultra-high drug loading capacity and biodegradability. For practical applications, it is essential for such nanomedicine to possess robust stability

  14. The creep and wear of highly cross-linked polyethylene: a three-year randomised, controlled trial using radiostereometric analysis.

    PubMed

    Glyn-Jones, S; McLardy-Smith, P; Gill, H S; Murray, D W

    2008-05-01

    The creep and wear behaviour of highly cross-linked polyethylene and standard polyethylene liners were examined in a prospective, double-blind randomised, controlled trial using radiostereometric analysis. We randomised 54 patients to receive hip replacements with either highly cross-linked polyethylene or standard liners and determined the three-dimensional penetration of the liners over three years. After three years the mean total penetration was 0.35 mm (SD 0.14) for the highly cross-linked polyethylene group and 0.45 mm (SD 0.19) for the standard group. The difference was statistically significant (p = 0.0184). From the pattern of penetration it was possible to discriminate creep from wear. Most (95%) of the creep occurred within six months of implantation and nearly all within the first year. There was no difference in the mean degree of creep between the two types of polyethylene (highly cross-linked polyethylene 0.26 mm, SD 0.17; standard 0.27 mm, SD 0.2; p = 0.83). There was, however, a significant difference (p = 0.012) in the mean wear rate (highly cross-linked polyethylene 0.03 mm/yr, SD 0.06; standard 0.07 mm/yr, SD 0.05). Creep and wear occurred in significantly different directions (p = 0.01); creep was predominantly proximal whereas wear was anterior, proximal and medial. We conclude that penetration in the first six months is creep-dominated, but after one year virtually all penetration is due to wear. Highly cross-linked polyethylene has a 60% lower rate of wear than standard polyethylene and therefore will probably perform better in the long term.

  15. Prediction of multiaxial mechanical behavior for conventional and highly crosslinked UHMWPE using a hybrid constitutive model.

    PubMed

    Bergström, J S; Rimnac, C M; Kurtz, S M

    2003-04-01

    The development of theoretical failure, fatigue, and wear models for ultra-high molecular weight polyethylene (UHMWPE) used in joint replacements has been hindered by the lack of a validated constitutive model that can accurately predict large deformation mechanical behavior under clinically relevant, multiaxial loading conditions. Recently, a new Hybrid constitutive model for unirradiated UHMWPE was developed Bergström et al., (Biomaterials 23 (2002) 2329) based on a physics-motivated framework which incorporates the governing micro-mechanisms of polymers into an effective and accurate continuum representation. The goal of the present study was to compare the predictive capability of the new Hybrid model with the J(2)-plasticity model for four conventional and highly crosslinked UHMWPE materials during multiaxial loading. After calibration under uniaxial loading, the predictive capabilities of the J(2)-plasticity and Hybrid model were tested by comparing the load-displacement curves from experimental multiaxial (small punch) tests with simulated load-displacement curves calculated using a finite element model of the experimental apparatus. The quality of the model predictions was quantified using the coefficient of determination (r(2)). The results of the study demonstrate that the Hybrid model outperforms the J(2)-plasticity model both for combined uniaxial tension and compression predictions and for simulating multiaxial large deformation mechanical behavior produced by the small punch test. The results further suggest that the parameters of the HM may be generalizable for a wide range of conventional, highly crosslinked, and thermally treated UHMWPE materials, based on the characterization of four material properties related to the elastic modulus, yield stress, rate of strain hardening, and locking stretch of the polymer chains. Most importantly, from a practical perspective, these four key material properties for the Hybrid constitutive model can be measured

  16. Study of crosslinking onset and hydrogen annealing of ultra-high molecular weight polyethylene irradiated with high-energy protons

    NASA Astrophysics Data System (ADS)

    Wilson, John Ford

    1997-09-01

    Ultra high molecular weight polyethylene (UHMW-PE) is used extensively in hip and knee endoprostheses. Radiation damage from the sterilization of these endoprostheses prior to surgical insertion results in polymer crosslinking and decreased oxidative stability. The motivation for this study was to determine if UHMW-PE could be crosslinked by low dose proton irradiation with minimal radiation damage and its subsequent deleterious effects. I found that low dose proton irradiation and post irradiation hydrogen annealing did crosslink UHMW-PE and limit post irradiation oxidation. Crosslinking onset was investigated for UHMW-PE irradiated with 2.6 and 30 MeV H+ ions at low doses from 5.7 × 1011-2.3 × 1014 ions/cm2. Crosslinking was determined from gel permeation chromatography (GPC) of 1,2,4 trichlorobenzene sol fractions and increased with dose. Fourier transform infrared spectroscopy (FTIR) showed irradiation resulted in increased free radicals confirmed from increased carbonyl groups. Radiation damage, especially at the highest doses observed, also showed up in carbon double bonds and increased methyl end groups. Hydrogen annealing after ion irradiation resulted in 40- 50% decrease in FTIR absorption associated with carbonyl. The hydrogen annealing prevented further oxidation after aging for 1024 hours at 80oC. Hydrogen annealing was successful in healing radiation damage through reacting with the free radicals generated during proton irradiation. Polyethylenes, polyesters, and polyamides are used in diverse applications by the medical profession in the treatment of orthopedic impairments and cardiovascular disease and for neural implants. These artificial implants are sterilized with gamma irradiation prior to surgery and the resulting radiation damage can lead to accelerated deterioration of the implant properties. The findings in this study will greatly impact the continued use of these materials through the elimination of many problems associated with radiation

  17. Once Annealed Highly Cross-Linked Polyethylene Exhibits Low Wear at 9 to 15 Years.

    PubMed

    D'Antonio, James; Capello, William N; Ramakrishnan, Rama

    2016-05-01

    A once annealed highly cross-linked polyethylene (HXLPE) was introduced in 1998. Concerns regarding its long-term performance and oxidative resistance exist because of the presence of retained free radicals. The authors studied 48 patients with 50 hip implants having an average age of 62 years. They were followed for 9 to 15 years. The purpose of this study was to determine linear wear rate and the incidence of osteolysis and/or mechanical failure. At an average follow-up of 12.2 years, the annual linear wear rate was 0.018 mm (SD, 0.024 mm). No mechanical failures or osteolysis have been found to date. The clinical performance of this HXLPE continues to meet expectations despite the presence of free radicals. [Orthopedics. 2016; 39(3):e565-e571.]. PMID:27088350

  18. Interfacial fracture between highly crosslinked polymer networks and a solid surface: Effect of interfacial bond density

    SciTech Connect

    STEVENS,MARK J.

    2000-03-23

    For highly crosslinked, polymer networks bonded to a solid surface, the effect of interfacial bond density as well as system size on interfacial fracture is studied molecular dynamics simulations. The correspondence between the stress-strain curve and the sequence of molecular deformations is obtained. The failure strain for a fully bonded surface is equal to the strain necessary to make taut the average minimal path through the network from the bottom solid surface to the top surface. At bond coverages less than full, nanometer scale cavities form at the surface yielding an inhomogeneous strain profile. The failure strain and stress are linearly proportional to the number of bonds at the interface unless the number of bonds is so few that van der Waals interactions dominate. The failure is always interfacial due to fewer bonds at the interface than in the bulk.

  19. Precipitated and chemically-crosslinked laccase over polyaniline nanofiber for high performance phenol sensing.

    PubMed

    Kim, Jae Hyun; Hong, Sung-Gil; Sun, Ho Jin; Ha, Su; Kim, Jungbae

    2016-01-01

    The present study aims at fabricating a laccase (LAC) based amperometric biosensor for detection of phenolic compounds. LAC was immobilized into the porous matrix of polyaniline nanofibers (PANFs) in a three-step process, consisting of enzyme adsorption, precipitation, and crosslinking (EAPC). Immobilized LAC on PANF in the form of EAPC was highly active and stable when compared to control samples of 'enzyme adsorption (EA)' and 'enzyme adsorption and crosslinking (EAC)' samples. For example, the activity of EAPC was 19.7 and 15.1 times higher than those of EA and EAC per unit weight of PANF, respectively. After 6days at room temperature, EAPC maintained 100% of its initial activity, while EA and EAC retained only 7.7% and 11% of their initial activities, respectively. When the samples were subjected to the heat treatment at 60°C over 3h, EAPC maintained 74% of its initial activity, while EA and EAC retained around 1% of their initial activities, respectively. To demonstrate the feasible application of EAPC in biosensors, the enzyme electrodes were prepared and used for detection of phenolic compounds, which are environmentally hazardous chemicals. The sensitivities of biosensors with EA, EAC, and EAPC were 20.3±5.9, 26.6±5.4 and 518±11μAmM(-1)cm(-2), respectively. At 50°C for 5h, EAPC electrode maintained 80% of its initial sensitivity, while EA and EAC electrode showed 0% and 19% of their initial sensitivities, respectively. Thus, LAC-based biosensor using EAPC protocol with PANFs showed a great promise for developing a highly sensitive and stable biosensor for detection of phenolic compounds.

  20. Precipitated and chemically-crosslinked laccase over polyaniline nanofiber for high performance phenol sensing.

    PubMed

    Kim, Jae Hyun; Hong, Sung-Gil; Sun, Ho Jin; Ha, Su; Kim, Jungbae

    2016-01-01

    The present study aims at fabricating a laccase (LAC) based amperometric biosensor for detection of phenolic compounds. LAC was immobilized into the porous matrix of polyaniline nanofibers (PANFs) in a three-step process, consisting of enzyme adsorption, precipitation, and crosslinking (EAPC). Immobilized LAC on PANF in the form of EAPC was highly active and stable when compared to control samples of 'enzyme adsorption (EA)' and 'enzyme adsorption and crosslinking (EAC)' samples. For example, the activity of EAPC was 19.7 and 15.1 times higher than those of EA and EAC per unit weight of PANF, respectively. After 6days at room temperature, EAPC maintained 100% of its initial activity, while EA and EAC retained only 7.7% and 11% of their initial activities, respectively. When the samples were subjected to the heat treatment at 60°C over 3h, EAPC maintained 74% of its initial activity, while EA and EAC retained around 1% of their initial activities, respectively. To demonstrate the feasible application of EAPC in biosensors, the enzyme electrodes were prepared and used for detection of phenolic compounds, which are environmentally hazardous chemicals. The sensitivities of biosensors with EA, EAC, and EAPC were 20.3±5.9, 26.6±5.4 and 518±11μAmM(-1)cm(-2), respectively. At 50°C for 5h, EAPC electrode maintained 80% of its initial sensitivity, while EA and EAC electrode showed 0% and 19% of their initial sensitivities, respectively. Thus, LAC-based biosensor using EAPC protocol with PANFs showed a great promise for developing a highly sensitive and stable biosensor for detection of phenolic compounds. PMID:26294327

  1. Synthesis of cellulose-based superabsorbent hydrogels by high-energy irradiation in the presence of crosslinking agent

    NASA Astrophysics Data System (ADS)

    Fekete, Tamás; Borsa, Judit; Takács, Erzsébet; Wojnárovits, László

    2016-01-01

    Superabsorbent hydrogels were prepared from aqueous solutions of four cellulose derivatives (carboxymethylcellulose Na-salt - CMC, methylcellulose - MC, hydroxyethylcellulose - HEC and hydroxypropylcellulose - HPC) by gamma irradiation initiated crosslinking. CMC was used for the majority of the measurements. N,N'-methylene-bis-acrylamide (MBA) crosslinking agent was used to modify the gel properties. The crosslink density increased with the MBA concentration, leading to an improved gel fraction and lower water uptake. The crosslinking efficiency was the highest up to 1 w/wpolymer% MBA concentration. Very high MBA content (10 w/wpolymer%) led to a heterogeneous gel structure. Gelation also occurred under milder conditions in the presence of MBA: good gel properties were achieved at significantly lower doses and solute concentrations as compared to crosslinker-free solutions. The time required to reach maximum water uptake increased with the degree of swelling in equilibrium. Swelling properties of CMC gels with lower water uptake showed lower sensitivity to the ionic strength of the solvent.

  2. Translational informatics: enabling high-throughput research paradigms

    PubMed Central

    Embi, Peter J.; Sen, Chandan K.

    2009-01-01

    A common thread throughout the clinical and translational research domains is the need to collect, manage, integrate, analyze, and disseminate large-scale, heterogeneous biomedical data sets. However, well-established and broadly adopted theoretical and practical frameworks and models intended to address such needs are conspicuously absent in the published literature or other reputable knowledge sources. Instead, the development and execution of multidisciplinary, clinical, or translational studies are significantly limited by the propagation of “silos” of both data and expertise. Motivated by this fundamental challenge, we report upon the current state and evolution of biomedical informatics as it pertains to the conduct of high-throughput clinical and translational research and will present both a conceptual and practical framework for the design and execution of informatics-enabled studies. The objective of presenting such findings and constructs is to provide the clinical and translational research community with a common frame of reference for discussing and expanding upon such models and methodologies. PMID:19737991

  3. Proton modification of ultra high molecular weight polyethylene to promote crosslinking for enhanced chemical and physical properties

    SciTech Connect

    Wilson, J.F.; Liu, J.R.; Romero-Borja, F.; Chu, W.K.

    1996-12-31

    Crosslinking onset was investigated for ultra high molecular weight polyethylene (UHMW-PE) implanted with 2.6 MeV H{sup +} ions at low doses from 6 {times} 10{sup 11}--3 {times} 10{sup 13} ions/cm{sup 2}. Crosslinking in the near surface region (20--40 {micro}m) was determined from gel permeation chromatography (GPC) of 1,2,4 trichlorobenzene sol fractions and increased with dose. Fourier transform infrared spectroscopy (FTIR) showed irradiation resulted in increased free radicals confirms from increased carbonyl groups. Hydrogen annealing after ion implantation resulted in 38--49% decrease in FTIR peak associated with carbonyl.

  4. The compressive behavior of isocyanate-crosslinked silica aerogel at high strain rates

    NASA Astrophysics Data System (ADS)

    Luo, H.; Lu, H.; Leventis, N.

    2006-06-01

    Aerogels are low-density, highly nano-porous materials. Their engineering applications are limited due to their brittleness and hydrophilicity. Recently, a strong lightweight crosslinked silica aerogel has been developed by encapsulating the skeletal framework of amine-modified silica aerogels with polyureas derived by isocyanate. The mesoporous structure of the underlying silica framework is preserved through conformal polymer coating, and the thermal conductivity remains low. Characterization has been conducted on the thermal, physical properties and the mechanical properties under quasi-static loading conditions. In this paper, we present results on the dynamic compressive behavior of the crosslinked silica aerogel (CSA) using a split Hopkinson pressure bar (SHPB). A new tubing pulse shaper was employed to help reach the dynamic stress equilibrium and constant strain rate. The stress-strain relationship was determined at high strain rates within 114-4386 s-1. The effects of strain rate, density, specimen thickness and water absorption on the dynamic behavior of the CSA were investigated through a series of dynamic experiments. The Young’s moduli (or 0.2% offset compressive yield strengths) at a strain rate ˜350 s-1 were determined as 10.96/2.08, 159.5/6.75, 192.2/7.68, 304.6/11.46, 407.0/20.91 and 640.5/30.47 MPa for CSA with densities 0.205, 0.454, 0.492, 0.551, 0.628 and 0.731 g cm-3, respectively. The deformation and failure behaviors of a native silica aerogel with density (0.472 g cm-3), approximately the same as a typical CSA sample were observed with a high speed digital camera. Digital image correlation technique was used to determine the surface strains through a series of images acquired using high speed photography. The relative uniform axial deformation indicated that localized compaction did not occur at a compressive strain level of ˜17%, suggesting most likely failure mechanism at high strain rate to be different from that under quasi

  5. The Compressive Behavior of Isocyanate-crosslinked Silica Aerogel at High Strain Rates

    NASA Technical Reports Server (NTRS)

    Luo, H.; Lu, H.; Leventis, N.

    2006-01-01

    Aerogels are low-density, highly nano-porous materials. Their engineering applications are limited due to their brittleness and hydrophilicity. Recently, a strong lightweight crosslinked silica aerogel has been developed by encapsulating the skeletal framework of amine-modified silica aerogels with polyureas derived by isocyanate. The mesoporous structure of the underlying silica framework is preserved through conformal polymer coating, and the thermal conductivity remains low. Characterization has been conducted on the thermal, physical properties and the mechanical properties under quasi-static loading conditions. In this paper, we present results on the dynamic compressive behavior of the crosslinked silica aerogel (CSA) using a split Hopkinson pressure bar (SHPB). A new tubing pulse shaper was employed to help reach the dynamic stress equilibrium and constant strain rate. The stress-strain relationship was determined at high strain rates within 114-4386/s. The effects of strain rate, density, specimen thickness and water absorption on the dynamic behavior of the CSA were investigated through a series of dynamic experiments. The Young's moduli (or 0.2% offset compressive yield strengths) at a strain rate approx.350/s were determined as 10.96/2.08, 159.5/6.75, 192.2/7.68, 304.6/11.46, 407.0/20.91 and 640.5/30.47 MPa for CSA with densities 0.205, 0.454, 0.492, 0.551,0.628 and 0.731 g/cu cm, respectively. The deformation and failure behaviors of a native silica aerogel with density (0.472 g/cu cm ), approximately the same as a typical CSA sample were observed with a high speed digital camera. Digital image correlation technique was used to determine the surface strains through a series of images acquired using high speed photography. The relative uniform axial deformation indicated that localized compaction did not occur at a compressive strain level of approx.17%, suggesting most likely failure mechanism at high strain rate to be different from that under quasi

  6. ASIC-enabled High Resolution Optical Time Domain Reflectometer

    NASA Astrophysics Data System (ADS)

    Skendzic, Sandra

    Fiber optics has become the preferred technology in communication systems because of what it has to offer: high data transmission rates, immunity to electromagnetic interference, and lightweight, flexible cables. An optical time domain reflectometer (OTDR) provides a convenient method of locating and diagnosing faults (e.g. break in a fiber) along a fiber that can obstruct crucial optical pathways. Both the ability to resolve the precise location of the fault and distinguish between two discrete, closely spaced faults are figures of merit. This thesis presents an implementation of a high resolution OTDR through the use of a compact and programmable ASIC (application specific integrated circuit). The integration of many essential OTDR functions on a single chip is advantageous over existing commercial instruments because it enables small, lightweight packaging, and offers low power and cost efficiency. Furthermore, its compactness presents the option of placing multiple ASICs in parallel, which can conceivably ease the characterization of densely populated fiber optic networks. The OTDR ASIC consists of a tunable clock, pattern generator, precise timer, electrical receiver, and signal sampling circuit. During OTDR operation, the chip generates narrow electrical pulse, which can then be converted to optical format when coupled with an external laser diode driver. The ASIC also works with an external photodetector to measure the timing and amplitude of optical reflections in a fiber. It has a 1 cm sampling resolution, which allows for a 2 cm spatial resolution. While this OTDR ASIC has been previously demonstrated for multimode fiber fault diagnostics, this thesis focuses on extending its functionality to single mode fiber. To validate this novel approach to OTDR, this thesis is divided into five chapters: (1) introduction, (2) implementation, (3), performance of ASIC-based OTDR, (4) exploration in optical pre-amplification with a semiconductor optical amplifier, and

  7. Cross-Linking Amine-Rich Compounds into High Performing Selective CO2 Absorbents

    PubMed Central

    Andreoli, Enrico; Dillon, Eoghan P.; Cullum, Laurie; Alemany, Lawrence B.; Barron, Andrew R.

    2014-01-01

    Amine-based absorbents play a central role in CO2 sequestration and utilization. Amines react selectively with CO2, but a drawback is the unproductive weight of solvent or support in the absorbent. Efforts have focused on metal organic frameworks (MOFs) reaching extremely high CO2 capacity, but limited selectivity to N2 and CH4, and decreased uptake at higher temperatures. A desirable system would have selectivity (cf. amine) and high capacity (cf. MOF), but also increased adsorption at higher temperatures. Here, we demonstrate a proof-of-concept where polyethyleneimine (PEI) is converted to a high capacity and highly selective CO2 absorbent using buckminsterfullerene (C60) as a cross-linker. PEI-C60 (CO2 absorption of 0.14 g/g at 0.1 bar/90°C) is compared to one of the best MOFs, Mg-MOF-74 (0.06 g/g at 0.1 bar/90°C), and does not absorb any measurable amount of CH4 at 50 bar. Thus, PEI-C60 can perform better than MOFs in the sweetening of natural gas. PMID:25467054

  8. Cross-linking amine-rich compounds into high performing selective CO2 absorbents.

    PubMed

    Andreoli, Enrico; Dillon, Eoghan P; Cullum, Laurie; Alemany, Lawrence B; Barron, Andrew R

    2014-12-03

    Amine-based absorbents play a central role in CO2 sequestration and utilization. Amines react selectively with CO2, but a drawback is the unproductive weight of solvent or support in the absorbent. Efforts have focused on metal organic frameworks (MOFs) reaching extremely high CO2 capacity, but limited selectivity to N2 and CH4, and decreased uptake at higher temperatures. A desirable system would have selectivity (cf. amine) and high capacity (cf. MOF), but also increased adsorption at higher temperatures. Here, we demonstrate a proof-of-concept where polyethyleneimine (PEI) is converted to a high capacity and highly selective CO2 absorbent using buckminsterfullerene (C(60)) as a cross-linker. PEI-C(60) (CO2 absorption of 0.14 g/g at 0.1 bar/90 °C) is compared to one of the best MOFs, Mg-MOF-74 (0.06 g/g at 0.1 bar/90 °C), and does not absorb any measurable amount of CH4 at 50 bar. Thus, PEI-C(60) can perform better than MOFs in the sweetening of natural gas.

  9. Direct measurement of crosslinks, pyridinoline, deoxypyridinoline, and pentosidine, in the hydrolysate of tissues using high-performance liquid chromatography.

    PubMed

    Takahashi, M; Hoshino, H; Kushida, K; Inoue, T

    1995-12-10

    Pyridinoline (Pyr) and deoxypyridinoline (Dpyr) are mature crosslinks which maintain the structure of the collagen fibril. Pentosidine (Pen) is a senescent crosslink and one of the advanced glycation end products. We developed a direct and one-injection method to measure Pyr, Dpyr, and Pen in the hydrolysate of tissues using reversed-phase high-performance liquid chromatography. Using a linear gradient of acetonitrile and a cleaning step, the objective crosslinks were well separated and continuously and automatically assayed. Recovery rates of Pyr, Dpyr, and Pen were 95-116, 94-110, and 92-120%, respectively (n = 5). The intraassay coefficients of variation for Pyr, Dpyr, and Pen were 5.3, 5.8, and 4.3%, respectively (n = 5), and the interassay coefficients of variation for Pyr, Dpyr, and Pen were 3.5, 4.6, and 5.7%, respectively (n = 5). Linear regression analysis showed the linearity (r = 0.999) of calibration line for each Pyr, Dpyr, and Pen. We measured the content of these crosslinks in the tissues from the young and old subjects. There was no difference in the content of Pyr and Dpyr between the young and the old group. On the other hand, the content of Pen in the old group was extremely higher than that in the young group. We demonstrated the direct method for measuring two kinds of major crosslinks which have different characters and believe that this method will be useful in determining the content of these crosslinks in tissues under various conditions.

  10. Dually cross-linked single network poly(acrylic acid) hydrogels with superior mechanical properties and water absorbency.

    PubMed

    Zhong, Ming; Liu, Yi-Tao; Liu, Xiao-Ying; Shi, Fu-Kuan; Zhang, Li-Qin; Zhu, Mei-Fang; Xie, Xu-Ming

    2016-06-28

    Poly(acrylic acid) (PAA) hydrogels with superior mechanical properties, based on a single network structure with dual cross-linking, are prepared by one-pot free radical polymerization. The network structure of the PAA hydrogels is composed of dual cross-linking: a dynamic and reversible ionic cross-linking among the PAA chains enabled by Fe(3+) ions, and a sparse covalent cross-linking enabled by a covalent cross-linker (Bis). Under deformation, the covalently cross-linked PAA chains remain intact to maintain their original configuration, while the Fe(3+)-enabled ionic cross-linking among the PAA chains is broken to dissipate energy and then recombined. It is found that the mechanical properties of the PAA hydrogels are significantly influenced by the contents of covalent cross-linkers, Fe(3+) ions and water, which can be adjusted within a substantial range and thus broaden the applications of the hydrogels. Meanwhile, the PAA hydrogels have excellent recoverability based on the dynamic and reversible ionic cross-linking enabled by Fe(3+) ions. Moreover, the swelling capacity of the PAA hydrogels is as high as 1800 times in deionized water due to the synergistic effects of ionic and covalent cross-linkings. The combination of balanced mechanical properties, efficient recoverability, high swelling capacity and facile preparation provides a new method to obtain high-performance hydrogels. PMID:27230478

  11. Radiation crosslinking of polypropylene

    NASA Astrophysics Data System (ADS)

    Sawasaki, T.; Nojiri, A.

    The radiation crosslinking of polypropylene (PP) with several of polyfunctional monomers has been examined. Formerly many kinds of PP crosslinking methods have been reported, but these have some problems, such as limitations on the thickness of sheets and the degradation of the resin caused by irradiation. We have found that the polyfunctional monomers can be classified into three types by the irradiation dose necessary for crosslinking. In particular, we have developed a new crosslinking method using a specific crosslinking coagent having an acryloyloxy group with a very low required irradiation dose. If this type of monomer is used, 0.5 Mrad is enough to saturate the crosslinking, while the other two types require more than 5 Mrad. The degree of crosslinking is estimated by the gel fraction, modulus of the molten sheet and that of degradation by elongation and oxidation induction time. The crosslinked PP obtained by this method has many good properties, such as a high modulus, large elongation, and high heat resistance. This method may be applied in the manufacture of foamy and other heat resistant materials.

  12. Highly Stable and Porous Cross-Linked Polymers for Efficient Photocatalysis

    SciTech Connect

    Xie, Zhigang; Wang, Cheng; deKrafft, Kathryn E.; Lin, Wenbin

    2011-02-23

    Porous cross-linked polymers (PCPs) with phosphorescent [Ru(bpy)₃]{sup 2+} and [Ir(ppy)₂(bpy)]{sup +} building blocks were obtained via octacarbonyldicobalt (Co₂(CO)₈)-catalyzed alkyne trimerization reactions. The resultant Ru- and Ir-PCPs exhibited high porosity with specific surface areas of 1348 and 1547 m²/g, respectively. They are thermally stable at up to 350 °C in air and do not dissolve or decompose in all solvents tested, including concentrated hydrochloric acid. The photoactive PCPs were shown to be highly effective, recyclable, and reusable heterogeneous photocatalysts for aza-Henry reactions, α-arylation of bromomalonate, and oxyamination of an aldehyde, with catalytic activities comparable to those of the homogeneous [Ru(bpy)₃]{sup 2+} and [Ir(ppy)₂(bpy)]{sup +} photocatalysts. This work highlights the potential of developing photoactive PCPs as highly stable, molecularly tunable, and recyclable and reusable heterogeneous photocatalysts for a variety of important organic transformations.

  13. Crosslinked Polyamide

    DOEpatents

    Huang, Zhi H.; McDonald, William F.; Wright, Stacy C.; Taylor, Andrew C.

    2002-06-04

    A crosslinked polyamide material and a process for preparing the crosslinked polyamide material are disclosed. The crosslinked polyamide material comprises a crosslinked chemical combination of (1) a polyamide of the formula: ##STR1## wherein n is between about 50 and 10,000, wherein each R is between 1 and 50 carbon atoms alone and is optionally substituted with heteroatoms, oxygen, nitrogen, sulfur, or phosphorus and combinations thereof, wherein multiple of the R are in vertically aligned spaced relationship along a backbone forming the polyamide, and wherein two or more of the R contain an amino group; and (2) a crosslinking agent containing at least two functional groups capable of reacting with the amino groups of the polyamide. In one embodiment of the invention, the crosslinking agent is an aliphatic or aromatic isocyanate compound having 2 or more --N.dbd.C.dbd.O groups. In another embodiment of the invention, the crosslinking agent is an aliphatic aldehyde or aromatic aldehyde compound having 2 or more --CHO groups. In still another embodiment of the invention, the crosslinking agent is selected from a phosphine having the general formula (A).sub.2 P(B) and mixtures thereof, wherein A is hydroxyalkyl, and B is hydroxyalkyl, alkyl, or aryl. In yet another embodiment of the invention, the crosslinking agent is selected from the group consisting of epoxy resins having more than one epoxide group per molecule.

  14. Textural performance of crosslinked or reduced-calcium milk protein ingredients in model high-protein nutrition bars.

    PubMed

    Banach, J C; Clark, S; Metzger, L E; Lamsal, B P

    2016-08-01

    Transglutaminase (Tgase) crosslinking and calcium reduction were investigated as ways to improve the texture and storage stability of high-protein nutrition (HPN) bars formulated with milk protein concentrate (MPC) and micellar casein concentrate (MCC). The MPC and MCC crosslinked at none, low, and high levels, and a reduced-calcium MPC (RCMPC) were each formulated into model HPN bars. Hardness, crumbliness, moisture content, pH, color, and water activity of the HPN bars were measured during accelerated storage. The HPN bars prepared with MPC were harder and more cohesive than those prepared with MCC. Higher levels of Tgase crosslinking improved HPN bar cohesiveness and decreased hardening during storage. The RCMPC produced softer, yet crumblier HPN bars. Small textural differences were observed for the HPN bars formulated with the transglutaminase crosslinked proteins or RCMPC when compared with their respective controls. However, modification only slightly improved protein ingredient ability to slow hardening while balancing cohesion and likely requires further improvement for increased applicability in soft-texture HPN bars. PMID:27236767

  15. Textural performance of crosslinked or reduced-calcium milk protein ingredients in model high-protein nutrition bars.

    PubMed

    Banach, J C; Clark, S; Metzger, L E; Lamsal, B P

    2016-08-01

    Transglutaminase (Tgase) crosslinking and calcium reduction were investigated as ways to improve the texture and storage stability of high-protein nutrition (HPN) bars formulated with milk protein concentrate (MPC) and micellar casein concentrate (MCC). The MPC and MCC crosslinked at none, low, and high levels, and a reduced-calcium MPC (RCMPC) were each formulated into model HPN bars. Hardness, crumbliness, moisture content, pH, color, and water activity of the HPN bars were measured during accelerated storage. The HPN bars prepared with MPC were harder and more cohesive than those prepared with MCC. Higher levels of Tgase crosslinking improved HPN bar cohesiveness and decreased hardening during storage. The RCMPC produced softer, yet crumblier HPN bars. Small textural differences were observed for the HPN bars formulated with the transglutaminase crosslinked proteins or RCMPC when compared with their respective controls. However, modification only slightly improved protein ingredient ability to slow hardening while balancing cohesion and likely requires further improvement for increased applicability in soft-texture HPN bars.

  16. Total Hip Arthroplasty Using Metal Head on a Highly Cross-linked Polyethylene Liner

    PubMed Central

    Kim, Min-Yook; Park, Ji-Hoon; Lee, Jung-Ho

    2015-01-01

    Purpose This retrospective study was performed to evaluate the clinical results and measure polyethylene liner wear in total hip arthroplasty (THA) with highly cross-linked polyethylene. Materials and Methods Except for patients who had died or were unable to have follow-up at least 2 years, 60 of 78 hips that underwent THA were included this study. The mean age was 64.5 years (range, 25-81 years) and the mean body mass index (BMI) was 23.0 kg/m2 (18.1-32.3 kg/m2). Diagnosis at the time of the operation was osteonecrois of the femoral head in 28 hips, primary osteoarthritis in 14, hip fracture in 13, and other diseases in 5. The mean follow-up period was 3.8 years (2.1-7.1 years). Harris hip score (HHS) was reviewed before THA and at the last follow-up. On the anteroposterior pelvic radiographs, acetabular cup inclination and ante-version were also measured. The annual linear wear rate was measured using Livermore's method on the radiographs. Results The mean HHS was 60.1 (28-94) before operation and 90.4 (47-100) at the last follow-up. In the immediate post-operation, the average inclination and anteversion angles of the acetabular cups were 46.3° (standard deviation, ±6.7°) and, 21.4°(±10.1°) respectively. The mean of the annual linear polyethylene wear was 0.079 mm/year (0.001-0.291 mm/year). Age, gender and BMI were not statistically related to linear polyethylene wear but the period of follow-up and the acetabular cup's inclination showed significant negative and positive correlation respectively. Conclusion The wear rate of a highly cross-linked polyethylene was shown to correlate negatively with duration of follow-up. However, our study was based on a short-term follow-up, so a long-term follow-up study is necessary in the future. PMID:27536629

  17. High internal quantum efficiency in fullerene solar cells based on crosslinked polymer donor networks

    NASA Astrophysics Data System (ADS)

    Liu, Bo; Png, Rui-Qi; Zhao, Li-Hong; Chua, Lay-Lay; Friend, Richard H.; Ho, Peter K. H.

    2012-12-01

    The power conversion efficiency of organic photovoltaic cells depends crucially on the morphology of their donor-acceptor heterostructure. Although tremendous progress has been made to develop new materials that better cover the solar spectrum, this heterostructure is still formed by a primitive spontaneous demixing that is rather sensitive to processing and hence difficult to realize consistently over large areas. Here we report that the desired interpenetrating heterostructure with built-in phase contiguity can be fabricated by acceptor doping into a lightly crosslinked polymer donor network. The resultant nanotemplated network is highly reproducible and resilient to phase coarsening. For the regioregular poly(3-hexylthiophene):phenyl-C61-butyrate methyl ester donor-acceptor model system, we obtained 20% improvement in power conversion efficiency over conventional demixed biblend devices. We reached very high internal quantum efficiencies of up to 0.9 electron per photon at zero bias, over an unprecedentedly wide composition space. Detailed analysis of the power conversion, power absorbed and internal quantum efficiency landscapes reveals the separate contributions of optical interference and donor-acceptor morphology effects.

  18. High internal quantum efficiency in fullerene solar cells based on crosslinked polymer donor networks.

    PubMed

    Liu, Bo; Png, Rui-Qi; Zhao, Li-Hong; Chua, Lay-Lay; Friend, Richard H; Ho, Peter K H

    2012-01-01

    The power conversion efficiency of organic photovoltaic cells depends crucially on the morphology of their donor-acceptor heterostructure. Although tremendous progress has been made to develop new materials that better cover the solar spectrum, this heterostructure is still formed by a primitive spontaneous demixing that is rather sensitive to processing and hence difficult to realize consistently over large areas. Here we report that the desired interpenetrating heterostructure with built-in phase contiguity can be fabricated by acceptor doping into a lightly crosslinked polymer donor network. The resultant nanotemplated network is highly reproducible and resilient to phase coarsening. For the regioregular poly(3-hexylthiophene):phenyl-C(61)-butyrate methyl ester donor-acceptor model system, we obtained 20% improvement in power conversion efficiency over conventional demixed biblend devices. We reached very high internal quantum efficiencies of up to 0.9 electron per photon at zero bias, over an unprecedentedly wide composition space. Detailed analysis of the power conversion, power absorbed and internal quantum efficiency landscapes reveals the separate contributions of optical interference and donor-acceptor morphology effects.

  19. Crosslinking metal nanoparticles into the polymer backbone of hydrogels enables preparation of soft, magnetic field-driven actuators with muscle-like flexibility.

    PubMed

    Fuhrer, Roland; Athanassiou, Evagelos Kimon; Luechinger, Norman Albert; Stark, Wendelin Jan

    2009-03-01

    The combination of force and flexibility is at the core of biomechanics and enables virtually all body movements in living organisms. In sharp contrast, presently used machines are based on rigid, linear (cylinders) or circular (rotator in an electrical engine) geometries. As a potential bioinspired alternative, magnetic elastomers can be realized through dispersion of micro- or nanoparticles in polymer matrices and have attracted significant interest as soft actuators in artificial organs, implants, and devices for controlled drug delivery. At present, magnetic particle loss and limited actuator strength have restricted the use of such materials to niche applications. We describe the direct incorporation of metal nanoparticles into the backbone of a hydrogel and application as an ultra-flexible, yet strong magnetic actuator. Covalent bonding of the particles prevents metal loss or leaching. Since metals have a far higher saturation magnetization and higher density than oxides, the resulting increased force/volume ratio afforded significantly stronger magnetic actuators with high mechanical stability, elasticity, and shape memory effect.

  20. Biomechanical Properties of Human Corneas Following Low- and High-Intensity Collagen Cross-Linking Determined With Scanning Acoustic Microscopy

    PubMed Central

    Beshtawi, Ithar M.; Akhtar, Riaz; Hillarby, M. Chantal; O'Donnell, Clare; Zhao, Xuegen; Brahma, Arun; Carley, Fiona; Derby, Brian; Radhakrishnan, Hema

    2013-01-01

    Purpose. To assess and compare changes in the biomechanical properties of the cornea following different corneal collagen cross-linking protocols using scanning acoustic microscopy (SAM). Methods. Ten donor human corneal pairs were divided into two groups consisting of five corneal pairs in each group. In group A, five corneas were treated with low-fluence (370 nm, 3 mW/cm2) cross-linking (CXL) for 30 minutes. In group B, five corneas were treated with high-fluence (370 nm, 9 mW/cm2) CXL for 10 minutes. The contralateral control corneas in both groups had similar treatment but without ultraviolet A. The biomechanical properties of all corneas were tested using SAM. Results. In group A, the mean speed of sound in the treated corneas was 1677.38 ± 10.70 ms−1 anteriorly and 1603.90 ± 9.82 ms−1 posteriorly, while it was 1595.23 ± 9.66 ms−1 anteriorly and 1577.13 ± 8.16 ms−1 posteriorly in the control corneas. In group B, the mean speed of sound of the treated corneas was 1665.06 ± 9.54 ms−1 anteriorly and 1589.89 ± 9.73 ms−1 posteriorly, while it was 1583.55 ± 8.22 ms−1 anteriorly and 1565.46 ± 8.13 ms−1 posteriorly in the untreated control corneas. The increase in stiffness between the cross-linked and control corneas in both groups was by a factor of 1.051×. Conclusions. SAM successfully detected changes in the corneal stiffness after application of collagen cross-linking. A higher speed-of-sound value was found in the treated corneas when compared with the controls. No significant difference was found in corneal stiffness between the corneas cross-linked with low- and high-intensity protocols. PMID:23847309

  1. Cross-linked lysozyme crystal templated synthesis of Au nanoparticles as high-performance recyclable catalysts.

    PubMed

    Liang, Miao; Wang, Libing; Liu, Xia; Qi, Wei; Su, Rongxin; Huang, Renliang; Yu, Yanjun; He, Zhimin

    2013-06-21

    Bio-nanomaterials fabricated using a bioinspired templating technique represent a novel class of composite materials with diverse applications in biomedical, electronic devices, drug delivery, and catalysis. In this study, Au nanoparticles (NPs) are synthesized within the solvent channels of cross-linked lysozyme crystals (CLLCs) in situ without the introduction of extra chemical reagents or physical treatments. The as-prepared AuNPs-in-protein crystal hybrid materials are characterized by light microscopy, transmission electron microscopy, x-ray diffraction, and Fourier-transform infrared spectroscopy analyses. Small AuNPs with narrow size distribution reveal the restriction effects of the porous structure in the lysozyme crystals. These composite materials are proven to be active heterogeneous catalysts for the reduction of 4-nitrophenol to 4-aminophenol. These catalysts can be easily recovered and reused at least 20 times because of the physical stability and macro-dimension of CLLCs. This work is the first to use CLLCs as a solid biotemplate for the preparation of recyclable high-performance catalysts.

  2. Probabilistic assessment of fatigue initiation data on highly crosslinked ultrahigh molecular weight polyethylenes.

    PubMed

    Pascual, F J; Przybilla, C; Gracia-Villa, L; Puértolas, J A; Fernández-Canteli, A

    2012-11-01

    Ultrahigh molecular weight polyethylenes (UHMWPE) showing wear resistance, oxidative stability and good mechanical performance go on being a relevant research area in biomaterials for total joint replacements, where fatigue happens to be a recurrent damage mode that needs to be investigated. While crack propagation lifetime has been extensively studied, fatigue initiation data are scarcely offered in the literature, often due to the higher costs implied in the experimental programs. Moreover, their analysis is not always suitable to obtain reliable guidance. Different deterministic and probabilistic methods, generally resting on empirical bases have been previously used to analyze the fatigue initiation data. In this work, the probabilistic Weibull regression model of Castillo et al., based on both physical and statistical conditions, such as weakest link principle and the necessary compatibility between life-time and stress range distributions, is applied for the first time in the assessment of fatigue results of polymers, particularly to highly crosslinked UHMWPEs (HXLPEs). Accordingly, different published experimental data corresponding to HXLPE stabilized by thermal treatments and with α-tocopherol (vitamin E) are re-analyzed. Additional data are incorporated to assess the influence of notched HXLPE on fatigue performance. New conclusions are drawn from this revision.

  3. "Severe" wear challenge to 36 mm mechanically enhanced highly crosslinked polyethylene hip liners.

    PubMed

    Bowsher, J G; Williams, P A; Clarke, I C; Green, D D; Donaldson, T K

    2008-07-01

    Our purpose was to compare the wear performance of mechanically enhanced 5Mrad highly crosslinked polyethylene (MEP, ArComXL) hip liners to (control) 3Mrad UHMWPE liners (ArCom) in 36 mm head size. As a more severe synergy of clinically relevant test models, we contrasted wear with custom roughened Co-Cr surfaces (Ra 500 nm) to the standard pristine Co-Cr heads (Ra < 20 nm) using a severe microseparation test mode in our hip simulator. We adopted a previously published model to estimate potential biological activity. On new Co-Cr heads, the MEP liners showed a 47% reduction in volumetric wear a 13% reduction in wear particle size and a 27% reduction in Functional Biological Activity (FBA) compared to our control. On rough Co-Cr heads, the MEP liners showed little advantage in terms of volumetric wear compared with the control. However, the MEP liners overall showed a 38% reduction in FBA compared to the control owing to a larger volume fraction of larger particles. Thus overall the MEP liners appeared to offer advantages in terms of reduced FBA indices.

  4. Cross-linked lysozyme crystal templated synthesis of Au nanoparticles as high-performance recyclable catalysts

    NASA Astrophysics Data System (ADS)

    Liang, Miao; Wang, Libing; Liu, Xia; Qi, Wei; Su, Rongxin; Huang, Renliang; Yu, Yanjun; He, Zhimin

    2013-06-01

    Bio-nanomaterials fabricated using a bioinspired templating technique represent a novel class of composite materials with diverse applications in biomedical, electronic devices, drug delivery, and catalysis. In this study, Au nanoparticles (NPs) are synthesized within the solvent channels of cross-linked lysozyme crystals (CLLCs) in situ without the introduction of extra chemical reagents or physical treatments. The as-prepared AuNPs-in-protein crystal hybrid materials are characterized by light microscopy, transmission electron microscopy, x-ray diffraction, and Fourier-transform infrared spectroscopy analyses. Small AuNPs with narrow size distribution reveal the restriction effects of the porous structure in the lysozyme crystals. These composite materials are proven to be active heterogeneous catalysts for the reduction of 4-nitrophenol to 4-aminophenol. These catalysts can be easily recovered and reused at least 20 times because of the physical stability and macro-dimension of CLLCs. This work is the first to use CLLCs as a solid biotemplate for the preparation of recyclable high-performance catalysts.

  5. Anisotropy and oxidative resistance of highly crosslinked UHMWPE after deformation processing by solid-state ram extrusion.

    PubMed

    Kurtz, Steven M; Mazzucco, Dan; Rimnac, Clare M; Schroeder, Dave

    2006-01-01

    Solid-state deformation processing is a promising technique for modifying the physical and mechanical properties of highly crosslinked ultra-high molecular weight polyethylene (UHMWPE) beyond simple thermal treatment cycles that have been employed previously. This study evaluates anisotropy and oxidative resistance in a novel, radiation crosslinked (50 kGy) UHMWPE material (ArComXL: Biomet, Inc., Warsaw, IN), incorporating solid-state, deformation processing by extrusion below the melt transition for application in total hip arthroplasty. Tensile, compression, and small punch tests were conducted to evaluate the material properties in the three principal axes of the resulting material. Furthermore, short-term oxidative resistance was evaluated using Fourier transform infrared spectroscopy and the small punch test in conjunction with accelerated shelf aging protocols. The results of this testing indicate that the material is anisotropic, with significantly enhanced strength oriented along the long axis of the rod. For certain other properties, the magnitude of the anisotropy was relatively slight, especially in the elastic regime, in which only a 20% difference was noted between the long axis of the rod and the orthogonal, radial direction. The highly crosslinked material contains detectable free radicals, at a concentration that is 90% less than control, gamma inert sterilized UHMWPE. An unexpected finding of this study was evidence of oxidative stability of the deformation-processed material, even after 4 weeks of accelerated aging in a pressure vessel containing five atmospheres of oxygen (ASTM F2003), which resulted in macroscopic embrittlement of the control material. The oxidative stability observed in ArComXL suggests that the deformation-processed material may be suitable for air-permeable packaging and gas sterilization, which has thus far been reserved for remelted highly crosslinked UHMWPE.

  6. Examining the influence of short-term implantation on oxidative degradation in retrieved highly crosslinked polyethylene tibial components.

    PubMed

    Willie, B M; Foot, L J; Prall, M W; Bloebaum, R D

    2008-05-01

    Concerns remain regarding the oxidative resistance of highly crosslinked polyethylene (PE). The study investigated the in vivo performance of Durasul highly crosslinked PE by comparing the oxidation index, density, and percent crystallinity in the weightbearing and nonweightbearing region of retrieved components with unused time zero tibial components. Retrieved and unused Sulene conventional PE tibial components were examined for comparison and the effects of shelf age, in vivo duration, and ex vivo duration were also investigated. The oxidation index was not significantly different between unused time zero and retrieved Durasul PE components. Regression analysis data supported these findings in that neither shelf age, in vivo duration, nor ex vivo duration was a significant predictor of oxidation index in the retrieved Durasul PE components. In contrast, the retrieved conventional PE components had significantly greater oxidation index, density, and percent crystallinity compared with unused time zero PE components. Regression data suggested that in vivo and ex vivo duration, but not shelf aging, influenced the changes observed in the conventional PE components. These data also showed that in vivo loading did not significantly affect the oxidation index, density, or percent crystallinity in either the retrieved Durasul or conventional PE tibial components. This investigation demonstrates that changes in oxidation index, density, and percent crystallinity of retrieved Durasul PE components after short-term in vivo durations are likely not a clinical concern. These data should be used as a benchmark to compare with future studies examining the long-term oxidative resistance of Durasul highly crosslinked PE tibial components.

  7. Riboflavin crosslinked high-density collagen gel for the repair of annular defects in intervertebral discs: An in vivo study.

    PubMed

    Grunert, Peter; Borde, Brandon H; Towne, Sara B; Moriguchi, Yu; Hudson, Katherine D; Bonassar, Lawrence J; Härtl, Roger

    2015-10-01

    Open annular defects compromise the ability of the annulus fibrosus to contain nuclear tissue in the disc space, and therefore lead to disc herniation with subsequent degenerative changes to the entire intervertebral disc. This study reports the use of riboflavin crosslinked high-density collagen gel for the repair of annular defects in a needle-punctured rat-tail model. High-density collagen has increased stiffness and greater hydraulic permeability than conventional low-density gels; riboflavin crosslinking further increases these properties. This study found that treating annular defects with crosslinked high-density collagen inhibited the progression of disc degeneration over 18 weeks compared to untreated control discs. Histological sections of FITC-labeled collagen gel revealed an early tight attachment to host annular tissue. The gel was subsequently infiltrated by host fibroblasts which remodeled it into a fibrous cap that bridged the outer disrupted annular fibers and partially repaired the defect. This repair tissue enhanced retention of nucleus pulposus tissue, maintained physiological disc hydration, and preserved hydraulic permeability, according to MRI, histological, and mechanical assessments. Degenerative changes were partially reversed in treated discs, as indicated by an increase in nucleus pulposus size and hydration between weeks 5 and 18. The collagen gel appeared to work as an instant sealant and by enhancing the intrinsic healing capabilities of the host tissue.

  8. WEAR RESISTANCE AND MECHANICAL PROPERTIES OF HIGHLY CROSSLINKED UHMWPE DOPED WITH VITAMIN-E

    PubMed Central

    Oral, Ebru; Christensen, Steven D.; Malhi, Arnaz S.; Wannomae, Keith K.; Muratoglu, Orhun K.

    2008-01-01

    Our hypothesis was that cross-linked UHMWPE stabilized with vitamin-E would be wear and fatigue resistant. Acetabular liners were radiation cross-linked, doped with vitamin E and γ-sterilized. Hip simulator wear rate of vitamin E-stabilized UHMWPE was approximately 1 and 6 mg/million-cycles in clean serum and in serum with third-body bone cement particles, respectively; a four to ten-fold decrease from that of conventional UHMWPE. The ultimate strength, yield strength, elongation-at-break and fatigue resistance of vitamin E-stabilized UHMWPE were significantly higher than that of 100-kGy irradiated and melted UHMWPE and were unaffected by accelerated aging. Rim impingement testing with 3.7 mm-thick acetabular liners up to 2 million-cycles showed no significant damage of the cross-linked liners compared to conventional, gamma-sterilized in inert UHMWPE vitamin-E stabilized liners. The data indicate good wear properties and improved mechanical and fatigue properties for vitamin-E stabilized cross-linked UHMWPE. PMID:16781413

  9. Temperature dependence of creep compliance of highly cross-linked epoxy: A molecular simulation study

    SciTech Connect

    Khabaz, Fardin Khare, Ketan S. Khare, Rajesh

    2014-05-15

    We have used molecular dynamics (MD) simulations to study the effect of temperature on the creep compliance of neat cross-linked epoxy. Experimental studies of mechanical behavior of cross-linked epoxy in literature commonly report creep compliance values, whereas molecular simulations of these systems have primarily focused on the Young’s modulus. In this work, in order to obtain a more direct comparison between experiments and simulations, atomistically detailed models of the cross-linked epoxy are used to study their creep compliance as a function of temperature using MD simulations. The creep tests are performed by applying a constant tensile stress and monitoring the resulting strain in the system. Our results show that simulated values of creep compliance increase with an increase in both time and temperature. We believe that such calculations of the creep compliance, along with the use of time temperature superposition, hold great promise in connecting the molecular insight obtained from molecular simulation at small length- and time-scales with the experimental behavior of such materials. To the best of our knowledge, this work is the first reported effort that investigates the creep compliance behavior of cross-linked epoxy using MD simulations.

  10. Highly conductive carbon nanotube buckypapers with improved doping stability via conjugational cross-linking

    NASA Astrophysics Data System (ADS)

    Chen, I.-Wen Peter; Liang, Richard; Zhao, Haibo; Wang, Ben; Zhang, Chuck

    2011-12-01

    Carbon nanotube (CNT) sheets or buckypapers have demonstrated promising electrical conductivity and mechanical performance. However, their electrical conductivity is still far below the requirements for engineering applications, such as using as a substitute for copper mesh, which is currently used in composite aircraft structures for lightning strike protection. In this study, different CNT buckypapers were stretched to increase their alignment, and then subjected to conjugational cross-linking via chemical functionalization. The conjugationally cross-linked buckypapers (CCL-BPs) demonstrated higher electrical conductivity of up to 6200 S cm - 1, which is more than one order increase compared to the pristine buckypapers. The CCL-BPs also showed excellent doping stability in over 300 h in atmosphere and were resistant to degradation at elevated temperatures. The tensile strength of the stretched CCL-BPs reached 220 MPa, which is about three times that of pristine buckypapers. We attribute these property improvements to the effective and stable conjugational cross-links of CNTs, which can simultaneously improve the electrical conductivity, doping stability and mechanical properties. Specifically, the electrical conductivity increase resulted from improving the CNT alignment and inter-tube electron transport capability. The conjugational cross-links provide effective 3D conductive paths to increase the mobility of electrons among individual nanotubes. The stable covalent bonding also enhances the thermal stability and load transfer. The significant electrical and mechanical property improvement renders buckypaper a multifunctional material for various applications, such as conducting composites, battery electrodes, capacitors, etc.

  11. Oxidation of Second Generation Sequentially Irradiated and Annealed Highly Cross-Linked X3™ Polyethylene Tibial Bearings.

    PubMed

    Kop, Alan M; Pabbruwe, Moreica B; Keogh, Catherine; Swarts, Eric

    2015-10-01

    Since the first use of ultra-high-molecular-weight polyethylene as a bearing material, research and development efforts have sought to improve wear resistance, increase longevity and lessen the potential for debris mediated adverse tissue responses. A series of second generation sequentially cross-linked and annealed tibial bearings were analysed after several bearings sent for routine retrieval analysis showed oxidative degradation including subsurface whitening, cracking and gross material loss. Evaluation incorporated visual and white banding assessment, mechanical testing and spectroscopy analysis. Whilst visual observation and white banding assessment confirmed oxidative changes, a decrease in mechanical properties and increasing ketone oxidation index as a function of time in vivo suggest time dependent oxidative degradation. Clinically relevant degradation of the sequentially cross-linked and annealed tibial bearings was observed.

  12. FLUIDIZED BED STEAM REFORMING ENABLING ORGANIC HIGH LEVEL WASTE DISPOSAL

    SciTech Connect

    Williams, M

    2008-05-09

    Waste streams planned for generation by the Global Nuclear Energy Partnership (GNEP) and existing radioactive High Level Waste (HLW) streams containing organic compounds such as the Tank 48H waste stream at Savannah River Site have completed simulant and radioactive testing, respectfully, by Savannah River National Laboratory (SRNL). GNEP waste streams will include up to 53 wt% organic compounds and nitrates up to 56 wt%. Decomposition of high nitrate streams requires reducing conditions, e.g. provided by organic additives such as sugar or coal, to reduce NOX in the off-gas to N2 to meet Clean Air Act (CAA) standards during processing. Thus, organics will be present during the waste form stabilization process regardless of the GNEP processes utilized and exists in some of the high level radioactive waste tanks at Savannah River Site and Hanford Tank Farms, e.g. organics in the feed or organics used for nitrate destruction. Waste streams containing high organic concentrations cannot be stabilized with the existing HLW Best Developed Available Technology (BDAT) which is HLW vitrification (HLVIT) unless the organics are removed by pretreatment. The alternative waste stabilization pretreatment process of Fluidized Bed Steam Reforming (FBSR) operates at moderate temperatures (650-750 C) compared to vitrification (1150-1300 C). The FBSR process has been demonstrated on GNEP simulated waste and radioactive waste containing high organics from Tank 48H to convert organics to CAA compliant gases, create no secondary liquid waste streams and create a stable mineral waste form.

  13. Phase Change of Gallium Enables Highly Reversible and Switchable Adhesion.

    PubMed

    Ye, Zhou; Lum, Guo Zhan; Song, Sukho; Rich, Steven; Sitti, Metin

    2016-07-01

    Gallium exhibits highly reversible and switchable adhesion when it undergoes a solid-liquid phase transition. The robustness of gallium is notable as it exhibits strong performance on a wide range of smooth and rough surfaces, under both dry and wet conditions. Gallium may therefore find numerous applications in transfer printing, robotics, electronic packaging, and biomedicine. PMID:27146217

  14. Plant respirometer enables high resolution of oxygen consumption rates

    NASA Technical Reports Server (NTRS)

    Foster, D. L.

    1966-01-01

    Plant respirometer permits high resolution of relatively small changes in the rate of oxygen consumed by plant organisms undergoing oxidative metabolism in a nonphotosynthetic state. The two stage supply and monitoring system operates by a differential pressure transducer and provides a calibrated output by digital or analog signals.

  15. Device enables calibration of microphones at high sound pressure levels

    NASA Technical Reports Server (NTRS)

    Gillen, A.

    1967-01-01

    Coupling device accurately calibrates microphones at high sound pressure intensities. The system which uses a liquid as the coupling medium can operate in an automatic mode by using a standard microphone as a control sensor. Feedback from the standard microphone controls the calibration signal level.

  16. Highly sensitive amyloid detection enabled by thioflavin T dimers.

    PubMed

    Qin, Luoheng; Vastl, Julian; Gao, Jianmin

    2010-10-01

    Fluorescent molecules that specifically target amyloid structures are highly desirable for amyloid research. Herein, we show a dimeric design of thioflavin T improves its binding affinity to Abeta amyloid by up to 70 fold, while not sacrificing the specificity and the "light-up" feature upon amyloid binding.

  17. Cross-linking of fibrinogen and fibrin by fibrin-stablizing factor (factor XIIIa).

    PubMed

    Kanaide, H; Shainoff, J R

    1975-04-01

    Factor XIIIa catalyzed intermolecular cross-linking of fibrinogen at initial rates that varied in direct (first order) proportion to the fibrinogen concentration, which differed from the well known zero order relationship in fibrin cross-linking. Preferential cross-linking of gamma-chains occurred with both substrates. The differences in rates and order of reaction were attributed mainly to effect of self-alignment of the gamma-chains in fibrin which enabled the cross-linking enzyme to interact with paired chains as a single rather than two independent entities. Studies on mixtures of fibrinogen and fibrin indicated factor XIIIa had near equal affinities for the two substrates. At low concentrations with which cross-linking of fibrinogen proceeded sluggishly compared to fibrin, fibrinogen inhibited stabilization of fibrin clots by competitively partitioning factor XIIIa away from the fribin. Additional inhibition arose from cross-linking of fibrin in soluble combination with fibrinogen in mixtures containing fibrinogen in large excess over fibrin. The observations demonstrate ways in which fibrinogen normally helps to suppress both polymerization and cross-linking of small amounts of fibrin produced within the circulation. At very high concentrations above 30 mg. per milliliter, fibrinogen underwent cross-linking at faster initial rates than the cross-linking of fibrin. Rapid cross-linking of concentrated fibrogen raises the possibility that filtration enrichment may be a factor contributing to abnormal formation of the highly insoluble fibrinogen deposits occurring in atheromatous tissue.

  18. Enabling Exploration of Deep Space: High Density Storage of Antimatter

    NASA Technical Reports Server (NTRS)

    Smith, Gerald A.; Kramer, Kevin J.

    1999-01-01

    Portable electromagnetic antiproton traps are now in a state of realization. This allows facilities like NASA Marshall Space Flight Center to conduct antimatter research remote to production sites. MSFC is currently developing a trap to store 10(exp 12) antiprotons for a twenty-day half-life period to be used in future experiments including antimatter plasma guns, antimatter-initiated microfusion, and the synthesis of antihydrogen for space propulsion applications. In 1998, issues including design, safety and transportation were considered for the MSFC High Performance Antimatter Trap (HiPAT). Radial diffusion and annihilation losses of antiprotons prompted the use of a 4 Tesla superconducting magnet and a 20 KV electrostatic potential at 10(exp -12) Torr pressure. Cryogenic fluids used to maintain a trap temperature of 4K were sized accordingly to provide twenty days of stand-alone storage time (half-life). Procurement of the superconducting magnet with associated cryostat has been completed. The inner, ultra-high vacuum system with electrode structures has been fabricated, tested and delivered to MSFC along with the magnet and cryostat. Assembly of these systems is currently in progress. Testing under high vacuum conditions, using electrons and hydrogen ions will follow in the months ahead.

  19. High-contrast and fast electrochromic switching enabled by plasmonics.

    PubMed

    Xu, Ting; Walter, Erich C; Agrawal, Amit; Bohn, Christopher; Velmurugan, Jeyavel; Zhu, Wenqi; Lezec, Henri J; Talin, A Alec

    2016-01-01

    With vibrant colours and simple, room-temperature processing methods, electrochromic polymers have attracted attention as active materials for flexible, low-power-consuming devices. However, slow switching speeds in devices realized to date, as well as the complexity of having to combine several distinct polymers to achieve a full-colour gamut, have limited electrochromic materials to niche applications. Here we achieve fast, high-contrast electrochromic switching by significantly enhancing the interaction of light--propagating as deep-subwavelength-confined surface plasmon polaritons through arrays of metallic nanoslits, with an electrochromic polymer--present as an ultra-thin coating on the slit sidewalls. The switchable configuration retains the short temporal charge-diffusion characteristics of thin electrochromic films, while maintaining the high optical contrast associated with thicker electrochromic coatings. We further demonstrate that by controlling the pitch of the nanoslit arrays, it is possible to achieve a full-colour response with high contrast and fast switching speeds, while relying on just one electrochromic polymer. PMID:26814453

  20. High-contrast and fast electrochromic switching enabled by plasmonics

    PubMed Central

    Xu, Ting; Walter, Erich C.; Agrawal, Amit; Bohn, Christopher; Velmurugan, Jeyavel; Zhu, Wenqi; Lezec, Henri J.; Talin, A. Alec

    2016-01-01

    With vibrant colours and simple, room-temperature processing methods, electrochromic polymers have attracted attention as active materials for flexible, low-power-consuming devices. However, slow switching speeds in devices realized to date, as well as the complexity of having to combine several distinct polymers to achieve a full-colour gamut, have limited electrochromic materials to niche applications. Here we achieve fast, high-contrast electrochromic switching by significantly enhancing the interaction of light—propagating as deep-subwavelength-confined surface plasmon polaritons through arrays of metallic nanoslits, with an electrochromic polymer—present as an ultra-thin coating on the slit sidewalls. The switchable configuration retains the short temporal charge-diffusion characteristics of thin electrochromic films, while maintaining the high optical contrast associated with thicker electrochromic coatings. We further demonstrate that by controlling the pitch of the nanoslit arrays, it is possible to achieve a full-colour response with high contrast and fast switching speeds, while relying on just one electrochromic polymer. PMID:26814453

  1. High-contrast and fast electrochromic switching enabled by plasmonics.

    PubMed

    Xu, Ting; Walter, Erich C; Agrawal, Amit; Bohn, Christopher; Velmurugan, Jeyavel; Zhu, Wenqi; Lezec, Henri J; Talin, A Alec

    2016-01-27

    With vibrant colours and simple, room-temperature processing methods, electrochromic polymers have attracted attention as active materials for flexible, low-power-consuming devices. However, slow switching speeds in devices realized to date, as well as the complexity of having to combine several distinct polymers to achieve a full-colour gamut, have limited electrochromic materials to niche applications. Here we achieve fast, high-contrast electrochromic switching by significantly enhancing the interaction of light--propagating as deep-subwavelength-confined surface plasmon polaritons through arrays of metallic nanoslits, with an electrochromic polymer--present as an ultra-thin coating on the slit sidewalls. The switchable configuration retains the short temporal charge-diffusion characteristics of thin electrochromic films, while maintaining the high optical contrast associated with thicker electrochromic coatings. We further demonstrate that by controlling the pitch of the nanoslit arrays, it is possible to achieve a full-colour response with high contrast and fast switching speeds, while relying on just one electrochromic polymer.

  2. High-contrast and fast electrochromic switching enabled by plasmonics

    DOE PAGES

    Xu, Ting; Walter, Erich C.; Agrawal, Amit; Bohn, Christopher; Velmurugan, Jeyavel; Zhu, Wenqi; Lezec, Henri J.; Talin, A. Alec

    2016-01-27

    With vibrant colours and simple, room-temperature processing methods, electrochromic polymers have attracted attention as active materials for flexible, low-power-consuming devices. However, slow switching speeds in devices realized to date, as well as the complexity of having to combine several distinct polymers to achieve a full-colour gamut, have limited electrochromic materials to niche applications. Here we achieve fast, high-contrast electrochromic switching by significantly enhancing the interaction of light—propagating as deep-subwavelength-confined surface plasmon polaritons through arrays of metallic nanoslits, with an electrochromic polymer—present as an ultra-thin coating on the slit sidewalls. The switchable configuration retains the short temporal charge-diffusion characteristics of thinmore » electrochromic films, while maintaining the high optical contrast associated with thicker electrochromic coatings. In conclusion, we further demonstrate that by controlling the pitch of the nanoslit arrays, it is possible to achieve a full-colour response with high contrast and fast switching speeds, while relying on just one electrochromic polymer.« less

  3. High-contrast and fast electrochromic switching enabled by plasmonics

    NASA Astrophysics Data System (ADS)

    Talin, Albert; Xu, Ting; Walter, Erich; Agrawal, Amit; Bohn, Christopher; Velmurugan, Jeyavel; Zhu, Wenqi; Lezec, Henri

    With vibrant colors and simple, room-temperature processing methods, electrochromic polymers have long attracted attention as active materials for flexible, low-power consuming devices such as smart windows and displays. However, despite their many advantages, slow switching speed and complexity of combining several separate polymers to achieve full-color gamut has limited electrochromic materials to niche applications. Here we exploit the enhanced light-matter interaction associated with the deep-subwavelength mode confinement of surface plasmon polaritons propagating in metallic nanoslit arrays coated with ultra-thin electrochromic polymers to build a novel configuration for achieving high-contrast and fast electrochromic switching. The switchable configuration retains the short temporal charge-diffusion characteristics of thin electrochromic films while maintaining the high optical-contrast associated with thicker electrochromic coatings. We further demonstrate that by controlling the pitch of the nanoslit arrays, it is possible to achieve a full-color response with high-contrast and fast switching-speeds while relying on just one electrochromic polymer.

  4. Transparent crosslinked ultrashort peptide hydrogel dressing with high shape-fidelity accelerates healing of full-thickness excision wounds.

    PubMed

    Seow, Wei Yang; Salgado, Giorgiana; Lane, E Birgitte; Hauser, Charlotte A E

    2016-09-07

    Wound healing is a major burden of healthcare systems worldwide and hydrogel dressings offer a moist environment conducive to healing. We describe cysteine-containing ultrashort peptides that self-assemble spontaneously into hydrogels. After disulfide crosslinking, the optically-transparent hydrogels became significantly stiffer and exhibited high shape fidelity. The peptide sequence (LIVAGKC or LK6C) was then chosen for evaluation on mice with full-thickness excision wounds. Crosslinked LK6C hydrogels are handled easily with forceps during surgical procedures and offer an improvement over our earlier study of a non-crosslinked peptide hydrogel for burn wounds. LK6C showed low allergenic potential and failed to provoke any sensitivity when administered to guinea pigs in the Magnusson-Kligman maximization test. When applied topically as a dressing, the medium-infused LK6C hydrogel accelerated re-epithelialization compared to controls. The peptide hydrogel is thus safe for topical application and promotes a superior rate and quality of wound healing.

  5. Transparent crosslinked ultrashort peptide hydrogel dressing with high shape-fidelity accelerates healing of full-thickness excision wounds.

    PubMed

    Seow, Wei Yang; Salgado, Giorgiana; Lane, E Birgitte; Hauser, Charlotte A E

    2016-01-01

    Wound healing is a major burden of healthcare systems worldwide and hydrogel dressings offer a moist environment conducive to healing. We describe cysteine-containing ultrashort peptides that self-assemble spontaneously into hydrogels. After disulfide crosslinking, the optically-transparent hydrogels became significantly stiffer and exhibited high shape fidelity. The peptide sequence (LIVAGKC or LK6C) was then chosen for evaluation on mice with full-thickness excision wounds. Crosslinked LK6C hydrogels are handled easily with forceps during surgical procedures and offer an improvement over our earlier study of a non-crosslinked peptide hydrogel for burn wounds. LK6C showed low allergenic potential and failed to provoke any sensitivity when administered to guinea pigs in the Magnusson-Kligman maximization test. When applied topically as a dressing, the medium-infused LK6C hydrogel accelerated re-epithelialization compared to controls. The peptide hydrogel is thus safe for topical application and promotes a superior rate and quality of wound healing. PMID:27600999

  6. Transparent crosslinked ultrashort peptide hydrogel dressing with high shape-fidelity accelerates healing of full-thickness excision wounds

    PubMed Central

    Seow, Wei Yang; Salgado, Giorgiana; Lane, E. Birgitte; Hauser, Charlotte A. E.

    2016-01-01

    Wound healing is a major burden of healthcare systems worldwide and hydrogel dressings offer a moist environment conducive to healing. We describe cysteine-containing ultrashort peptides that self-assemble spontaneously into hydrogels. After disulfide crosslinking, the optically-transparent hydrogels became significantly stiffer and exhibited high shape fidelity. The peptide sequence (LIVAGKC or LK6C) was then chosen for evaluation on mice with full-thickness excision wounds. Crosslinked LK6C hydrogels are handled easily with forceps during surgical procedures and offer an improvement over our earlier study of a non-crosslinked peptide hydrogel for burn wounds. LK6C showed low allergenic potential and failed to provoke any sensitivity when administered to guinea pigs in the Magnusson-Kligman maximization test. When applied topically as a dressing, the medium-infused LK6C hydrogel accelerated re-epithelialization compared to controls. The peptide hydrogel is thus safe for topical application and promotes a superior rate and quality of wound healing. PMID:27600999

  7. Fracture Behavior of High-Toughness, Ionically Cross-linked Triblock Copolymer Hydrogels

    NASA Astrophysics Data System (ADS)

    Henderson, Kevin; Otim, Kathryn; Shull, Kenneth

    2011-03-01

    Mechanisms for enhancing energy dissipation and hence toughness are important for the generation of robust synthetic soft materials for biomedical applications. Ionic cross-linking in particular has been explored in triblock copolymer hydrogels and affords a remarkable change in mechanical performance comparable to non-cross-linked analogs. Here we employ a physically associated base triblock copolymer network composed of hydrophobic poly(methyl methacrylate) endblocks and a hydrophilic poly(methacrylic acid) midblock capable of complexing with divalent cations. Increases in stiffness and strength have previously been reported, with the extent dependent upon the identity, concentration, and pH of a cross-linking cation solution. We delineate the measured toughness in such systems using tensile tear tests and relate the mechanical performance to a damage zone model reminiscent of loading behavior observed in double network hydrogels.

  8. Enabling Efficient Climate Science Workflows in High Performance Computing Environments

    NASA Astrophysics Data System (ADS)

    Krishnan, H.; Byna, S.; Wehner, M. F.; Gu, J.; O'Brien, T. A.; Loring, B.; Stone, D. A.; Collins, W.; Prabhat, M.; Liu, Y.; Johnson, J. N.; Paciorek, C. J.

    2015-12-01

    A typical climate science workflow often involves a combination of acquisition of data, modeling, simulation, analysis, visualization, publishing, and storage of results. Each of these tasks provide a myriad of challenges when running on a high performance computing environment such as Hopper or Edison at NERSC. Hurdles such as data transfer and management, job scheduling, parallel analysis routines, and publication require a lot of forethought and planning to ensure that proper quality control mechanisms are in place. These steps require effectively utilizing a combination of well tested and newly developed functionality to move data, perform analysis, apply statistical routines, and finally, serve results and tools to the greater scientific community. As part of the CAlibrated and Systematic Characterization, Attribution and Detection of Extremes (CASCADE) project we highlight a stack of tools our team utilizes and has developed to ensure that large scale simulation and analysis work are commonplace and provide operations that assist in everything from generation/procurement of data (HTAR/Globus) to automating publication of results to portals like the Earth Systems Grid Federation (ESGF), all while executing everything in between in a scalable environment in a task parallel way (MPI). We highlight the use and benefit of these tools by showing several climate science analysis use cases they have been applied to.

  9. Enabling high confidence detections of gravitational-wave bursts

    NASA Astrophysics Data System (ADS)

    Littenberg, Tyson B.; Kanner, Jonah B.; Cornish, Neil J.; Millhouse, Margaret

    2016-08-01

    Extracting astrophysical information from gravitational-wave detections is a well-posed problem and thoroughly studied when detailed models for the waveforms are available. However, one motivation for the field of gravitational-wave astronomy is the potential for new discoveries. Recognizing and characterizing unanticipated signals requires data analysis techniques which do not depend on theoretical predictions for the gravitational waveform. Past searches for short-duration unmodeled gravitational-wave signals have been hampered by transient noise artifacts, or "glitches," in the detectors. We have put forth the BayesWave algorithm to differentiate between generic gravitational-wave transients and glitches, and to provide robust waveform reconstruction and characterization of the astrophysical signals. Here we study BayesWave's capabilities for rejecting glitches while assigning high confidence to detection candidates through analytic approximations to the Bayesian evidence. Analytic results are tested with numerical experiments by adding simulated gravitational-wave transient signals to LIGO data collected between 2009 and 2010 and found to be in good agreement.

  10. Stabilisation of crosslinked ultra-high molecular weight polyethylene (UHMW-PE)-acetabular components with alpha-tocopherol.

    PubMed

    Wolf, C; Maninger, J; Lederer, K; Frühwirth-Smounig, H; Gamse, T; Marr, R

    2006-12-01

    A stabilisation of crosslinked ultra-high molecular weight polyethylene (UHMW-PE) with alpha-tocopherol (vitamin E) used for endoprostheses can increase its resistance against oxidative degradation remarkably. However, the method used for conventional UHMW-PE of adding alpha-tocopherol to the UHMW-PE powder before processing can not be applied for crosslinked UHMW-PE, since the alpha-tocopherol hinders the crosslinking process, which would be accompanied by a heavy degradation of this vitamin. The alpha-tocopherol has therefore to be added after the crosslinking process. This paper presents two methods for a stabilisation of finished products with alpha-tocopherol. In method 1, UHMW-PE-cubes (20 x 20 x 20 mm3) were stored in pure alpha-tocopherol under inert atmosphere at temperatures from 100 degrees C to 150 degrees C resulting in a high mass fraction of alpha-tocopherol in the edge zones. For further homogenisation, the cubes were stored in inert atmosphere at temperatures from 160 degrees C to 200 degrees C. In method 2, supercritical CO2 was used to incorporate the vitamin into the UHMW-PE. In an autoclave vessel, the cubes were treated with alpha-tocopherol dissolved in supercritical CO2 for several hours at temperatures from 100 degrees C to 170 degrees C. In both cases, the mass fraction of alpha-tocopherol was detected with the help of a FTIR-microscope. Both methods are well suited to stabilise crosslinked UHMW-PE with alpha-tocopherol. A stabilisation of the sensitive edge layer as well as a nearly homogenous distribution with varying alpha-tocopherol content may be realised by varying the process parameters. Using method 2, standard hip cups were stabilized nearly homogeneously with varying mass fraction of alpha-tocopherol. No oxidation of the UHMW-PE could be detected by infrared spectroscopy (FTIR) and HPLC studies showed a very low degradation of the alpha-tocopherol for both processes. PMID:17143764

  11. A constitutive model of nanocomposite hydrogels with nanoparticle crosslinkers

    NASA Astrophysics Data System (ADS)

    Wang, Qiming; Gao, Zheming

    2016-09-01

    Nanocomposite hydrogels with only nanoparticle crosslinkers exhibit extraordinarily higher stretchability and toughness than the conventional organically crosslinked hydrogels, thus showing great potential in the applications of artificial muscles and cartilages. Despite their potential, the microscopic mechanics details underlying their mechanical performance have remained largely elusive. Here, we develop a constitutive model of the nanoparticle hydrogels to elucidate the microscopic mechanics behaviors, including the microarchitecture and evolution of the nanoparticle crosslinked polymer chains during the mechanical deformation. The constitutive model enables us to understand the Mullins effect of the nanocomposite hydrogels, and the effects of nanoparticle concentrations and sizes on their cyclic stress-strain behaviors. The theory is quantitatively validated by the tensile tests on a nanocomposite hydrogel with nanosilica crosslinkers. The theory can also be extended to explain the mechanical behaviors of existing hydrogels with nanoclay crosslinkers, and the necking instability of the composite hydrogels with both nanoparticle crosslinkers and organic crosslinkers. We expect that this constitutive model can be further exploited to reveal mechanics behaviors of novel particle-polymer chain interactions, and to design unprecedented hydrogels with both high stretchability and toughness.

  12. Radiation and chemical crosslinking promote strain hardening behavior and molecular alignment in ultra high molecular weight polyethylene during multi-axial loading conditions.

    PubMed

    Kurtz, S M; Pruitt, L A; Jewett, C W; Foulds, J R; Edidin, A A

    1999-08-01

    The mechanical behavior and evolution of crystalline morphology during large deformation of eight types of virgin and crosslinked ultra high molecular weight polyethylene (UHMWPE) were studied using the small punch test and transmission electron microscopy (TEM). We investigated the hypothesis that both radiation and chemical crosslinking hinder molecular mobility at large deformations, and hence promote strain hardening and molecular alignment during the multiaxial loading of the small punch test. Chemical crosslinking of UHMWPE was performed using 0.25% dicumyl peroxide (GHR 8110, GUR 1020 and 1050), and radiation crosslinking was performed using 150 kGy of electron beam radiation (GUR 1150). Crosslinking increased the ultimate load at failure and decreased the ultimate displacement of the polyethylenes during the small punch test. Crosslinking also increased the near-ultimate hardening behavior of the polyethylenes. Transmission electron microscopy was used to characterize the crystalline morphology of the bulk material, undeformed regions of the small punch test specimens, and deformed regions of the specimens oriented perpendicular and parallel to the punch direction. In contrast with the virgin polyethylenes, which showed only subtle evidence of lamellar alignment, the crosslinked polyethylenes exhibited enhanced crystalline lamellae orientation after the small punch test, predominantly in the direction parallel to the punch direction or deformation axis. Thus, the results of this study support the hypothesis that crosslinking promotes strain hardening during multiaxial loading because of increased resistance to molecular mobility at large deformations effected by molecular alignment. The data also illustrate the sensitivity of large deformation mechanical behavior and crystalline morphology to the method of crosslinking and resin of polyethylene. PMID:10458558

  13. Three-dimensionally presented anti-fouling zwitterionic motifs sequester and enable high-efficiency delivery of therapeutic proteins

    PubMed Central

    Liu, Pingsheng; Skelly, Jordan D.; Song, Jie

    2014-01-01

    Zwitterions are well known for their anti-biofouling properties. Past investigations of zwitterionic materials for biomedical uses have been centered on exploiting their ability to inhibit non-specific adsorption of proteins. Here, we report that zwitterionic motifs, when 3-dimensionally (3D) presented (e.g. in crosslinked hydrogels), could effectively sequester osteogenic bone morphogenetic protein-2 (rhBMP-2). The ionic interactions between rhBMP-2 and the 3D zwitterionic network enabled dynamic sequestering and sustained release of the protein with preserved bioactivity. We further demonstrated that the zwitterionic hydrogel confers high-efficiency in vivo local delivery of rhBMP-2. It can template the functional healing of critical-size femoral segmental defects in rats with rhBMP-2 at a loading dose substantially lower than those required for current natural or synthetic polymeric carriers. These findings reveal a novel function of zwitterionic materials beyond their commonly perceived anti-biofouling property, and may establish 3D zwitterionic matrices as novel high-efficiency vehicles for protein/ionic drug therapeutic delivery. PMID:24956565

  14. Gas-Phase Intramolecular Protein Crosslinking via Ion/Ion Reactions: Ubiquitin and a Homobifunctional sulfo-NHS Ester

    NASA Astrophysics Data System (ADS)

    Webb, Ian K.; Mentinova, Marija; McGee, William M.; McLuckey, Scott A.

    2013-05-01

    Gas-phase intra-molecular crosslinking of protein ubiquitin cations has been demonstrated via ion/ion reactions with anions of a homobifunctional N-hydroxysulfosuccinimide (sulfo-NHS) ester reagent. The ion/ion reaction between multiply-protonated ubiquitin and crosslinker monoanions produces a stable, charge-reduced complex. Covalent crosslinking is indicated by the consecutive loss of 2 molecules of sulfo-NHS under ion trap collisional activation conditions. Covalent modification is verified by the presence of covalently crosslinked sequence ions produced by ion-trap collision-induced dissociation of the ion generated from the losses of sulfo-NHS. Analysis of the crosslinked sequence fragments allows for the localization of crosslinked primary amines, enabling proximity mapping of the gas-phase 3-D structures. The presence of two unprotonated reactive sites within the distance constraint of the crosslinker is required for successful crosslinking. The ability to covalently crosslink is, therefore, sensitive to protein charge state. As the charge state increases, fewer reactive sites are available and protein structure is more likely to become extended because of intramolecular electrostatic repulsion. At high charge states, the reagent shows little evidence for covalent crosslinking but does show evidence for `electrostatic crosslinking' in that the binding of the sulfonate groups to the protein is sufficiently strong that backbone cleavages are favored over reagent detachment under ion trap collisional activation conditions.

  15. Gas-phase intramolecular protein crosslinking via ion/ion reactions: ubiquitin and a homobifunctional sulfo-NHS ester.

    PubMed

    Webb, Ian K; Mentinova, Marija; McGee, William M; McLuckey, Scott A

    2013-05-01

    Gas-phase intra-molecular crosslinking of protein ubiquitin cations has been demonstrated via ion/ion reactions with anions of a homobifunctional N-hydroxysulfosuccinimide (sulfo-NHS) ester reagent. The ion/ion reaction between multiply-protonated ubiquitin and crosslinker monoanions produces a stable, charge-reduced complex. Covalent crosslinking is indicated by the consecutive loss of 2 molecules of sulfo-NHS under ion trap collisional activation conditions. Covalent modification is verified by the presence of covalently crosslinked sequence ions produced by ion-trap collision-induced dissociation of the ion generated from the losses of sulfo-NHS. Analysis of the crosslinked sequence fragments allows for the localization of crosslinked primary amines, enabling proximity mapping of the gas-phase 3-D structures. The presence of two unprotonated reactive sites within the distance constraint of the crosslinker is required for successful crosslinking. The ability to covalently crosslink is, therefore, sensitive to protein charge state. As the charge state increases, fewer reactive sites are available and protein structure is more likely to become extended because of intramolecular electrostatic repulsion. At high charge states, the reagent shows little evidence for covalent crosslinking but does show evidence for 'electrostatic crosslinking' in that the binding of the sulfonate groups to the protein is sufficiently strong that backbone cleavages are favored over reagent detachment under ion trap collisional activation conditions. PMID:23463545

  16. A simple and high-resolution stereolithography-based 3D bioprinting system using visible light crosslinkable bioinks.

    PubMed

    Wang, Zongjie; Abdulla, Raafa; Parker, Benjamin; Samanipour, Roya; Ghosh, Sanjoy; Kim, Keekyoung

    2015-12-22

    Bioprinting is a rapidly developing technique for biofabrication. Because of its high resolution and the ability to print living cells, bioprinting has been widely used in artificial tissue and organ generation as well as microscale living cell deposition. In this paper, we present a low-cost stereolithography-based bioprinting system that uses visible light crosslinkable bioinks. This low-cost stereolithography system was built around a commercial projector with a simple water filter to prevent harmful infrared radiation from the projector. The visible light crosslinking was achieved by using a mixture of polyethylene glycol diacrylate (PEGDA) and gelatin methacrylate (GelMA) hydrogel with eosin Y based photoinitiator. Three different concentrations of hydrogel mixtures (10% PEG, 5% PEG + 5% GelMA, and 2.5% PEG + 7.5% GelMA, all w/v) were studied with the presented systems. The mechanical properties and microstructure of the developed bioink were measured and discussed in detail. Several cell-free hydrogel patterns were generated to demonstrate the resolution of the solution. Experimental results with NIH 3T3 fibroblast cells show that this system can produce a highly vertical 3D structure with 50 μm resolution and 85% cell viability for at least five days. The developed system provides a low-cost visible light stereolithography solution and has the potential to be widely used in tissue engineering and bioengineering for microscale cell patterning.

  17. A simple and high-resolution stereolithography-based 3D bioprinting system using visible light crosslinkable bioinks.

    PubMed

    Wang, Zongjie; Abdulla, Raafa; Parker, Benjamin; Samanipour, Roya; Ghosh, Sanjoy; Kim, Keekyoung

    2015-01-01

    Bioprinting is a rapidly developing technique for biofabrication. Because of its high resolution and the ability to print living cells, bioprinting has been widely used in artificial tissue and organ generation as well as microscale living cell deposition. In this paper, we present a low-cost stereolithography-based bioprinting system that uses visible light crosslinkable bioinks. This low-cost stereolithography system was built around a commercial projector with a simple water filter to prevent harmful infrared radiation from the projector. The visible light crosslinking was achieved by using a mixture of polyethylene glycol diacrylate (PEGDA) and gelatin methacrylate (GelMA) hydrogel with eosin Y based photoinitiator. Three different concentrations of hydrogel mixtures (10% PEG, 5% PEG + 5% GelMA, and 2.5% PEG + 7.5% GelMA, all w/v) were studied with the presented systems. The mechanical properties and microstructure of the developed bioink were measured and discussed in detail. Several cell-free hydrogel patterns were generated to demonstrate the resolution of the solution. Experimental results with NIH 3T3 fibroblast cells show that this system can produce a highly vertical 3D structure with 50 μm resolution and 85% cell viability for at least five days. The developed system provides a low-cost visible light stereolithography solution and has the potential to be widely used in tissue engineering and bioengineering for microscale cell patterning. PMID:26696527

  18. Crosslinking of agarose bioplastic using citric acid.

    PubMed

    Awadhiya, Ankur; Kumar, David; Verma, Vivek

    2016-10-20

    We report chemical crosslinking of agarose bioplastic using citric acid. Crosslinking was confirmed using Fourier transform infrared (FTIR) spectroscopy. The effects of crosslinking on the tensile strength, swelling, thermal stability, and degradability of the bioplastic were studied in detail. The tensile strength of the bioplastic films increased from 25.1MPa for control films up to a maximum of 52.7MPa for citric acid crosslinked films. At 37°C, the amount of water absorbed by crosslinked agarose bioplastic was only 11.5% of the amount absorbed by non-crosslinked controls. Thermogravimetric results showed that the crosslinked samples retain greater mass at high temperature (>450°C) than control samples. Moreover, while the crosslinked films were completely degradable, the rate of degradation was lower compared to non-crosslinked controls.

  19. Crosslinking of agarose bioplastic using citric acid.

    PubMed

    Awadhiya, Ankur; Kumar, David; Verma, Vivek

    2016-10-20

    We report chemical crosslinking of agarose bioplastic using citric acid. Crosslinking was confirmed using Fourier transform infrared (FTIR) spectroscopy. The effects of crosslinking on the tensile strength, swelling, thermal stability, and degradability of the bioplastic were studied in detail. The tensile strength of the bioplastic films increased from 25.1MPa for control films up to a maximum of 52.7MPa for citric acid crosslinked films. At 37°C, the amount of water absorbed by crosslinked agarose bioplastic was only 11.5% of the amount absorbed by non-crosslinked controls. Thermogravimetric results showed that the crosslinked samples retain greater mass at high temperature (>450°C) than control samples. Moreover, while the crosslinked films were completely degradable, the rate of degradation was lower compared to non-crosslinked controls. PMID:27474543

  20. Measurement of cross-linked elastin synthesis in bleomycin-induced pulmonary fibrosis using a highly sensitive assay for desmosine and isodesmosine

    SciTech Connect

    Cantor, J.O.; Osman, M.; Keller, S.; Cerreta, J.M.; Mandl, I.; Turino, G.M.

    1984-03-01

    Cross-linked elastin synthesis was measured in the intratracheal bleomycin model of interstitial pulmonary fibrosis by incorporation of 14C-lysine into the elastin-specific crosslinks, desmosine and isodesmosine. Detection of the labeled crosslinks was facilitated by development of a highly sensitive assay utilizing thin-layer electrophoresis. The results indicate that crosslinked elastin synthesis is significantly elevated from controls (p less than 0.05) at 1 to 3 weeks after exposure to bleomycin and returns to normal by 5 weeks. The increases in labeled elastin synthesis are not directly related to changes in either total lung protein synthesis or the pool size of the 14C-lysine. In comparison with collagen and glycosaminoglycan synthesis in this model of lung injury, maximal increases in cross-linked elastin formation occur later, but overlap with the elevated synthesis of these other connective tissue components. The marked increase from normal in cross-linked elastin synthesis in this model suggests that this tissue component is an important part of the fibrotic response of the pulmonary parenchyma and may play a role in the observed alterations in lung structure and function.

  1. Structural and chemical changes in ultra-high-molecular-weight polyethylene due to gamma radiation-induced crosslinking and annealing in air.

    PubMed

    Viano, A M; Spence, K E; Shanks, M A; Scott, M A; Redfearn, R D; Carlson, C W; Holm, T A; Ray, A K

    2007-01-01

    Ultra-High-Molecular-Weight-Polyethylene (UHMWPE) is the material of choice for one of the articulating surfaces in many total joint replacements, notably hip and knee prostheses. The various methods used by the orthopaedic biomaterials industry to sterilize and anneal UHMWPE components, and the resulting oxidation and crosslinking, affect the mechanical wear resistance properties in ways still unknown at the microscopic and molecular levels. Transmission electron microscopy and chemical pyrolysis were used to quantify crosslinking induced by gamma irradiation and annealing in air. Changes in lamellar stacking and the amount of crosslinking suggest two types of crosslinking: relatively unstable crosslinks in the amorphous region initially resulting from gamma irradiation which are later replaced by more thermally stable crosslinks resulting from rearrangements at the annealing temperature. Lamellar mobility, the ability of crystalline lamellae to flow in the material, is enhanced during the transition from one type of bond to the other, and this appears to optimize near eight hours of annealing time. Results from decomposition and percent crystallinity measurements provide further support for this theory.

  2. Synthesis of tetravalent LacNAc-glycoclusters as high-affinity cross-linker against Erythrina cristagalli agglutinin.

    PubMed

    Ogata, Makoto; Chuma, Yasushi; Yasumoto, Yoshinori; Onoda, Takashi; Umemura, Myco; Usui, Taichi; Park, Enoch Y

    2016-01-01

    Four kinds of tetravalent double-headed glycoclusters [(LacNAc)4-DHGs] were designed with linkers of varying lengths consisting of alkanedioic carboxyamido groups (C6, C12, C18 and C24) between two bi-antennary LacNAc-glycosides. These glycoclusters served as high-affinity cross-linking ligands for the LacNAc-binding lectin Erythrina cristagalli agglutinin (ECA). The binding activity and cross-linking between each ligand and ECA were characterized by a hemagglutination inhibition (HI) assay, isothermal titration calorimetry (ITC), a quantitative precipitation assay and dynamic light scattering (DLS). For the precipitation assay and DLS measurement, the synthesized (LacNAc)4-DHGs were found to be capable of binding and precipitating the ECA as multivalent ligands. ITC analysis indicated the binding of (LacNAc)4-DHGs was driven by a favorable enthalpy change. Furthermore, the entropy penalty from binding (LacNAc)4-DHGs clearly decreased in a spacer length-dependent manner. The binding affinities of flexible (LacNAc)4-DHGs (C18 and C24) with long spacers were found to be more favorable than those of the clusters having short spacers (C6 and C12). These results were supported by molecular dynamics simulations with explicit water molecules for the tetravalent glycoclusters with ECA. We concluded that the subtle modification in the epitope-presenting scaffolds exerts the significant effect in the recognition efficiency involved in the LacNAc moieties by ECA.

  3. Highly Cross-Linked Polyethylene in Total Hip and Knee Replacement: Spatial Distribution of Molecular Orientation and Shape Recovery Behavior

    PubMed Central

    Masaoka, Toshinori; Pezzotti, Giuseppe; Shishido, Takaaki; Tateiwa, Toshiyuki; Kubo, Kosuke

    2014-01-01

    The present study investigated effects of processing procedures on morphology of highly cross-linked and re-melted UHMWPE (XLPE) in total hip and knee arthroplasty (THA, TKA). The shape recovery behavior was also monitored via uniaxial compression test at room temperature after non-destructive characterizations of the in-depth microstructure by confocal/polarized Raman spectroscopy. The goal of this study was to relate the manufacturing-induced morphology to the in vivo micromechanical performance, and ultimately to explore an optimal structure in each alternative joint bearing. It was clearly confirmed that the investigated XLPE hip and knee implants, which were produced from different orthopaedic grade resins (GUR 1050 and GUR 1020), consisted of two structural regions in the as-received states: the near-surface transitional anisotropic layer (≈100 μm thickness) and the bulk isotropic structural region. These XLPEs exhibited a different crystalline anisotropy and molecular texture within the near-surface layers. In addition, the knee insert showed a slightly higher efficiency of shape recovery against the applied strain over the hip liner owing to a markedly higher percentage of the bulk amorphous phase with intermolecular cross-linking. The quantitative data presented in this study might contribute to construct manufacturing strategies for further rationalized structures as alternative bearings in THA and TKA. PMID:25243183

  4. Synthesis of tetravalent LacNAc-glycoclusters as high-affinity cross-linker against Erythrina cristagalli agglutinin.

    PubMed

    Ogata, Makoto; Chuma, Yasushi; Yasumoto, Yoshinori; Onoda, Takashi; Umemura, Myco; Usui, Taichi; Park, Enoch Y

    2016-01-01

    Four kinds of tetravalent double-headed glycoclusters [(LacNAc)4-DHGs] were designed with linkers of varying lengths consisting of alkanedioic carboxyamido groups (C6, C12, C18 and C24) between two bi-antennary LacNAc-glycosides. These glycoclusters served as high-affinity cross-linking ligands for the LacNAc-binding lectin Erythrina cristagalli agglutinin (ECA). The binding activity and cross-linking between each ligand and ECA were characterized by a hemagglutination inhibition (HI) assay, isothermal titration calorimetry (ITC), a quantitative precipitation assay and dynamic light scattering (DLS). For the precipitation assay and DLS measurement, the synthesized (LacNAc)4-DHGs were found to be capable of binding and precipitating the ECA as multivalent ligands. ITC analysis indicated the binding of (LacNAc)4-DHGs was driven by a favorable enthalpy change. Furthermore, the entropy penalty from binding (LacNAc)4-DHGs clearly decreased in a spacer length-dependent manner. The binding affinities of flexible (LacNAc)4-DHGs (C18 and C24) with long spacers were found to be more favorable than those of the clusters having short spacers (C6 and C12). These results were supported by molecular dynamics simulations with explicit water molecules for the tetravalent glycoclusters with ECA. We concluded that the subtle modification in the epitope-presenting scaffolds exerts the significant effect in the recognition efficiency involved in the LacNAc moieties by ECA. PMID:26672510

  5. Crosslinked, porous, polyacrylate beads

    NASA Technical Reports Server (NTRS)

    Rembaum, Alan (Inventor); Yen, Shiao-Ping S. (Inventor); Dreyer, William J. (Inventor)

    1977-01-01

    Uniformly-shaped, porous, round beads are prepared by the co-polymerization of an acrylic monomer and a cross-linking agent in the presence of 0.05 to 5% by weight of an aqueous soluble polymer such as polyethylene oxide. Cross-linking proceeds at high temperature above about 50.degree. C or at a lower temperature with irradiation. Beads of even shape and even size distribution of less than 2 micron diameter are formed. The beads will find use as adsorbents in chromatography and as markers for studies of cell surface receptors.

  6. Crosslinked, porous, polyacrylate beads

    NASA Technical Reports Server (NTRS)

    Rembaum, Alan (Inventor); Yen, Shiao-Ping Siao (Inventor); Dreyer, William J. (Inventor)

    1976-01-01

    Uniformly-shaped, porous, round beads are prepared by the co-polymerization of an acrylic monomer and a cross-linking agent in the presence of 0.05 to 5% by weight of an aqueous soluble polymer such as polyethylene oxide. Cross-linking proceeds at high temperature above about 50.degree.C or at a lower temperature with irradiation. Beads of even shape and even size distribution of less than 2 micron diameter are formed. The beads will find use as adsorbents in chromatography and as markers for studies of cell surface receptors.

  7. The effect of real-time aging on the oxidation and wear of highly cross-linked UHMWPE acetabular liners.

    PubMed

    Wannomae, Keith K; Christensen, Steven D; Freiberg, Andrew A; Bhattacharyya, Shayan; Harris, William H; Muratoglu, Orhun Kamil

    2006-03-01

    Irradiation decreases the wear of ultra-high molecular weight polyethylene (UHMWPE) but generates residual free radicals, precursors to long-term oxidation. Melting or annealing is used in quenching free radicals. We hypothesized that irradiated and once-annealed UHMWPE would oxidize while irradiated and melted UHMWPE would not, and that the oxidation in the former would increase wear. Acetabular liners were real-time aged by immersion in an aqueous environment that closely mimicked the temperature and oxygen concentration of synovial fluid. After 95 weeks of real-time aging, once-annealed components were oxidized; the melted components were not. The wear rate of the real-time aged irradiated and once-annealed components was higher than the literature reported values of other contemporary highly cross-linked UHMWPEs. Single annealing after irradiation used with terminal gamma sterilization may adversely affect the long-term oxidative stability of UHMWPE components.

  8. Cross-linked carbon network with hierarchical porous structure for high performance solid-state electrochemical capacitor

    NASA Astrophysics Data System (ADS)

    Cheng, Yongliang; Huang, Liang; Xiao, Xu; Yao, Bin; Hu, Zhimi; Li, Tianqi; Liu, Kang; Zhou, Jun

    2016-09-01

    The development of portable electronics strongly requires flexible, lightweight, and inexpensive energy-storage devices with high power density, long cycling stability, and high reliability. In this work, we prepare a flexible solid-state electrochemical capacitor using cross-linked hierarchical porous carbon network as electrode material via electrospinning and carbonization process. This device can reversibly deliver a maximum energy density of 10.18 W h/kg with excellent cycling stability which achieves 95% capacitance retention after 20000 charge/discharge cycles. Moreover, it also demonstrates outstanding mechanical flexibility and excellent capacitance retention even when the device is repeatedly bended 10000 cycles under 90°. All of these results suggest its promising perspective in flexible energy storage device.

  9. High-efficiency loading and controlled release of highly water-soluble drug, pravastatin sodium by use of cross-linked β-cyclodextrin

    PubMed Central

    Kumar, Yatendra; Philip, Betty; Pathak, Kamla

    2011-01-01

    Aim: The aim of the project was to develop cross-linked b-cyclodextrin (CL β-CD) microparticles for controlled delivery of a highly water-soluble drug. Materials and Methods: CL β-CD microparticles were prepared by emulsification phase separation technique using epichlorohydrin as a cross-linking reagent. The developed microparticles were compared with β-CD for their pharmacotechnical properties. A highly water-soluble model drug, pravastatin sodium (PS) was loaded within these hydrophobic microparticles by active drug loading method using nonionic surfactant Tween 80 as the loading facilitator. Results: Maximal drug fixation (216.8 mg/g beads) was observed in pH 4 at 20°C. In vitro release studies of PS-loaded CL β-CD microparticles in simulated gastric fluid and simulated intestinal fluid resulted in modified dissolution profiles. Modeling of release profiles confirmed controlled release (r2 = 0.9910) of PS from the cross-linked system. Conclusion: Controlled release CL β-CD microparticles PS that have the potential to enhance its therapeutic properties by offering the advantage of less frequent dosing and decreased fluctuations in the blood levels during the dosing interval were successfully developed. PMID:23071914

  10. Mechanisms of plastic deformation in highly cross-linked UHMWPE for total hip components--the molecular physics viewpoint.

    PubMed

    Takahashi, Yasuhito; Shishido, Takaaki; Yamamoto, Kengo; Masaoka, Toshinori; Kubo, Kosuke; Tateiwa, Toshiyuki; Pezzotti, Giuseppe

    2015-02-01

    Plastic deformation is an unavoidable event in biomedical polymeric implants for load-bearing application during long-term in-vivo service life, which involves a mass transfer process, irreversible chain motion, and molecular reorganization. Deformation-induced microstructural alterations greatly affect mechanical properties and durability of implant devices. The present research focused on evaluating, from a molecular physics viewpoint, the impact of externally applied strain (or stress) in ultra-high molecular weight polyethylene (UHMWPE) prostheses, subjected to radiation cross-linking and subsequent remelting for application in total hip arthroplasty (THA). Two different types of commercial acetabular liners, which belong to the first-generation highly cross-linked UHMWPE (HXLPE), were investigated by means of confocal/polarized Raman microprobe spectroscopy. The amount of crystalline region and the spatial distribution of molecular chain orientation were quantitatively analyzed according to a combined theory including Raman selection rules for the polyethylene orthorhombic structure and the orientation distribution function (ODF) statistical approach. The structurally important finding was that pronounced recrystallization and molecular reorientation increasingly appeared in the near-surface regions of HXLPE liners with increasing the amount of plastic (compressive) deformation stored in the microstructure. Such molecular rearrangements, occurred in response to external strains, locally increase surface cross-shear (CS) stresses, which in turn trigger microscopic wear processes in HXLPE acetabular liners. Thus, on the basis of the results obtained at the molecular scale, we emphasize here the importance of minimizing the development of irrecoverable deformation strain in order to retain the pristine and intrinsically high wear performance of HXLPE components. PMID:25460925

  11. Mechanisms of plastic deformation in highly cross-linked UHMWPE for total hip components--the molecular physics viewpoint.

    PubMed

    Takahashi, Yasuhito; Shishido, Takaaki; Yamamoto, Kengo; Masaoka, Toshinori; Kubo, Kosuke; Tateiwa, Toshiyuki; Pezzotti, Giuseppe

    2015-02-01

    Plastic deformation is an unavoidable event in biomedical polymeric implants for load-bearing application during long-term in-vivo service life, which involves a mass transfer process, irreversible chain motion, and molecular reorganization. Deformation-induced microstructural alterations greatly affect mechanical properties and durability of implant devices. The present research focused on evaluating, from a molecular physics viewpoint, the impact of externally applied strain (or stress) in ultra-high molecular weight polyethylene (UHMWPE) prostheses, subjected to radiation cross-linking and subsequent remelting for application in total hip arthroplasty (THA). Two different types of commercial acetabular liners, which belong to the first-generation highly cross-linked UHMWPE (HXLPE), were investigated by means of confocal/polarized Raman microprobe spectroscopy. The amount of crystalline region and the spatial distribution of molecular chain orientation were quantitatively analyzed according to a combined theory including Raman selection rules for the polyethylene orthorhombic structure and the orientation distribution function (ODF) statistical approach. The structurally important finding was that pronounced recrystallization and molecular reorientation increasingly appeared in the near-surface regions of HXLPE liners with increasing the amount of plastic (compressive) deformation stored in the microstructure. Such molecular rearrangements, occurred in response to external strains, locally increase surface cross-shear (CS) stresses, which in turn trigger microscopic wear processes in HXLPE acetabular liners. Thus, on the basis of the results obtained at the molecular scale, we emphasize here the importance of minimizing the development of irrecoverable deformation strain in order to retain the pristine and intrinsically high wear performance of HXLPE components.

  12. Resorbable elastomeric networks prepared by photocrosslinking of high-molecular-weight poly(trimethylene carbonate) with photoinitiators and poly(trimethylene carbonate) macromers as crosslinking aids.

    PubMed

    Bat, Erhan; van Kooten, Theo G; Feijen, Jan; Grijpma, Dirk W

    2011-05-01

    Resorbable and elastomeric poly(trimethylene carbonate) (PTMC) networks were efficiently prepared by photoinitiated crosslinking of linear high-molecular-weight PTMC. To crosslink PTMC films, low-molecular-weight PTMC macromers with methacrylate end groups were synthesized and used as crosslinking aids. By exposing PTMC films containing only photoinitiator (Irgacure(®) 2959) or both photoinitiator and PTMC macromers to ultraviolet light, PTMC networks with high gel contents (87-95%) could be obtained. The crosslink density could be readily varied by adjusting the irradiation time or the amount of crosslinking aid used. The formed networks were flexible, with low elastic modulus values ranging from 7.1 to 7.5MPa, and also showed excellent resistance to creep in cyclic tests. In vitro experiments showed that the photocrosslinked PTMC networks could be eroded by macrophages, and upon incubation in aqueous cholesterol esterase enzyme- or potassium dioxide solutions. The rate of surface erosion of photocrosslinked PTMC networks was significantly lower than that observed for films prepared from linear PTMC. These resorbable PTMC elastomeric networks are compatible with cells and may find application in tissue engineering and controlled release. PMID:21232640

  13. High-Resolution N6-Methyladenosine (m6A) Map Using Photo-Crosslinking-Assisted m6A Sequencing**

    PubMed Central

    Chen, Kai; Lu, Zhike; Wang, Xiao; Fu, Ye; Luo, Guan-Zheng; Liu, Nian; Han, Dali; Dominissini, Dan; Dai, Qing; Pan, Tao; He, Chuan

    2015-01-01

    N6-methyladenosine (m6A) is an abundant internal modification in eukaryotic mRNA and plays regulatory roles in mRNA metabolism. However, methods to precisely locate the m6A modification remain limited. We present here a photo-crosslinking-assisted m6A sequencing strategy (PA-m6A-seq) to more accurately define sites with m6A modification. Using this strategy, we obtained a high-resolution map of m6A in a human transcriptome. The map resembles the general distribution pattern observed previously, and reveals new m6A sites at base resolution. Our results provide insight into the relationship between the methylation regions and the binding sites of RNA-binding proteins. PMID:25491922

  14. Three Year RSA Evaluation of Vitamin E Diffused Highly Cross-linked Polyethylene Liners and Cup Stability.

    PubMed

    Sillesen, Nanna H; Greene, Meridith E; Nebergall, Audrey K; Nielsen, Poul T; Laursen, Mogens B; Troelsen, Anders; Malchau, Henrik

    2015-07-01

    Vitamin E diffusion into highly cross-linked polyethylene (E-XLPE) is a method for enhancing oxidative stability of acetabular liners. The purpose of this study was to evaluate in vivo penetration of E-XLPE using radiostereometric analysis (RSA). Eighty-four hips were recruited into a prospective 10-year RSA. This is the first evaluation of the multicenter cohort after 3-years. All patients received E-XLPE liners (E1, Biomet) and porous-titanium coated cups (Regenerex, Biomet). There was no difference (P=0.450) in median femoral head penetration into the E-XLPE liners at 3-years comparing cobalt-chrome heads (-0.028mm; inter-quartile range (IQR) - 0.065 to 0.047) with ceramic heads (-0.043mm, IQR - 0.143to0.042). The 3-year follow-up indicates minimal E-XLPE liner penetration regardless of head material and minimal early cup movement.

  15. Laser welding and collagen crosslinks

    SciTech Connect

    Reiser, K.M.; Last, J.A.; Small, W. IV; Maitland, D.J.; Heredia, N.J.; Da Silva, L.B.; Matthews, D.L.

    1997-02-20

    Strength and stability of laser-welded tissue may be influenced, in part, by effects of laser exposure on collagen crosslinking. We therefore studied effects of diode laser exposure (805 nm, 1-8 watts, 30 seconds) + indocyanine green dye (ICG) on calf tail tendon collagen crosslinks. Effect of ICG dye alone on crosslink content prior to laser exposure was investigated; unexpectedly, we found that ICG-treated tissue had significantly increased DHLNL and OHP, but not HLNL. Laser exposure after ICG application reduced elevated DHLNL and OHP crosslink content down to their native levels. The monohydroxylated crosslink HLNL was inversely correlated with laser output (p<0.01 by linear regression analysis). DHLNL content was highly correlated with content of its maturational product, OHP, suggesting that precursor-product relations are maintained. We conclude that: (1)ICG alone induces DHLNL and OHP crosslink formation; (2)subsequent laser exposure reduces the ICG-induced crosslinks down to native levels; (3)excessive diode laser exposure destroys normally occurring HLNL crosslinks.

  16. A versatile, highly reactive, cross-linking reagent: 2,2'-sulfonylbis[3-methoxy-(E,E)-2-propenenitrile].

    PubMed

    Hosmane, R S; Bertha, C M

    1990-01-30

    Adequate aqueous stability and cross-linking ability of the novel title reagent, recently discovered in this laboratory, have been demonstrated by comparison of its rate of hydrolysis with the rate of reaction with an amine nucleophile and by cross-linking deoxy- and oxyhemoglobins, as an example.

  17. The effects of peroxide content on the wear behavior, microstructure and mechanical properties of peroxide crosslinked ultra-high molecular weight polyethylene used in total hip replacement.

    PubMed

    Gul, Rizwan M

    2008-06-01

    The wear of the ultra-high molecular weight polyethylene (UHMWPE) acetabular components and wear debris induced osteolysis are the major causes of failure in total hip replacements. Crosslinking has been shown to improve the wear resistance of UHMWPE by producing a network structure, resisting the plastic deformation of the surface layer. In this study organic peroxides were used to crosslink two different types of UHMWPE resins, using hot isostatic pressing as the processing method. The effects of peroxide content on the different properties were investigated, along with the effect of the crosslink density on the wear behavior. An increase in peroxide content decreases the melting point and the degree of crystallinity, which results in a decrease in the yield strength. The ultimate tensile strength remains essentially unchanged. The molecular weight between crosslinks decreases with an increase in the peroxide content and reaches a saturation limit at around 0.3-0.5 weight percent peroxide, its value at the saturation limit is a function of the virgin resin used for processing. The wear rate decreases linearly with the increase in crosslink density. PMID:18219557

  18. Optical signal processing for enabling high-speed, highly spectrally efficient and high capacity optical systems

    NASA Astrophysics Data System (ADS)

    Fazal, Muhammad Irfan

    The unabated demand for more capacity due to the ever-increasing internet traffic dictates that the boundaries of the state of the art maybe pushed to send more data through the network. Traditionally, this need has been satisfied by multiple wavelengths (wavelength division multiplexing), higher order modulation formats and coherent communication (either individually or combined together). WDM has the ability to reduce cost by using multiple channels within the same physical fiber, and with EDFA amplifiers, the need for O-E-O regenerators is eliminated. Moreover the availability of multiple colors allows for wavelength-based routing and network planning. Higher order modulation formats increases the capacity of the link by their ability to encode data in both the phase and amplitude of light, thereby increasing the bits/sec/Hz as compared to simple on-off keyed format. Coherent communications has also emerged as a primary means of transmitting and receiving optical data due to its support of formats that utilize both phase and amplitude to further increase the spectral efficiency of the optical channel, including quadrature amplitude modulation (QAM) and quadrature phase shift keying (QPSK). Polarization multiplexing of channels can double capacity by allowing two channels to share the same wavelength by propagating on orthogonal polarization axis and is easily supported in coherent systems where the polarization tracking can be performed in the digital domain. Furthermore, the forthcoming IEEE 100 Gbit/s Ethernet Standard, 802.3ba, provides greater bandwidth, higher data rates, and supports a mixture of modulation formats. In particular, Pol-MUX QPSK is increasingly becoming the industry's format of choice as the high spectral efficiency allows for 100 Gbit/s transmission while still occupying the current 50 GHz/channel allocation of current 10 Gbit/s OOK fiber systems. In this manner, 100 Gbit/s transfer speeds using current fiber links, amplifiers, and filters

  19. High performance of transferring lithium ion for polyacrylonitrile-interpenetrating crosslinked polyoxyethylene network as gel polymer electrolyte.

    PubMed

    Kuo, Ping-Lin; Wu, Ching-An; Lu, Chung-Yu; Tsao, Chin-Hao; Hsu, Chun-Han; Hou, Sheng-Shu

    2014-03-12

    A polyacrylonitrile (PAN)-interpenetrating cross-linked polyoxyethylene (PEO) network (named XANE) was synthesized acting as separator and as gel polymer electrolytes simultaneously. SEM images show that the surface of the XANE membrane is nonporous, comparing to the surface of the commercial separator to be porous. This property results in excellent electrolyte uptake amount (425 wt %), and electrolyte retention for XANE membrane, significantly higher than that of commercial separator (200 wt %). The DSC result indicates that the PEO crystallinity is deteriorated by the cross-linked process and was further degraded by the interpenetration of the PAN. The XANE membrane shows significantly higher ionic conductivity (1.06-8.21 mS cm(-1)) than that of the commercial Celgard M824 separator (0.45-0.90 mS cm(-1)) ascribed to the high electrolyte retention ability of XANE (from TGA), the deteriorated PEO crystallinity (from DSC) and the good compatibility between XANE and electrode (from measuring the interfacial-resistance). For battery application, under all charge/discharge rates (from 0.1 to 3 C), the specific half-cell capacities of the cell composed of the XANE membrane are all higher than those of the aforementioned commercial separator. More specifically, the cell composed of the XANE membrane has excellent cycling stability, that is, the half-cell composed of the XANE membrane still exhibited more than 97% columbic efficiency after 100 cycles at 1 C. The above-mentioned advantageous properties and performances of the XANE membrane allow it to act as both an ionic conductor as well as a separator, so as to work as separator-free gel polymer electrolytes.

  20. High performance of transferring lithium ion for polyacrylonitrile-interpenetrating crosslinked polyoxyethylene network as gel polymer electrolyte.

    PubMed

    Kuo, Ping-Lin; Wu, Ching-An; Lu, Chung-Yu; Tsao, Chin-Hao; Hsu, Chun-Han; Hou, Sheng-Shu

    2014-03-12

    A polyacrylonitrile (PAN)-interpenetrating cross-linked polyoxyethylene (PEO) network (named XANE) was synthesized acting as separator and as gel polymer electrolytes simultaneously. SEM images show that the surface of the XANE membrane is nonporous, comparing to the surface of the commercial separator to be porous. This property results in excellent electrolyte uptake amount (425 wt %), and electrolyte retention for XANE membrane, significantly higher than that of commercial separator (200 wt %). The DSC result indicates that the PEO crystallinity is deteriorated by the cross-linked process and was further degraded by the interpenetration of the PAN. The XANE membrane shows significantly higher ionic conductivity (1.06-8.21 mS cm(-1)) than that of the commercial Celgard M824 separator (0.45-0.90 mS cm(-1)) ascribed to the high electrolyte retention ability of XANE (from TGA), the deteriorated PEO crystallinity (from DSC) and the good compatibility between XANE and electrode (from measuring the interfacial-resistance). For battery application, under all charge/discharge rates (from 0.1 to 3 C), the specific half-cell capacities of the cell composed of the XANE membrane are all higher than those of the aforementioned commercial separator. More specifically, the cell composed of the XANE membrane has excellent cycling stability, that is, the half-cell composed of the XANE membrane still exhibited more than 97% columbic efficiency after 100 cycles at 1 C. The above-mentioned advantageous properties and performances of the XANE membrane allow it to act as both an ionic conductor as well as a separator, so as to work as separator-free gel polymer electrolytes. PMID:24521309

  1. Correlation of in Situ Oxazolidine Formation with Highly Synergistic Cytotoxicity and DNA Cross-Linking in Cancer Cells from Combinations of Doxorubicin and Formaldehyde.

    PubMed

    Barthel, Benjamin L; Mooz, Erin L; Wiener, Laura Elizabeth; Koch, Gary G; Koch, Tad H

    2016-03-10

    Anthracyclines are a class of antitumor compounds that are successful and widely used but suffer from cardiotoxicity and acquired tumor resistance. Formaldehyde interacts with anthracyclines to enhance antitumor efficacy, bypass resistance mechanisms, improve the therapeutic profile, and change the mechanism of action from a topoisomerase II poison to a DNA cross-linker. Contrary to current dogma, we show that both efficient DNA cross-linking and potent synergy in combination with formaldehyde correlate with the anthracycline's ability to form cyclic formaldehyde conjugates as oxazolidine moieties and that the cyclic conjugates are better cross-linking agents and cytotoxins than acyclic conjugates. We also provide evidence that suggests that the oxazolidine forms in situ, since cotreatment with doxorubicin and formaldehyde is highly cytotoxic to dox-resistant tumor cell lines, and that this benefit is absent in combinations of formaldehyde and epirubicin, which cannot form stable oxazolidines. These results have potential clinical implications in the active field of anthracycline prodrug design and development.

  2. High-resolution nuclear magnetic resonance spectroscopy studies of polysaccharides crosslinked by sodium trimetaphosphate: a proposal for the reaction mechanism.

    PubMed

    Lack, Stéphane; Dulong, Virginie; Picton, Luc; Le Cerf, Didier; Condamine, Eric

    2007-05-21

    An NMR spectroscopy study ((31)P, (1)H, (13)C) of the postulated crosslinking mechanism of sodium trimetaphosphate (STMP) on polysaccharides is reported using methyl alpha-D-glucopyranoside as a model. In a first step, reaction of STMP with Glc-OMe gives grafted sodium tripolyphosphate (STPP(g)). On the one hand, STTP(g) can react with a second alcohol functionality to give a crosslinked monophosphate. On the other hand, a monophosphate (grafted phosphate) could be obtained by alkaline degradation of STPP(g). NMR spectroscopy allows to detect the various species formed and to obtain the crosslinking density of STMP-polysaccharides hydrogels. PMID:17303095

  3. "Fastening" porphyrin in highly cross-linked polyphosphazene hybrid nanoparticles: powerful red fluorescent probe for detecting mercury ion.

    PubMed

    Hu, Ying; Meng, Lingjie; Lu, Qinghua

    2014-04-22

    It is a significant issue to overcome the concentration-quenching effect of the small fluorescent probes and maintain the high fluorescent efficiency at high concentration for sensitive and selective fluorescent mark or detection. We developed a new strategy to "isolate" and "fasten" porphyrin moieties in a highly cross-linked poly(tetraphenylporphyrin-co-cyclotriphosphazene) (TPP-PZS) by the polycondensation of hexachlorocyclotriphosphazene (HCCP) and 5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrin (TPP-(OH)4) in a suitable solvent. The resulting TPP-PZS particles were characterized with transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier transform infrared (FTIR), (31)P nuclear magnetic resonance (NMR), and ultraviolet and visible (UV-vis) absorption spectra. Remarkably, TPP-PZS particles obtained in acetone emitted a bright red fluorescence both in powder state and in solution because the aggregation of porphyrin moieties in "H-type" (face-to-face) and "J-type" (edge-to-edge) was effectively blocked. The fluorescent TPP-PZS particles also showed superior resistance to photobleaching, and had a high sensitivity and selectivity for the detection of Hg(2+) ions. The TPP-PZS particles were therefore used as an ideal material for preparing test strips to quickly detect/monitor the Hg(2+) ions in a facile way.

  4. Preparation and characterization of highly cross-linked polyimide aerogels based on polyimide containing trimethoxysilane side groups.

    PubMed

    Pei, Xueliang; Zhai, Wentao; Zheng, Wenge

    2014-11-11

    In this study, highly cross-linked and completely imidized polyimide aerogels were prepared from polyimide containing trimethoxysilane side groups, which was obtained as the condensation product of polyimide containing acid chloride side groups and 3-aminopropyltrimethoxysilane. After adding water and acid catalyst, the trimethoxysilane side groups hydrolyzed and condensed one another, and a continuous increase in the complex viscosities of the polyimide solutions with time was observed. The formed polyimide gels were dried by freeze-drying from tert-butyl alcohol to obtain polyimide aerogels, which consisted of a three-dimensional network of polyimide fibers tangled together. By varying the solution concentration of the polyimide containing trimethoxysilane side groups, polyimide aerogels with different densities (ranging from 0.19 to 0.42 g/cm(3)) were obtained. The resulting polyimide aerogels had small pore diameter (ranging from 20.7 to 58.3 nm), high surface area (ranging from 310 to 344 m(2)/g), high 5% weight loss temperature in air (at about 440 °C), and an excellent mechanical property. In addition, the glass transition temperature (349 °C) of the polyimide aerogels was much higher than that (210 °C) of the corresponding linear polyimide. So, even after being heated at 300 °C for 30 min, the porous structure of the polyimide aerogels was not completely destroyed. PMID:25340747

  5. Soft metal plating enables hard metal seal to operate successfully in low temperature, high pressure environment

    NASA Technical Reports Server (NTRS)

    Lamvermeyer, D. J.

    1967-01-01

    Soft metal plating of hard metal lip seal enables successful operation of seal in a cryogenic fluid line under high pressure. The seal is coated with a thin film of 24 carat gold on the lip area to provide antigall and seal properties.

  6. Enablers and Inhibitors to English Language Learners' Research Process in a High School Setting

    ERIC Educational Resources Information Center

    Kim, Sung Un

    2015-01-01

    This researcher sought to examine enablers and inhibitors to English language learner (ELL) students' research process within the framework of Carol C. Kuhlthau's Information Search Process (ISP). At a high school forty-eight ELL students in three classes, an English as a Second Language (ESL) teacher, and a biology teacher participated in the…

  7. High-Temperature Cross-Linking of Carbon Nanotube Multi-Yarn Using Polyvinylpyrrolidone as a Binding Agent.

    PubMed

    Misak, H; Asmatulu, R; Whitman, J; Mall, S

    2015-03-01

    Carbon nanotube (CNT) multi-yarn was cross-linked together at elevated temperatures using a poly- mer, with the intent of improving their strength and electrical conductivity. They were functionalized using an acid treatment and immersed in a bath of different concentrations (0.5%, 0.1%, and 0.2%) of polyvinylpyrrolidone (PVP). Then they were placed in an oven at various temperatures (180 °C, 200 °C, and 220 °C) in order to cause cross-linking among the carbon nanotube yarns. The phys- ical, chemical, electrical, and mechanical properties of the cross-linked yarns were investigated. The yarns cross-linked at higher temperatures and greater concentrations of PVP had a greater increase in linear mass density, indicating that the cross-linking process had worked as expected. Yarns that were cross-linked at lower temperatures had greater tensile strength and better spe- cific electrical conductivity. Those that were treated with a greater concentration of polymer had a greater ultimate tensile strength. All these results are encouraging first step, but still need further development if CNT yarn is to replace copper wire. PMID:26413653

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

    PubMed Central

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

    2016-01-01

    Background The choice of bearing articulation for total hip arthroplasty in younger patients is amenable to debate. We compared mid-term patient-reported outcomes and survivorship across 2 different bearing articulations in a young patient cohort. Methods We reviewed patients with cobalt-chrome or oxidized zirconium on highly crosslinked polyethylene who were followed prospectively between 2004 and 2012. Kaplan–Meier analysis was used to determine predicted cumulative survivorship at 5 years with all-cause and aseptic revisions as the outcome. We compared patient-reported outcomes, including the Harris hip score (HHS), Western Ontario and McMaster University Osteoarthritis Index (WOMAC) and Short-form 12 (SF-12) scores. Results A total of 622 patients were followed during the study period. Mean follow-up was 8.2 (range 2.0–10.6) years for cobalt-chrome and 7.8 (range 2.1–10.7) years for oxidized zirconium. Mean age was 54.9 ± 10.6 years for cobalt-chrome and 54.8 ± 10.7 years for oxidized zirconium. Implant survivorship was 96.0% (95% confidence interval [CI] 94.9%–97.1%) for cobalt-chrome and 98.7% (95% CI 98.0%–99.4%) for oxidized zirconium on highly crosslinked polyethylene for all-cause revisions, and 97.2% (95% CI 96.2%–98.2%) for cobalt-chrome and 99.0% (95% CI 98.4%–99.6%) for oxidized zirconium for aseptic revisions. An age-, sex- and diagnosis-matched comparison of the HHS, WOMAC and SF-12 scores demonstrated no significant changes in clinical outcomes across the groups. Conclusion Both bearing surface couples demonstrated excellent mid-term survivorship and outcomes in young patient cohorts. Future analyses on wear and costs are warranted to elicit differences between the groups at long-term follow-up. PMID:26812409

  9. Long-term Results of a First-Generation Annealed Highly Cross-Linked Polyethylene in Young, Active Patients.

    PubMed

    Ranawat, Chitranjan S; Ranawat, Amar S; Ramteke, Alankar A; Nawabi, Danyal; Meftah, Morteza

    2016-01-01

    The survivorship of total hip arthroplasty in younger patients is dependent on the wear characteristics of the bearing surfaces. Long-term results with conventional polyethylene in young patients show a high failure rate. This study assessed the long-term results of a first-generation annealed highly cross-linked polyethylene (HCLPE) in uncemented total hip arthroplasty in young, active patients. Between 1999 and 2003, 112 total hip arthroplasty procedures performed in 91 patients with an average University of California Los Angeles activity score of 8 and mean age of 53 years (range, 24-65 years) were included from a prospective database. In all patients, a 28-mm metal femoral head on annealed HCLPE (Crossfire; Stryker, Mahwah, New Jersey) was used. At minimum 10-year follow-up (11.5±0.94 years), Kaplan-Meier survivorship was 97% for all failures (1 periprosthetic infection and 1 late dislocation) and 100% for mechanical failure (no revisions for osteolysis or loosening). This study showed low revision rates for wear-related failure and superior survivorship in young, active patients. Oxidation causing failure of the locking mechanism has not been a problem with Crossfire for up to 10 years. PMID:26811959

  10. Enabling High Performance Instruments for Astronomy and Space Exploration and ALD

    NASA Technical Reports Server (NTRS)

    Greer, Frank; Lee, M. C.; Hoenk, M. E.; Jones, T. J.; Jacquot, B. C.; Dickie, M.; Monacos, S.; Nikzad, S.; Day, P.; Leduc, R.; Hamden, E.; Schiminovich, D.; Beasley, M.; Gantner, B.; Morrissey, P.; Martin, C.

    2012-01-01

    Benefits of ALD for NASA instruments and applications: a) Ultrathin, highly conformal, and uniform films over arbitrarily large surface area. b). High quality films (density, roughness, conductivity, etc.) . Angstrom level control of stoichiometry, interfaces, and surface properties: 1) Multilayer nanolaminates/nanocomposites. 2) Low temperature surface engineering. Flight applications enabled by ALD: a) Anti-reflective coatings/Mirrors/Filters/Optics for UV/Vis/NIR Detectors. b) Superconducting Films for Submillimeter Astronomy.

  11. Enabling High Performance Instruments for UV Astronomy and Space Exploration with ALD

    NASA Technical Reports Server (NTRS)

    Greer, F.; Hoenk, M. E.; Jones, T. J.; Jacquot, B. C.; Monacos, S.; Nikzad, S.; Hamden, E.; Schiminovich, D.

    2011-01-01

    Benefits of Atomic Layer Deposition (ALD) for UV instruments and application are: (1) Ultrathin, highly conformal, and uniform films over arbitrarily large surface area (2) High quality films (density, roughness, conductivity, etc.) (3) Angstrom level control of stoichiometry, interfaces, and surface properties (3a) Multilayer nanolaminates/nanocomposites (3b) Low temperature surface engineering UV flight applications enabled by ALD. (1) Anti -reflective coatings/Mirrors/Filters/Optics for UV/Vis/NIR Detectors (2) Surface Passivation for III -N detectors

  12. Strain-induced microstructural rearrangement in ultra-high molecular weight polyethylene for hip joints: A comparison between conventional and vitamin E-infused highly-crosslinked liners.

    PubMed

    Takahashi, Yasuhito; Yamamoto, Kengo; Shishido, Takaaki; Masaoka, Toshinori; Tateiwa, Toshiyuki; Puppulin, Leonardo; Pezzotti, Giuseppe

    2014-03-01

    Infusion of vitamin E (α-tocopherol) in highly crosslinked ultra-high molecular weight polyethylene (UHMWPE) liners has been conceived to achieve superior oxidation stability while preserving enhanced mechanical properties as compared to post-irradiation remelted liners. However, the presence of an antioxidant in the material microstructure brings an issue of concern in whether a "foreign substance" might reduce radiation crosslinking efficiency and/or change microstructural characteristics by diffusing into UHMWPE. The key to clarify this fundamental issue resides in performing a quantitative evaluation of the obtained material structure and its polymeric chain mobility on the molecular scale. In this paper, a Raman spectroscopic examination is presented of molecular orientation and phase fractions in as-processed vitamin E-infused UHMWPE acetabular liners in comparison with a model (undoped and unirradiated/uncrosslinked) and a conventional (undoped and 33kGy-sterilized by gamma-irradiation) UHMWPE liners. The microstructural responses of structurally different liners to externally applied compressive strain were also monitored. The main results of the spectroscopic analyses can be summarized as follows: (i) preliminary gamma irradiation reduced the fraction of amorphous phase and increased the degree of molecular alignment, the vitamin E-infused liner preserving the crystallinity level achieved by the 100-kGy irradiation injected before infusion; (ii) the presence of vitamin E significantly promoted orientational randomness, which increased with increasing compressive strain magnitude, a phenomenon beneficial to minimize strain-softening-assisted wear phenomena.

  13. 3D Bi2S3/TiO2 cross-linked heterostructure: An efficient strategy to improve charge transport and separation for high photoelectrochemical performance

    NASA Astrophysics Data System (ADS)

    Han, Minmin; Jia, Junhong

    2016-10-01

    A novel 3D cross-linked heterostructure of TiO2 nanorods connecting with each other via ultrathin Bi2S3 nanosheets is constructed by a facile and effective strategy. The growth mechanism has been investigated and proposed based on the evolution of microstructure by changing the reaction parameters. Benefiting from the unique cross-linked heterostructure, the as-prepared Bi2S3 nanosheets modified TiO2 nanorods arrays could achieve a high energy conversion efficiency of 3.29% which is the highest value to date for Bi2S3-only sensitized solar cells as the reported highest value is 2.23% and other reported values are less than 1%. Furthermore, the photoelectrochemical studies clearly reveal that the novel cross-linked heterostructure exhibits much better activity than 0D nanoparticles decorated TiO2 nanorods under visible light irradiation, which may be primarily ascribed to the efficient electron transfer from 2D ultrathin Bi2S3 nanosheets to 1D TiO2 nanorod arrays. The promising results in this work confirm the advantages of cross-linked heterostructure and also undoubtedly offer an attractive synthesis strategy to fabricate other nanorod-based hierarchical architecture as well as nano-devices for solar energy conversion.

  14. Radiographic and retrieval wear analyses of the first generation highly cross-linked polyethylene cup against a ceramic femoral head.

    PubMed

    Oonishi, Hiroyuki; Kyomoto, Masayuki; Iwamoto, Mikio; Ueno, Masaru; Oonishi, Hironobu

    2013-11-01

    In this study, the in vivo wear of highly cross-linked polyethylene (CLPE) cups against alumina ceramic femoral heads was evaluated by radiographic and retrieval analysis. The radiographic wear of six ethylene oxide gas-sterilized (i.e., non-cross-linked) conventional polyethylene (PE) cups with the mean follow-up of 20.9 years and 60 CLPE cups with the mean follow-up of 7.4 years was measured. The retrieved 16 PE cups with clinical use for mean 21.5 years and 10 CLPE cups with clinical use for mean 2.9 years was evaluated as a retrieval analysis. In the radiographic analysis, the linear wear of CLPE cups was significantly lower (99% reduction) compared to conventional polyethylene cups. The results of retrieval analyses for both cups were similar to those of radiographic analyses. Even when third-body wear occurred during clinical use, no surface damage was observed on the surface of ceramic femoral heads. The surface is not sensitive to third-body wear, and hence, the ceramic femoral head has a great advantage in terms of the wear of CLPE under third-body wear conditions. In conclusion, CLPE cups used with alumina ceramic femoral heads in total hip arthroplasty should have favorable wear resistance in several in vivo situations.

  15. Graphene oxide-immobilized NH₂-terminated silicon nanoparticles by cross-linked interactions for highly stable silicon negative electrodes.

    PubMed

    Sun, Cheng; Deng, Yuanfu; Wan, Lina; Qin, Xusong; Chen, Guohua

    2014-07-23

    There is a great interest in the utilization of silicon-based anodes for lithium-ion batteries. However, its poor cycling stability, which is caused by a dramatic volume change during lithium-ion intercalation, and intrinsic low electric conductivity hamper its industrial applications. A facile strategy is reported here to fabricate graphene oxide-immobilized NH2-terminated silicon nanoparticles (NPs) negative electrode (Si@NH2/GO) directed by hydrogen bonding and cross-linked interactions to enhance the capacity retention of the anode. The NH2-modified Si NPs first form strong hydrogen bonds and covalent bonds with GO. The Si@NH2/GO composite further forms hydrogen bonds and covalent bonds with sodium alginate, which acts as a binder, to yield a stable composite negative electrode. These two chemical cross-linked/hydrogen bonding interactions-one between NH2-modified Si NPs and GO, and another between the GO and sodium alginate-along with highly mechanically flexible graphene oxide, produced a robust network in the negative electrode system to stabilize the electrode during discharge and charge cycles. The as-prepared Si@NH2/GO electrode exhibits an outstanding capacity retention capability and good rate performance, delivering a reversible capacity of 1000 mAh g(-1) after 400 cycles at a current of 420 mA g(-1) with almost 100% capacity retention. The results indicated the importance of system-level strategy for fabricating stable electrodes with improved electrochemical performance.

  16. Facial Synthesis of Three-Dimensional Cross-Linked Cage for High-Performance Lithium Storage.

    PubMed

    Sun, Zixu; Wang, Xinghui; Ying, Hangjun; Wang, Guangjin; Han, Wei-Qiang

    2016-06-22

    Silicon/C composite is a promising anode material for high-energy Li-ion batteries. However, synthesizing high-performance Si-based materials at large scale and low cost remains a huge challenge. Here, we for the first time report the preparation of an interconnected three-dimensional (3D) porous Si-hybrid architecture by using a spray drying method. In this unique structure, the highly robust C-CNT-RGO cages not only can improve the conductivity of the electrode and buffer the volume expansion but also suppress the Si nanoparticles aggregation. As a result, the 3D Si@po-C/CNT/RGO electrode achieves long-life cycling stability at high rates (a reversible capacity of 854.9 mA h g(-1) at 2 A g(-1) after 500 cycles and capacity decay less than 0.013% per cycle) and good rate capability (1454.7, 1198.8, 949.2, 597.8, and 150 mA h g(-1) at current densities of 1, 2, 4, 10, and 20 A g(-1), respectively). Moreover, this novel electrode could deliver high reversible capacities and long-life stabilities even with high mass loading density (764.9 mA h g(-1) at 1.0 mg cm(-2) after 500 cycles and 472.2 mA h g(-1) at 1.5 mg cm(-2) after 400 cycles, respectively). This cheap and scalable strategy can be extended to fabricate other materials with large volume expansion (Sn, Ge, transition-metal oxides) and 3D porous carbon for other potential applications. PMID:27236924

  17. Ionic modified crosslinked salep: a highly loaded and efficient heterogeneous organocatalyst.

    PubMed

    Pourjavadi, Ali; Hosseini, Seyed Hassan; Fakoorpoor, Seyed Mahmoud

    2013-02-15

    In this work, a novel heterogeneous organocatalyst was synthesized by immobilization of hydroxide ions on the modified salep as a natural polymer. Because of the grafting of ionic polymer chains onto the salep backbone, catalyst has high loading level of hydroxide ions (3.01 mmol/g). The resulting catalyst shows excellent activity in the synthesis of 4H-benzo[b]pyrans in water at room temperature in short reaction times. The present catalyst and protocol represent a simple, ecologically safe and cost-effective route to synthesize 4H-benzo[b]pyrans with high product yield, as well as easy catalyst recycling.

  18. Wear resistant performance of highly cross-linked and annealed ultra-high molecular weight polyethylene against ceramic heads in total hip arthroplasty.

    PubMed

    Sato, Taishi; Nakashima, Yasuharu; Akiyama, Mio; Yamamoto, Takuaki; Mawatari, Taro; Itokawa, Takashi; Ohishi, Masanobu; Motomura, Goro; Hirata, Masanobu; Iwamoto, Yukihide

    2012-12-01

    The purpose of this study was to examine the effects of ceramic femoral head material, size, and implantation periods on the wear of annealed, cross-linked ultra-high molecular weight polyethylene (UHMWPE) (XLPE) in total hip arthroplasty compared to non-cross-linked conventional UHMWPE (CPE). XLPE was fabricated by cross-linking with 60 kGy irradiation and annealing. Femoral heads made from zirconia and alumina ceramics and cobalt-chrome (CoCr) of 22 or 26 mm diameter were used. In this retrospective cohort study, the femoral head penetration into the cup was measured digitally on radiographs of 367 hips with XLPE and 64 hips with CPE. The average follow-up periods were 6.3 and 11.9 years, respectively. Both XLPE creep and wear rates were significantly lower than those of CPE (0.19 mm vs. 0.44 mm, 0.0001 mm/year vs. 0.09 mm/year, respectively). Zirconia displayed increased wear rates compared to alumina in CPE; however, there was no difference among head materials in XLPE (0.0008, 0.00007, and -0.009 mm/year for zirconia, alumina, and CoCr, respectively). Neither head size or implantation period impacted XLPE wear. In contrast to CPE, XLPE displayed low wear rates surpassing the effects of varying femoral head material, size, implantation period, and patient demographics. Further follow-up is required to determine the long-term clinical performance of the annealed XLPE.

  19. High-Strength, Tough, Fatigue Resistant, and Self-Healing Hydrogel Based on Dual Physically Cross-Linked Network.

    PubMed

    Gong, Zhengyu; Zhang, Guoping; Zeng, Xiaoliang; Li, Jinhui; Li, Gang; Huang, Wangping; Sun, Rong; Wong, Chingping

    2016-09-14

    Hydrogels usually suffer from low mechanical strength, which largely limit their application in many fields. In this Research Article, we prepared a dual physically cross-linked hydrogel composed of poly(acrylamide-co-acrylic acid) (PAM-co-PAA) and poly(vinyl alcohol) (PVA) by simple two-steps methods of copolymerization and freezing/thawing. The hydrogen bond-associated entanglement of copolymer chains formed as cross-linking points to construct the first network. After being subjected to the freezing/thawing treatment, PVA crystalline domains were formed to serve as knots of the second network. The hydrogels were demonstrated to integrate strength and toughness (1230 ± 90 kPa and 1250 ± 50 kJ/m(3)) by the introduction of second physically cross-linked network. What̀s more, the hydrogels exhibited rapid recovery, excellent fatigue resistance, and self-healing property. The dynamic property of the dual physically cross-linked network contributes to the excellent energy dissipation and self-healing property. Therefore, this work provides a new route to understand the toughness mechanism of dual physically cross-linked hydrogels, hopefully promoting current hydrogel research and expanding their applications. PMID:27548327

  20. A New Dry Etching Method with the High Etching Rate for Patterning Cross-Linked SU-8 Thick Films

    NASA Astrophysics Data System (ADS)

    Han, Jingning; Yin, Zhifu; Zou, Helin; Wang, Wenqiang; Feng, Jianbo

    2016-05-01

    Photo sensitive polymer SU-8, owing to its excellent mechanical properties and dielectric properties on polymerization, is widely used in MEMS device fabrications. However, the removing, stripping or re-patterning of the cross-linked SU-8 is a difficult issue. In this paper, CF4/O2 gas mixture provided by a plasma asher equipment was used for the patterning of cross-linked SU-8 material. The RF power, the temperature of the substrate holder, chamber pressure and gas concentration were optimized for the cross-linked SU-8 etching process. When the CF4/O2 mixture contains about 5%CF4 by volume, the etching rate can be reached at 5.2 μm/min.

  1. Medium-term results of cementation of a highly cross-linked polyethylene liner into a well-fixed acetabular shell in revision hip arthroplasty.

    PubMed

    Lim, Seung-Jae; Lee, Keun-Ho; Park, Shin-Hyung; Park, Youn-Soo

    2014-03-01

    The present study was undertaken to document outcomes of cementation of a highly cross-linked polyethylene (PE) liner into a well-fixed acetabular metal shell in 36 hips. All operations were performed by a single surgeon using only one type of liner. Patients were followed for a mean of 6.1 years (range, 3-8 years). Mean Harris hip score improved from 58 points preoperatively to 91 points postoperatively. There were no cases of PE liner dislodgement or progressive osteolysis. 1 hip (2.8%) required revision surgery for acetabular cup loosening with greater trochanteric fracture. Complications included 1 peroneal nerve palsy and 1 dislocation. The results of this study and previous reports demonstrated that cementation of highly cross-linked PE liner into well-fixed metal shell could provide good midterm durability.

  2. Highly Cross-Linked Versus Conventional Polyethylene in Posterior-Stabilized Total Knee Arthroplasty at a Mean 5-Year Follow-up.

    PubMed

    Meneghini, R Michael; Lovro, Luke R; Smits, Shelly A; Ireland, Philip H

    2015-10-01

    Concerns of highly cross-linked polyethylene (XLPE) in total knee arthroplasty (TKA) exist regarding fatigue resistance and oxidation, particularly in posterior-stabilized (PS) designs. A prospective cohort study of 114 consecutive PS TKAs utilized conventional polyethylene in 50 knees and second-generation annealed XLPE in 64 TKAs. Clinical (Short-Form 36, Knee Society Scores, and LEAS) and radiographic outcomes were evaluated at a mean of 5 years in 103 TKAs. Mean KSS scores were 12 points higher (P=0.01) and SF-36 physical function subset 14 points higher (P=0.005) in the XLPE group. There was no radiographic osteolysis or mechanical failure related to the tibial polyethylene in either group. At 5-year follow-up, no deleterious effects related to highly cross-linked posterior stabilized tibial polyethylene inserts were observed.

  3. Persistent high fertility in Uganda: young people recount obstacles and enabling factors to use of contraceptives

    PubMed Central

    2010-01-01

    Background High fertility among young people aged 15-24 years is a public health concern in Uganda. Unwanted pregnancy, unsafe induced abortions and associated high morbidity and mortality among young women may be attributed to low contraceptive use. This study aims at exploring reasons for low contraceptive use among young people. Methods In 16 focus group discussions, the views of young people about obstacles and enabling factors to contraceptive use in Mityana and Mubende districts, Uganda were explored. The groups were homogeneously composed by married and unmarried men and women, between the ages of 15-24. The data obtained was analyzed using qualitative content analysis. Results Young men and women described multiple obstacles to contraceptive use. The obstacles were categorized as misconceptions and fears related to contraception, gender power relations, socio-cultural expectations and contradictions, short term planning, and health service barriers. Additionally, young people recounted several enabling factors that included female strategies to overcome obstacles, changing perceptions to contraceptive use, and changing attitude towards a small family size. Conclusions Our findings suggest changing perceptions and behavior shift towards contraceptive use and a small family size although obstacles still exist. Personalized strategies to young women and men are needed to motivate and assist young people plan their future families, adopt and sustain use of contraceptives. Reducing obstacles and reinforcing enabling factors through education, culturally sensitive behavior change strategies have the potential to enhance contraceptives use. Alternative models of contraceptive service delivery to young people are proposed. PMID:20813069

  4. Wear resistance and mechanical properties of highly cross-linked, ultrahigh-molecular weight polyethylene doped with vitamin E.

    PubMed

    Oral, Ebru; Christensen, Steven D; Malhi, Arnaz S; Wannomae, Keith K; Muratoglu, Orhun K

    2006-06-01

    Our hypothesis was that cross-linked, ultrahigh-molecular weight polyethylene (UHMWPE) stabilized with vitamin E (alpha-tocopherol) would be wear-resistant and fatigue-resistant. Acetabular liners were radiation cross-linked, doped with vitamin E, and gamma-sterilized. Hip simulator wear rate of vitamin E-stabilized UHMWPE was approximately 1 and 6 mg/million-cycles in clean serum and in serum with third-body particles, respectively, a 4-fold to 10-fold decrease from that of conventional UHMWPE. The ultimate strength, yield strength, elongation at break, and fatigue resistance of vitamin E-stabilized UHMWPE were significantly higher than that of 100 kGy-irradiated and melted UHMWPE, and were unaffected by accelerated aging. Rim impingement testing with 3.7-mm-thick acetabular liners up to 2 million-cycles showed no significant damage of the cross-linked liners compared with conventional, gamma-sterilized in inert UHMWPE, vitamin E-stabilized liners. The data indicate good in vitro wear properties and improved mechanical and fatigue properties for vitamin E-stabilized, cross-linked UHMWPE.

  5. Crosslink Density and Molecular Weight Effects on the Viscoelastic Response of a Glassy High-Performance Polyimide

    NASA Technical Reports Server (NTRS)

    Nicholson, Lee M.; Whitley, Karen S.; Gates, Thomas S.

    2001-01-01

    Durability and long-term performance are among the primary concerns for the use of advanced polymer matrix composites (PMCs) in modern aerospace structural applications. For a PMC subJected to long-term exposure at elevated temperatures. the viscoelastic nature of the polymer matrix will contribute to macroscopic changes in composite stiffness, strength and fatigue life. Over time. changes in the polymer due to physical aging will have profound effects on tile viscoelastic compliance of the material, hence affecting its long-term durability. Thus, the ability to predict material performance using intrinsic properties, such as crosslink density and molecular weight, would greatly enhance the efficiency of design and development of PMCs. The objective of this paper is to discuss and present the results of an experimental study that considers the effects of crosslink density, molecular weight and temperature on the viscoelastic behavior including physical aging of an advanced polymer. Five distinct variations in crosslink density were used to evaluate the differences in mechanical performance of an advanced polyimide. The physical aging behavior was isolated by conducting sequenced, short-term isothermal creep compliance tests in tension. These tests were performed over a range of sub-glass transition temperatures. The material constants, material master curves and physical aging-related parameters were evaluated as a function of temperature crosslink density and molecular weight using time-temperature and time-aging time superposition techniques.

  6. Space-to-Space Power Beaming Enabling High Performance Rapid Geocentric Orbit Transfer

    NASA Technical Reports Server (NTRS)

    Dankanich, John W.; Vassallo, Corinne; Tadge, Megan

    2015-01-01

    The use of electric propulsion is more prevalent than ever, with industry pursuing all electric orbit transfers. Electric propulsion provides high mass utilization through efficient propellant transfer. However, the transfer times become detrimental as the delta V transitions from near-impulsive to low-thrust. Increasing power and therefore thrust has diminishing returns as the increasing mass of the power system limits the potential acceleration of the spacecraft. By using space-to-space power beaming, the power system can be decoupled from the spacecraft and allow significantly higher spacecraft alpha (W/kg) and therefore enable significantly higher accelerations while maintaining high performance. This project assesses the efficacy of space-to-space power beaming to enable rapid orbit transfer while maintaining high mass utilization. Concept assessment requires integrated techniques for low-thrust orbit transfer steering laws, efficient large-scale rectenna systems, and satellite constellation configuration optimization. This project includes the development of an integrated tool with implementation of IPOPT, Q-Law, and power-beaming models. The results highlight the viability of the concept, limits and paths to infusion, and comparison to state-of-the-art capabilities. The results indicate the viability of power beaming for what may be the only approach for achieving the desired transit times with high specific impulse.

  7. Heat transfer performance of a phase-change thermal energy storage water heater using cross-linked high density polyethylene pellets

    SciTech Connect

    Jotshi, C.K.; Klausner, J.F.; Goswami, D.Y.; Hsieh, C.K.; Santhosh, M.K.; Colacino, F.

    1996-12-31

    The objective of this investigation was to develop an efficient water heater that stores thermal energy in a mixture of cross-linked high density polyethylene (HDPE) pellets and propylene glycol. Properties of cross-linked HDPE, such as melting and crystallization temperatures, heat of fusion and crystallization, and volume change were measured in the laboratory. The heat transfer coefficient for the mixture was also measured in a laboratory test. A prototype model of a storage water heater using a mixture of cross-linked HDPE pellets and propylene glycol was designed and fabricated. A copper finned heat transfer coil was used to extract the heat from the storage tank by passing water through it. The heat transfer efficiency (heat extracted by water/heat stored) was measured to be about 70%. To increase the efficiency, the storage unit was modified. In the modified unit, the length of the heat transfer coil was increased and coil spacing optimized. With the modification, the heat transfer efficiency was measured to be about 90%. In addition, a variable heat flux heating element, having high heat flux at the bottom and low heat flux at top, was used to reduce thermal stratification of the propylene glycol/HDPE pellet mixture.

  8. Heat shrinkable behavior, physico-mechanical and structure properties of electron beam cross-linked blends of high-density polyethylene with acrylonitrile-butadiene rubber

    NASA Astrophysics Data System (ADS)

    Reinholds, Ingars; Kalkis, Valdis; Merijs-Meri, Remo; Zicans, Janis; Grigalovica, Agnese

    2016-03-01

    In this study, heat-shrinkable composites of electron beam irradiated high-density polyethylene (HDPE) composites with acrylonitrile-butadiene rubber (NBR) were investigated. HDPE/NBR blends at a ratio of components 100/0, 90/10, 80/20, 50/50 and 20/80 wt% were prepared using a two-roll mill. The compression molded films were irradiated high-energy (5 MeV) accelerated electrons up to irradiation absorbed doses of 100-300 kGy. The effect of electron beam induced cross-linking was evaluated by the changes of mechanical properties, gel content and by the differences of thermal properties, detected by differential scanning calorimetry. The thermo-shrinkage forces were determined as the kinetics of thermorelaxation and the residual shrinkage stresses of previously oriented (stretched up to 100% at above melting temperature of HDPE and followed by cooling to room temperature) specimens of irradiated HDPE/NBR blends under isometric heating-cooling mode. The compatibility between the both components was enhanced due to the formation of cross-linked sites at amorphous interphase. The results showed increase of mechanical stiffness of composites with increase of irradiation dose. The values of gel fraction compared to thermorelaxation stresses increased with the growth of irradiation dose level, as a result of formation cross-linked sites in amorphous PP/NBR interphase.

  9. Ionic liquid enabled FeS2 for high-energy-density lithium-ion batteries.

    PubMed

    Evans, Tyler; Piper, Daniela Molina; Kim, Seul Cham; Han, Sang Sub; Bhat, Vinay; Oh, Kyu Hwan; Lee, Se-Hee

    2014-11-19

    High-energy-density FeS2 cathodes en-abled by a bis(trifluoromethanesulfonyl)imide (TFSI-) anion-based room temperature ionic liquid (RTIL) electrolyte are demonstrated. A TFSI-based ionic liquid (IL) significantly mitigates polysulfide dissolution, and therefore the parasitic redox shuttle mechanism, that plagues sulfur-based electrode chemistries. FeS2 stabilization with a TFSI(-) -based IL results in one of the highest energy density cathodes, 542 W h kg(-1) (normalized to cathode composite mass), reported to date.

  10. Development of Microfluidic Systems Enabling High-Throughput Single-Cell Protein Characterization

    PubMed Central

    Fan, Beiyuan; Li, Xiufeng; Chen, Deyong; Peng, Hongshang; Wang, Junbo; Chen, Jian

    2016-01-01

    This article reviews recent developments in microfluidic systems enabling high-throughput characterization of single-cell proteins. Four key perspectives of microfluidic platforms are included in this review: (1) microfluidic fluorescent flow cytometry; (2) droplet based microfluidic flow cytometry; (3) large-array micro wells (microengraving); and (4) large-array micro chambers (barcode microchips). We examine the advantages and limitations of each technique and discuss future research opportunities by focusing on three key performance parameters (absolute quantification, sensitivity, and throughput). PMID:26891303

  11. The Stanford Automated Mounter: Enabling High-Throughput Protein Crystal Screening at SSRL

    SciTech Connect

    Smith, C.A.; Cohen, A.E.

    2009-05-26

    The macromolecular crystallography experiment lends itself perfectly to high-throughput technologies. The initial steps including the expression, purification, and crystallization of protein crystals, along with some of the later steps involving data processing and structure determination have all been automated to the point where some of the last remaining bottlenecks in the process have been crystal mounting, crystal screening, and data collection. At the Stanford Synchrotron Radiation Laboratory, a National User Facility that provides extremely brilliant X-ray photon beams for use in materials science, environmental science, and structural biology research, the incorporation of advanced robotics has enabled crystals to be screened in a true high-throughput fashion, thus dramatically accelerating the final steps. Up to 288 frozen crystals can be mounted by the beamline robot (the Stanford Auto-Mounting System) and screened for diffraction quality in a matter of hours without intervention. The best quality crystals can then be remounted for the collection of complete X-ray diffraction data sets. Furthermore, the entire screening and data collection experiment can be controlled from the experimenter's home laboratory by means of advanced software tools that enable network-based control of the highly automated beamlines.

  12. Predisposing, enabling, and need factors associated with high service use in a public mental health system.

    PubMed

    Lindamer, Laurie A; Liu, Lin; Sommerfeld, David H; Folsom, David P; Hawthorne, William; Garcia, Piedad; Aarons, Gregory A; Jeste, Dilip V

    2012-05-01

    The purpose of this study was twofold: (1) To investigate the individual- and system-level characteristics associated with high utilization of acute mental health services according to a widely-used theory of service use-Andersen's Behavioral Model of Health Service Use -in individuals enrolled in a large, public-funded mental health system; and (2) To document service utilization by high use consumers prior to a transformation of the service delivery system. We analyzed data from 10,128 individuals receiving care in a large public mental health system from fiscal years 2000-2004. Subjects with information in the database for the index year (fiscal year 2000-2001) and all of the following 3 years were included in this study. Using logistic regression, we identified predisposing, enabling, and need characteristics associated with being categorized as a single-year high use consumer (HU: >3 acute care episodes in a single year) or multiple-year HU (>3 acute care episodes in more than 1 year). Thirteen percent of the sample met the criteria for being a single-year HU and an additional 8% met the definition for multiple-year HU. Although some predisposing factors were significantly associated with an increased likelihood of being classified as a HU (younger age and female gender) relative to non-HUs, the characteristics with the strongest associations with the HU definition, when controlling for all other factors, were enabling and need factors. Homelessness was associated with 115% increase in the odds of ever being classified as a HU compared to those living independently or with family and others. Having insurance was associated with increased odds of being classified as a HU by about 19% relative to non-HUs. Attending four or more outpatient visits was an enabling factor that decreased the chances of being defined as a HU. Need factors, such as having a diagnosis of schizophrenia, bipolar disorder or other psychotic disorder or having a substance use disorder

  13. Predisposing, enabling, and need factors associated with high service use in a public mental health system.

    PubMed

    Lindamer, Laurie A; Liu, Lin; Sommerfeld, David H; Folsom, David P; Hawthorne, William; Garcia, Piedad; Aarons, Gregory A; Jeste, Dilip V

    2012-05-01

    The purpose of this study was twofold: (1) To investigate the individual- and system-level characteristics associated with high utilization of acute mental health services according to a widely-used theory of service use-Andersen's Behavioral Model of Health Service Use -in individuals enrolled in a large, public-funded mental health system; and (2) To document service utilization by high use consumers prior to a transformation of the service delivery system. We analyzed data from 10,128 individuals receiving care in a large public mental health system from fiscal years 2000-2004. Subjects with information in the database for the index year (fiscal year 2000-2001) and all of the following 3 years were included in this study. Using logistic regression, we identified predisposing, enabling, and need characteristics associated with being categorized as a single-year high use consumer (HU: >3 acute care episodes in a single year) or multiple-year HU (>3 acute care episodes in more than 1 year). Thirteen percent of the sample met the criteria for being a single-year HU and an additional 8% met the definition for multiple-year HU. Although some predisposing factors were significantly associated with an increased likelihood of being classified as a HU (younger age and female gender) relative to non-HUs, the characteristics with the strongest associations with the HU definition, when controlling for all other factors, were enabling and need factors. Homelessness was associated with 115% increase in the odds of ever being classified as a HU compared to those living independently or with family and others. Having insurance was associated with increased odds of being classified as a HU by about 19% relative to non-HUs. Attending four or more outpatient visits was an enabling factor that decreased the chances of being defined as a HU. Need factors, such as having a diagnosis of schizophrenia, bipolar disorder or other psychotic disorder or having a substance use disorder

  14. Correlation of in Situ Oxazolidine Formation with Highly Synergistic Cytotoxicity and DNA Cross-Linking in Cancer Cells from Combinations of Doxorubicin and Formaldehyde.

    PubMed

    Barthel, Benjamin L; Mooz, Erin L; Wiener, Laura Elizabeth; Koch, Gary G; Koch, Tad H

    2016-03-10

    Anthracyclines are a class of antitumor compounds that are successful and widely used but suffer from cardiotoxicity and acquired tumor resistance. Formaldehyde interacts with anthracyclines to enhance antitumor efficacy, bypass resistance mechanisms, improve the therapeutic profile, and change the mechanism of action from a topoisomerase II poison to a DNA cross-linker. Contrary to current dogma, we show that both efficient DNA cross-linking and potent synergy in combination with formaldehyde correlate with the anthracycline's ability to form cyclic formaldehyde conjugates as oxazolidine moieties and that the cyclic conjugates are better cross-linking agents and cytotoxins than acyclic conjugates. We also provide evidence that suggests that the oxazolidine forms in situ, since cotreatment with doxorubicin and formaldehyde is highly cytotoxic to dox-resistant tumor cell lines, and that this benefit is absent in combinations of formaldehyde and epirubicin, which cannot form stable oxazolidines. These results have potential clinical implications in the active field of anthracycline prodrug design and development. PMID:26881291

  15. Vitamin-E blended and infused highly cross-linked polyethylene for total hip arthroplasty: a comparison of three-dimensional crystalline morphology and strain recovery behavior.

    PubMed

    Takahashi, Yasuhito; Masaoka, Toshinori; Yamamoto, Kengo; Shishido, Takaaki; Tateiwa, Toshiyuki; Kubo, Kosuke; Pezzotti, Giuseppe

    2014-08-01

    Vitamin-E (α-tocopherol) is now recognized worldwide as one of the most promising antioxidant agents for highly cross-linked polyethylene (HXLPE) used in total joint replacements. In the contemporary manufacturing processes, two alternative methods are currently accepted to incorporate this antioxidant into polyethylene microstructure: (i) blending vitamin-E before consolidation and radiation crosslinking; (ii) infusing vitamin-E via a homogenizing heat treatment after radiation crosslinking. However, the effects of these technological differences on crystalline morphology and mechanical behavior of polyethylene remains to be fully elucidated. The aim of this paper is to quantitatively evaluate the microstructural differences of commercially available vitamin-E blended and infused HXLPE liner (referred to as Liner BL and IF, respectively). For this purpose, confocal/polarized Raman spectroscopy was used to systematically examine the three-phase percentages (amorphous (αa), crystalline (αc), and intermediate third phase (αt)), preferential molecular orientation (θp), and degree of crystalline anisotropy (〈P2(cosβ)〉). Additionally, we compared the time-dependent deformation of Liner BL and IF as obtained by uniaxial stress relaxation tests followed by strain recovery. Distinctive features of the near-surface αc, θp, and〈P2(cosβ)〉 were clearly observed within the first 35μm in the two studied liners. Despite the equivalent level of the bulk αc and 〈P2(cosβ)〉, higher restoring force against a uniaxial strain was observed in Liner IF, which reflects a higher crosslink density in its amorphous phase. On the other hands, a higher degree of surface orientational randomness was detected in Liner BL, which is structurally more beneficial for minimizing the in-vivo occurrence of strain-softening-assisted wear.

  16. In situ thermally cross-linked polyacrylonitrile as binder for high-performance silicon as lithium ion battery anode.

    PubMed

    Shen, Lanyao; Shen, Lian; Wang, Zhaoxiang; Chen, Liquan

    2014-07-01

    Electrode integrity and electric contact between particles and between particle and current collector are critical for electrochemical performance, especially for that of electrode materials with large volume change during cycling and with poor electric conductivity. We report on the in situ thermally cross-linked polyacrylonitrile (PAN) as a binder for silicon-based anodes of lithium-ion batteries. The electrode delivers excellent cycle life and rate capability with a reversible capacity of about 1450 mA h g(-1) even after 100 cycles. The improved electrochemical performance of such silicon electrodes is attributed to heat-treatment-induced cross-linking and the formation of conjugated PAN. These findings open new avenues to explore other polymers for both anode and cathode electrodes of rechargeable batteries.

  17. In situ thermally cross-linked polyacrylonitrile as binder for high-performance silicon as lithium ion battery anode.

    PubMed

    Shen, Lanyao; Shen, Lian; Wang, Zhaoxiang; Chen, Liquan

    2014-07-01

    Electrode integrity and electric contact between particles and between particle and current collector are critical for electrochemical performance, especially for that of electrode materials with large volume change during cycling and with poor electric conductivity. We report on the in situ thermally cross-linked polyacrylonitrile (PAN) as a binder for silicon-based anodes of lithium-ion batteries. The electrode delivers excellent cycle life and rate capability with a reversible capacity of about 1450 mA h g(-1) even after 100 cycles. The improved electrochemical performance of such silicon electrodes is attributed to heat-treatment-induced cross-linking and the formation of conjugated PAN. These findings open new avenues to explore other polymers for both anode and cathode electrodes of rechargeable batteries. PMID:24782265

  18. Enabling Earth-Abundant Pyrite (FeS2) Semiconductor Nanostructures for High Performance Photovoltaic Devices

    SciTech Connect

    Jin, Song

    2014-11-18

    This project seeks to develop nanostructures of iron pyrite, an earth-abundant semiconductor, to enable their applications in high-performance photovoltaic (PV) devices. Growth of high purity iron pyrite nanostructures (nanowires, nanorods, and nanoplates), as well as iron pyrite thin films and single crystals, has been developed and their structures characterized. These structures have been fundamentally investigated to understand the origin of the low solar energy conversion efficiency of iron pyrite and various passivation strategies and doping approaches have been explored in order to improve it. By taking advantage of the high surface-to-bulk ratio in nanostructures and effective electrolyte gating, we fully characterized both the surface inversion and bulk electrical transport properties for the first time through electrolyte-gated Hall measurements of pyrite nanoplate devices and show that pyrite is n-type in the bulk and p-type near the surface due to strong inversion, which has important consequences to using nanocrystalline pyrite for efficient solar energy conversion. Furthermore, through a comprehensive investigation on n-type iron pyrite single crystals, we found the ionization of high-density bulk deep donor states, likely resulting from bulk sulfur vacancies, creates a non-constant charge distribution and a very narrow surface space charge region that limits the total barrier height, thus satisfactorily explains the limited photovoltage and poor photoconversion efficiency of iron pyrite single crystals. These findings suggest new ideas on how to improve single crystal pyrite and nanocrystalline or polycrystalline pyrite films to enable them for high performance solar applications.

  19. High Dielectric and Mechanical Properties Achieved in Cross-Linked PVDF/α-SiC Nanocomposites with Elevated Compatibility and Induced Polarization at the Interface.

    PubMed

    Feng, Yefeng; Miao, Bei; Gong, Honghong; Xie, Yunchuan; Wei, Xiaoyong; Zhang, Zhicheng

    2016-07-27

    Remarkably improved dielectric properties including high-k, low loss, and high breakdown strength combined with promising mechanical performance such as high flexibility, good heat, and chemical resistivity are hard to be achieved in high-k dielectric composites based on the current composite fabrication strategy. In this work, a family of high-k polymer nanocomposites has been fabricated from a facile suspension cast process followed by chemical cross-linking at elevated temperature. Internal double bonds bearing poly(vinylidene fluoride-chlorotrifluoroethylene) (P(VDF-CTFE-DB)) in total amorphous phase are employed as cross-linkable polymer matrix. α-SiC particles with a diameter of 500 nm are surface modified with 3-aminpropyltriethoxysilane (KH-550) as fillers for their comparable dielectric performance with PVDF polymer matrix, low conductivity, and high breakdown strength. The interface between SiC particles and PVDF matrix has been finely tailored, which leads to the significantly elevated dielectric constant from 10 to over 120 in SiC particles due to the strong induced polarization. As a result, a remarkably improved dielectric constant (ca. 70) has been observed in c-PVDF/m-SiC composites bearing 36 vol % SiC, which could be perfectly predicted by the effective medium approximation (EMA) model. The optimized interface and enhanced compatibility between two components are also responsible for the depressed conductivity and dielectric loss in the resultant composites. Chemical cross-linking constructed in the composites results in promising mechanical flexibility, good heat and chemical stability, and elevated tensile performance of the composites. Therefore, excellent dielectric and mechanical properties are finely balanced in the PVDF/α-SiC composites. This work might provide a facile and effective strategy to fabricate high-k dielectric composites with promising comprehensive performance. PMID:27377185

  20. High Dielectric and Mechanical Properties Achieved in Cross-Linked PVDF/α-SiC Nanocomposites with Elevated Compatibility and Induced Polarization at the Interface.

    PubMed

    Feng, Yefeng; Miao, Bei; Gong, Honghong; Xie, Yunchuan; Wei, Xiaoyong; Zhang, Zhicheng

    2016-07-27

    Remarkably improved dielectric properties including high-k, low loss, and high breakdown strength combined with promising mechanical performance such as high flexibility, good heat, and chemical resistivity are hard to be achieved in high-k dielectric composites based on the current composite fabrication strategy. In this work, a family of high-k polymer nanocomposites has been fabricated from a facile suspension cast process followed by chemical cross-linking at elevated temperature. Internal double bonds bearing poly(vinylidene fluoride-chlorotrifluoroethylene) (P(VDF-CTFE-DB)) in total amorphous phase are employed as cross-linkable polymer matrix. α-SiC particles with a diameter of 500 nm are surface modified with 3-aminpropyltriethoxysilane (KH-550) as fillers for their comparable dielectric performance with PVDF polymer matrix, low conductivity, and high breakdown strength. The interface between SiC particles and PVDF matrix has been finely tailored, which leads to the significantly elevated dielectric constant from 10 to over 120 in SiC particles due to the strong induced polarization. As a result, a remarkably improved dielectric constant (ca. 70) has been observed in c-PVDF/m-SiC composites bearing 36 vol % SiC, which could be perfectly predicted by the effective medium approximation (EMA) model. The optimized interface and enhanced compatibility between two components are also responsible for the depressed conductivity and dielectric loss in the resultant composites. Chemical cross-linking constructed in the composites results in promising mechanical flexibility, good heat and chemical stability, and elevated tensile performance of the composites. Therefore, excellent dielectric and mechanical properties are finely balanced in the PVDF/α-SiC composites. This work might provide a facile and effective strategy to fabricate high-k dielectric composites with promising comprehensive performance.

  1. Effects of simulated oxidation on the in vitro wear and mechanical properties of irradiated and melted highly crosslinked UHMWPE.

    PubMed

    Oral, Ebru; Neils, Andrew L; Doshi, Brinda N; Fu, Jun; Muratoglu, Orhun K

    2016-02-01

    Radiation crosslinked ultrahigh molecular weight polyethylene (UHMWPE) have reduced the wear rate of the bearing surface in total joint arthroplasty and the incidence of peri-prosthetic bone loss due to wear particles. The oxidation potential afforded to the material by the trapped residual free radicals after irradiation was addressed in first generation crosslinked UHMWPEs by using thermal treatments such as annealing or melting after irradiation. Postirradiation melted crosslinked UHMWPE did not contain detectable free radicals at the time of implantation and was expected to be resistant against oxidation for the lifetime of the implants. Recent analyses of long-term retrievals showed it was possible for irradiated and melted UHMWPEs to oxidize in vivo but studies on the effects of oxidation on these materials have been limited. In this study, we determined the effects of in vitro aging on the wear and mechanical properties of irradiated and melted UHMWPE as a function of radiation dose and found that even small amount of oxidation (oxidation index of 0.1) can have detrimental effects on its mechanical properties. There was a gradual increase in the wear rate below an oxidation index of 1 and a drastic increase thereafter. Therefore, it was shown in a simulated environment that oxidation can have detrimental effects to the clinically relevant properties of irradiated and melted UHMWPEs.

  2. Highly cross-linked Cu/a-Si core-shell nanowires for ultra-long cycle life and high rate lithium batteries

    NASA Astrophysics Data System (ADS)

    Wang, Hongxiang; Song, Hucheng; Lin, Zixia; Jiang, Xiaofan; Zhang, Xiaowei; Yu, Linwei; Xu, Jun; Pan, Lijia; Wang, Junzhuan; Zheng, Mingbo; Shi, Yi; Chen, Kunji

    2016-01-01

    Seeking long cycle lifetime and high rate performance are still challenging aspects to promote the application of silicon-loaded lithium ion batteries (LIBs), where optimal structural and compositional design are critical to maximize a synergistic effect in composite core-shell nanowire anode structures. We here propose and demonstrate a high quality conformal coating of an amorphous Si (a-Si) thin film over a matrix of highly cross-linked CuO nanowires (NWs). The conformal a-Si coating can serve as both a high capacity storage medium and a high quality binder that joins crossing CuO NWs into a continuous network. And the CuO NWs can be reduced into highly conductive Cu cores in low temperature H2 annealing. In this way, we have demonstrated an excellent cycling stability that lasts more than 700 (or 1000) charge/discharge cycles at a current density of 3.6 A g-1 (or 1 A g-1), with a high capacity retention rate of 80%. Remarkably, these Cu/a-Si core-shell anode structures can survive an extremely high charging current density of 64 A g-1 for 25 runs, and then recover 75% initial capacity when returning to 1 A g-1. We also present the first and straightforward experimental proof that these robust highly-cross-linked core-shell networks can preserve the structural integrity even after 1000 runs of cycling. All these results indicate a new and convenient strategy towards a high performance Si-loaded battery application.Seeking long cycle lifetime and high rate performance are still challenging aspects to promote the application of silicon-loaded lithium ion batteries (LIBs), where optimal structural and compositional design are critical to maximize a synergistic effect in composite core-shell nanowire anode structures. We here propose and demonstrate a high quality conformal coating of an amorphous Si (a-Si) thin film over a matrix of highly cross-linked CuO nanowires (NWs). The conformal a-Si coating can serve as both a high capacity storage medium and a high

  3. Enabling cost-effective high-current burst-mode operation in superconducting accelerators

    SciTech Connect

    Sheffield, Richard L.

    2015-06-01

    Superconducting (SC) accelerators are very efficient for CW or long-pulse operation, and normal conducting (NC) accelerators are cost effective for short-pulse operation. The addition of a short NC linac section to a SC linac can correct for the energy droop that occurs when pulsed high-current operation is required that exceeds the capability of the klystrons to replenish the cavity RF fields due to the long field fill-times of SC structures, or a requirement to support a broad range of beam currents results in variable beam loading. This paper describes the implementation of this technique to enable microseconds of high beam-current, 90 mA or more, in a 12 GeV SC long-pulse accelerator designed for the MaRIE 42-keV XFEL proposed for Los Alamos National Laboratory.

  4. Enabling cost-effective high-current burst-mode operation in superconducting accelerators

    DOE PAGES

    Sheffield, Richard L.

    2015-06-01

    Superconducting (SC) accelerators are very efficient for CW or long-pulse operation, and normal conducting (NC) accelerators are cost effective for short-pulse operation. The addition of a short NC linac section to a SC linac can correct for the energy droop that occurs when pulsed high-current operation is required that exceeds the capability of the klystrons to replenish the cavity RF fields due to the long field fill-times of SC structures, or a requirement to support a broad range of beam currents results in variable beam loading. This paper describes the implementation of this technique to enable microseconds of high beam-current,more » 90 mA or more, in a 12 GeV SC long-pulse accelerator designed for the MaRIE 42-keV XFEL proposed for Los Alamos National Laboratory.« less

  5. DOE High Performance Computing Operational Review (HPCOR): Enabling Data-Driven Scientific Discovery at HPC Facilities

    SciTech Connect

    Gerber, Richard; Allcock, William; Beggio, Chris; Campbell, Stuart; Cherry, Andrew; Cholia, Shreyas; Dart, Eli; England, Clay; Fahey, Tim; Foertter, Fernanda; Goldstone, Robin; Hick, Jason; Karelitz, David; Kelly, Kaki; Monroe, Laura; Prabhat,; Skinner, David; White, Julia

    2014-10-17

    U.S. Department of Energy (DOE) High Performance Computing (HPC) facilities are on the verge of a paradigm shift in the way they deliver systems and services to science and engineering teams. Research projects are producing a wide variety of data at unprecedented scale and level of complexity, with community-specific services that are part of the data collection and analysis workflow. On June 18-19, 2014 representatives from six DOE HPC centers met in Oakland, CA at the DOE High Performance Operational Review (HPCOR) to discuss how they can best provide facilities and services to enable large-scale data-driven scientific discovery at the DOE national laboratories. The report contains findings from that review.

  6. MEMS-enabled Dip Pen Nanolithography for directed nanoscale deposition and high-throughput nanofabrication

    NASA Astrophysics Data System (ADS)

    Haaheim, J. R.; Nafday, O. A.; Levesque, T.; Fragala, J.; Shile, R.

    2009-02-01

    Precision nanoscale deposition is a fundamental requirement for nanoscience research, development, and commercial implementation. Dip Pen Nanolithography(R) (DPN) is an inherently additive SPM-based technique which operates under ambient conditions, making it suitable to deposit a wide range of biological and inorganic materials. This technique is fundamentally enabled by a portfolio of MEMS devices tailored for microfluidic ink delivery, directed placement of nanoscale materials via actuated cantilevers, and cm2 tip arrays for high-throughput nanofabrication. Multiplexed deposition of nanoscale materials is a challenging problem, but we have implemented InkWells(TM) to enable selective delivery of ink materials to different tips in multiple probe arrays, while preventing cross-contamination. Active Pens(TM) can take advantage of this, directly place a variety of materials in nanoscale proximity, and do so in a "clean" fashion since the cantilevers can be manipulated in Z. Further, massively parallel two-dimensional nanopatterning with DPN is now commercially available via NanoInk's 2D nano PrintArray(TM), making DPN a highthroughput, flexible and versatile method for precision nanoscale pattern formation. By fabricating 55,000 tip-cantilevers across a 1 cm2 chip, we leverage the inherent versatility of DPN and demonstrate large area surface coverage, routinely achieving throughputs of 3×107 μm2 per hour. Further, we have engineered the device to be easy to use, wire-free, and fully integrated with the NSCRIPTOR's scanner, stage, and sophisticated lithography routines. In this talk we discuss the methods of operating this commercially available device, and subsequent results showing sub-100 nm feature sizes and excellent uniformity (standard deviation < 16%). Finally, we will discuss applications enabled by this MEMS portfolio including: 1) rapidly and flexibly generating nanostructures; 2) chemically directed assembly and 3) directly writing biological materials.

  7. In Vivo Imaging Enables High Resolution Preclinical Trials on Patients’ Leukemia Cells Growing in Mice

    PubMed Central

    Terziyska, Nadia; Alves, Catarina Castro; Groiss, Volker; Schneider, Katja; Farkasova, Katarina; Ogris, Manfred; Wagner, Ernst; Ehrhardt, Harald; Brentjens, Renier J.; zur Stadt, Udo; Horstmann, Martin; Quintanilla-Martinez, Leticia; Jeremias, Irmela

    2012-01-01

    Background Xenograft mouse models represent helpful tools for preclinical studies on human tumors. For modeling the complexity of the human disease, primary tumor cells are by far superior to established cell lines. As qualified exemplary model, patients’ acute lymphoblastic leukemia cells reliably engraft in mice inducing orthotopic disseminated leukemia closely resembling the disease in men. Unfortunately, disease monitoring of acute lymphoblastic leukemia in mice is hampered by lack of a suitable readout parameter. Design and Methods Patients’ acute lymphoblastic leukemia cells were lentivirally transduced to express the membrane-bound form of Gaussia luciferase. In vivo imaging was established in individual patients’ leukemias and extensively validated. Results Bioluminescence in vivo imaging enabled reliable and continuous follow-up of individual mice. Light emission strictly correlated to post mortem quantification of leukemic burden and revealed a logarithmic, time and cell number dependent growth pattern. Imaging conveniently quantified frequencies of leukemia initiating cells in limiting dilution transplantation assays. Upon detecting a single leukemia cell within more than 10,000 bone marrow cells, imaging enabled monitoring minimal residual disease, time to tumor re-growth and relapse. Imaging quantified therapy effects precisely and with low variances, discriminating treatment failure from partial and complete responses. Conclusions For the first time, we characterized in detail how in vivo imaging reforms preclinical studies on patient-derived tumors upon increasing monitoring resolution. In the future, in vivo imaging will enable performing precise preclinical studies on a broad range of highly demanding clinical challenges, such as treatment failure, resistance in leukemia initiating cells, minimal residual disease and relapse. PMID:23300782

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

    PubMed

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

    2015-11-01

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

  9. Towards enabling ultrasound guidance in cervical cancer high-dose-rate brachytherapy

    NASA Astrophysics Data System (ADS)

    Wong, Adrian; Sojoudia, Samira; Gaudet, Marc; Yap, Wan Wan; Chang, Silvia D.; Abolmaesumi, Purang; Aquino-Parsons, Christina; Moradi, Mehdi

    2014-03-01

    MRI and Computed Tomography (CT) are used in image-based solutions for guiding High Dose Rate (HDR) brachytherapy treatment of cervical cancer. MRI is costly and CT exposes the patients to ionizing radiation. Ultrasound, on the other hand, is affordable and safe. The long-term goal of our work is to enable the use of multiparametric ultrasound imaging in image-guided HDR for cervical cancer. In this paper, we report the development of enabling technology for ultrasound guidance and tissue typing. We report a system to obtain the 3D freehand transabdominal ultrasound RF signals and B-mode images of the uterus, and a method for registration of ultrasound to MRI. MRI and 3D ultrasound images of the female pelvis were registered by contouring the uterus in the two modalities, creating a surface model, followed by rigid and B-spline deformable registration. The resulting transformation was used to map the location of the tumor from the T2-weighted MRI to ultrasound images and to determine cancerous and normal areas in ultrasound. B-mode images show a contrast for cancer vs. normal tissue. Our study shows the potential and the challenges of ultrasound imaging in guiding cervical cancer treatments.

  10. Enabling linear alkyl carbonate electrolytes for high voltage Li-ion cells

    NASA Astrophysics Data System (ADS)

    Xia, Jian; Petibon, Remi; Xiong, Deijun; Ma, Lin; Dahn, J. R.

    2016-10-01

    Some of the problems of current electrolytes for high voltage Li-ion cells originate from ethylene carbonate (EC) which is thought to be an essential electrolyte component for Li-ion cells. Ethylene carbonate-free electrolytes containing 1 M LiPF6 in ethylmethyl carbonate (EMC) with small loadings of vinylene carbonate, fluoroethylene carbonate, or (4R,5S)-4,5-Difluoro-1,3-dioxolan-2-one acting as "enablers" were developed. These electrolytes used in Li(Ni0.4Mn0.4Co0.2)O2/graphite pouch type Li-ion cells tested at 4.2 V and 4.5 V yielded excellent charge-discharge cycling and storage properties. The results for cells containing linear alkyl carbonate electrolytes with no EC were compared to those of cells with EC-containing electrolytes incorporating additives proven to enhance cyclability of cells. The combination of EMC with appropriate amounts of these enablers yields cells with better performance than cells with EC-containing electrolytes incorporating additives tested to 4.5 V. Further optimizing these linear alkyl carbonate electrolytes with appropriate co-additives may represent a viable path to the successful commercial utilization of NMC/graphite Li-ion cells operated to 4.5 V and above.

  11. High-Speed Friction-Stir Welding To Enable Aluminum Tailor-Welded Blanks

    SciTech Connect

    Hovanski, Yuri; Upadhyay, Piyush; Carsley, John; Luzanski, Tom; Carlson, Blair; Eisenmenger, Mark; Soulami, Ayoub; Marshall, Dustin; Landino, Brandon; Hartfield-Wunsch, Susan

    2015-05-01

    Current joining technologies for automotive aluminum alloys are utilized in low-volume and niche applications, and have yet to be scaled for the high-volume vehicle market. This study targeted further weight reduction, part reduction, and cost savings by enabling tailor-welded blank technology for aluminum alloys at high-volumes. While friction stir welding has been traditionally applied at linear velocities less than one meter per minute, high volume production applications demand the process be extended to higher velocities more amenable to cost sensitive production environments. Unfortunately, weld parameters and performance developed and characterized at low to moderate welding velocities do not directly translate to high speed linear friction stir welding. Therefore, in order to facilitate production of high volume aluminum welded components, parameters were developed with a minimum welding velocity of three meters per minute. With an emphasis on weld quality, welded blanks were evaluated for post-weld formability utilizing a combination of numerical and experimental methods. Evaluation across scales was ultimately validated by stamping full-size production door inner panels made from dissimilar thickness aluminum tailor-welded blanks, which provided validation of the numerical and experimental analysis of laboratory scale tests.

  12. Enabling high speed friction stir welding of aluminum tailor welded blanks

    NASA Astrophysics Data System (ADS)

    Hovanski, Yuri

    Current welding technologies for production of aluminum tailor-welded blanks (TWBs) are utilized in low-volume and niche applications, and have yet to be scaled for the high-volume vehicle market. This study targeted further weight reduction, part reduction, and cost savings by enabling tailor-welded blank technology for aluminum alloys at high-volumes. While friction stir welding (FSW) has traditionally been applied at linear velocities less than one meter per minute, high volume production applications demand the process be extended to higher velocities more amenable to cost sensitive production environments. Unfortunately, weld parameters and performance developed and characterized at low to moderate welding velocities do not directly translate to high speed linear friction stir welding. Therefore, in order to facilitate production of high volume aluminum FSW components, parameters were developed with a minimum welding velocity of three meters per minute. With an emphasis on weld quality, welded blanks were evaluated for post-weld formability using a combination of numerical and experimental methods. Evaluation across scales was ultimately validated by stamping full-size production door inner panels made from dissimilar thickness aluminum tailor-welded blanks, which provided validation of the numerical and experimental analysis of laboratory scale tests.

  13. High-Speed Friction-Stir Welding to Enable Aluminum Tailor-Welded Blanks

    NASA Astrophysics Data System (ADS)

    Hovanski, Yuri; Upadhyay, Piyush; Carsley, John; Luzanski, Tom; Carlson, Blair; Eisenmenger, Mark; Soulami, Ayoub; Marshall, Dustin; Landino, Brandon; Hartfield-Wunsch, Susan

    2015-05-01

    Current welding technologies for production of aluminum tailor-welded blanks (TWBs) are utilized in low-volume and niche applications, and they have yet to be scaled for the high-volume vehicle market. This study targeted further weight reduction, part reduction, and cost savings by enabling tailor-welded blank technology for aluminum alloys at high volumes. While friction-stir welding (FSW) has been traditionally applied at linear velocities less than 1 m/min, high-volume production applications demand the process be extended to higher velocities more amenable to cost-sensitive production environments. Unfortunately, weld parameters and performance developed and characterized at low-to-moderate welding velocities do not directly translate to high-speed linear FSW. Therefore, to facilitate production of high-volume aluminum FSW components, parameters were developed with a minimum welding velocity of 3 m/min. With an emphasis on weld quality, welded blanks were evaluated for postweld formability using a combination of numerical and experimental methods. An evaluation across scales was ultimately validated by stamping full-size production door inner panels made from dissimilar thickness aluminum TWBs, which provided validation of the numerical and experimental analysis of laboratory-scale tests.

  14. Stress management as an enabling technology for high-field superconducting dipole magnets

    NASA Astrophysics Data System (ADS)

    Holik, Eddie Frank, III

    This dissertation examines stress management and other construction techniques as means to meet future accelerator requirement demands by planning, fabricating, and analyzing a high-field, Nb3Sn dipole. In order to enable future fundamental research and discovery in high energy accelerator physics, bending magnets must access the highest fields possible. Stress management is a novel, propitious path to attain higher fields and preserve the maximum current capacity of advanced superconductors by managing the Lorentz stress so that strain induced current degradation is mitigated. Stress management is accomplished through several innovative design features. A block-coil geometry enables an Inconel pier and beam matrix to be incorporated in the windings for Lorentz Stress support and reduced AC loss. A laminar spring between windings and mica paper surrounding each winding inhibit any stress transferral through the support structure and has been simulated with ALGORRTM. Wood's metal filled, stainless steel bladders apply isostatic, surface-conforming preload to the pier and beam support structure. Sufficient preload along with mica paper sheer release reduces magnet training by inhibiting stick-slip motion. The effectiveness of stress management is tested with high-precision capacitive stress transducers and strain gauges. In addition to stress management, there are several technologies developed to assist in the successful construction of a high-field dipole. Quench protection has been designed and simulated along with full 3D magnetic simulation with OPERARTM. Rutherford cable was constructed, and cable thermal expansion data was analysed after heat treatment. Pre-impregnation analysis techniques were developed due to elemental tin leakage in varying quantities during heat treatment from each coil. Robust splicing techniques were developed with measured resistivites consistent with nO joints. Stress management has not been incorporated by any other high field dipole

  15. Cross-linking of epidermal growth factor receptors in intact cells: detection of initial stages of receptor clustering and determination of molecular weight of high-affinity receptors

    SciTech Connect

    Fanger, B.O.; Austin, K.S.; Earp, H.S.; Cidlowski, J.A.

    1986-10-21

    A method was developed to label epidermal growth factor (EGF) receptors with /sup 125/I-EGF in whole cells using chemical cross-linking reagents. Polyacrylamide gel electrophoresis resolved an M/sub r/ approx. 180,000 EGF-receptor complex and larger M/sub r/ greater than or equal to 360,000 aggregates. The formation of the larger complexes was timed and temperature dependent and appeared to represent the initial events of EGF receptor clustering. Alteration of the ratio of /sup 125/I-EGF-labeled high- and low- affinity complexes by competition with unlabeled EGF or by induction of additional high-affinity sites with dexamethasone suggested that both sites were represented by the M/sub r/ approx. 180,000 /sup 125/I-EGF-receptor complexes. Digestion of cells before cross-linking detected a small population of trypsin-resistant M/sub r/ approx. 180,000 receptors, which could represent previously described cryptic and/or high-affinity receptors. Few of the M/sub r/ approx. 360,000 receptors were trypsin resistant. Glucocorticoid induction of high-affinity EGF receptors failed to induce detectable changes in the microclustering of EGF receptors but did result in a 50% increase in EGF-induced receptor phosphorylation in HeLa S/sub 3/ cell membranes at 4/sup 0/C. Thus, glucocorticoids increase high-affinity EGF binding sites, EGF-induced receptor phosphorylation, and cell growth.

  16. Size and thickness effect on creep behavior in conventional and vitamin E-diffused highly crosslinked polyethylene for total hip arthroplasty.

    PubMed

    Takahashi, Yasuhito; Tateiwa, Toshiyuki; Shishido, Takaaki; Masaoka, Toshinori; Kubo, Kosuke; Yamamoto, Kengo

    2016-09-01

    Since the early 2000s, the use of large femoral heads is becoming increasingly popular in total hip arthroplasty (THA), which provides an improved range of motion and joint stability. Large femoral heads commonly necessitate to be coupled with thinner acetabular liners than the conventionally used because of the limited sizes of outer shells (especially for patients with small pelvic size). However, the influence of the liner thinning on the mechanical performance is still not clearly understood. The objective of this study was to experimentally clarify the size and thickness effect on the rates of compressive creep strain in conventional (virgin low-crosslinked) and vitamin E-diffused highly crosslinked, ultra-high molecular weight polyethylene (UHMWPE) acetabular liners. We applied uniaxial compression to these liners of various internal diameters (28, 32 and 36mm) and thicknesses (4.8, 6.8 and 8.9mm) up to 4320min under the constant load of 3000N. Vitamin E-diffused highly crosslinked UHMWPE components showed significantly greater creep resistance than the conventional ones. In the both types of UHMWPE, the rates of creep strain significantly decreased by increasing the internal diameter and thickness. Varying the component thickness contributed more largely to the creep behavior rather than the internal diameter. Our results suggest the positive mechanical advantage of using large femoral heads, but at the same time, a considerable liner thinning is not recommended for minimizing creep strain. Therefore, the further in-vitro as well as in-vivo research are necessary to conclude the optimal balance of head diameter and liner thickness within the limited sizes of outer shells. PMID:27261923

  17. High Performance Ultrathin GaAs Solar Cells Enabled with Heterogeneously Integrated Dielectric Periodic Nanostructures.

    PubMed

    Lee, Sung-Min; Kwong, Anthony; Jung, Daehwan; Faucher, Joseph; Biswas, Roshni; Shen, Lang; Kang, Dongseok; Lee, Minjoo Larry; Yoon, Jongseung

    2015-10-27

    Due to their favorable materials properties including direct bandgap and high electron mobilities, epitaxially grown III-V compound semiconductors such as gallium arsenide (GaAs) provide unmatched performance over silicon in solar energy harvesting. Nonetheless, their large-scale deployment in terrestrial photovoltaics remains challenging mainly due to the high cost of growing device quality epitaxial materials. In this regard, reducing the thickness of constituent active materials under appropriate light management schemes is a conceptually viable option to lower the cost of GaAs solar cells. Here, we present a type of high efficiency, ultrathin GaAs solar cell that incorporates bifacial photon management enabled by techniques of transfer printing to maximize the absorption and photovoltaic performance without compromising the optimized electronic configuration of planar devices. Nanoimprint lithography and dry etching of titanium dioxide (TiO2) deposited directly on the window layer of GaAs solar cells formed hexagonal arrays of nanoscale posts that serve as lossless photonic nanostructures for antireflection, diffraction, and light trapping in conjunction with a co-integrated rear-surface reflector. Systematic studies on optical and electrical properties and photovoltaic performance in experiments, as well as numerical modeling, quantitatively describe the optimal design rules for ultrathin, nanostructured GaAs solar cells and their integrated modules.

  18. Enabling Astronomy in the Extremes: Developing the Antarctic High Plateau for Science

    NASA Astrophysics Data System (ADS)

    Burton, Michael

    2015-08-01

    The high plateau of Antarctica provides the driest, coldest and most stable environment on the Earth's surface, facets that facilitate astronomical observations. New windows are opened in the atmosphere in the terahertz bands, low sky backgrounds improve sensitivities across the infrared bands, and the stability enables precision photometry. Of course, the Antarctic high plateau is a challenging environment for humans to work in, logistics is difficult and access only possible for limited periods of the year. Operation is akin to space, albeit at less cost, using robotic facilities installed and serviced over the summer months.This talk will discuss astronomical developments on the Antarctic high plateau, in particular at its highest location, Dome A and the nearby Ridge A. At the former China is building the Kunlun Observatory, with mid-scale facilities for IR and THz astronomy planned. Currently a series of pathfinder optical / IR telescopes are in operation and being developed (the three 50cm AST telescopes). At Ridge A, the 60cm HEAT telescope is in operation, surveying the Galactic plane at 0.5 and 0.8 THz.

  19. Modulation of orthogonal body waves enables high maneuverability in sidewinding locomotion

    NASA Astrophysics Data System (ADS)

    Astley, Henry; Gong, Chaohui; Travers, Matt; Serrano, Miguel; Vela, Patricio; Choset, Howie; Mendelson, Joseph, III; Hu, David; Goldman, Daniel

    2015-03-01

    To simplify control of high degree of freedom bodies, organisms may target a set of simple shape changes (a ``template''). Recent work has revealed that the locomotion of sidewinder rattlesnakes can be described by a combination of horizontal and vertical body waves with a phase difference of +/- π/2, representing a possible control template. These animals display high maneuverability which we hypothesize emerges from their ability to independently modulate these waves. Snakes used two distinct turning methods which we term differential turning (24° turn per cycle) and reversal turning (80°). Kinematic data suggested that during differential turning the animals imposed an amplitude modulation in the horizontal wave while in reversal turning they shifted the phase of the vertical wave by π. We tested these mechanisms in the robot, generating differential and reversal turning. Further manipulations of the two-wave system revealed a third turning mode, ``frequency turning,'' not observed in biological snakes which allowed the robot to execute large (127°) in-place turns. The two-wave system enables unprecedented maneuverability of high degree-of-freedom systems, revealing a practical benefits of the search for control templates. Zoo Atlanta

  20. Cross-linked biopolymer bundles: Cross-link reversibility leads to cooperative binding/unbinding phenomena

    NASA Astrophysics Data System (ADS)

    Vink, Richard L. C.; Heussinger, Claus

    2012-01-01

    We consider a biopolymer bundle consisting of filaments that are cross-linked together. The cross-links are reversible: they can dynamically bind and unbind adjacent filament pairs as controlled by a binding enthalpy. The bundle is subjected to a bending deformation and the corresponding distribution of cross-links is measured. For a bundle consisting of two filaments, upon increasing the bending amplitude, a first-order transition is observed. The transition is from a state where the filaments are tightly coupled by many bound cross-links, to a state of nearly independent filaments with only a few bound cross-links. For a bundle consisting of more than two filaments, a series of first-order transitions is observed. The transitions are connected with the formation of an interface between regions of low and high cross-link densities. Combining umbrella sampling Monte Carlo simulations with analytical calculations, we present a detailed picture of how the competition between cross-link shearing and filament stretching drives the transitions. We also find that, when the cross-links become soft, collective behavior is not observed: the cross-links then unbind one after the other leading to a smooth decrease of the average cross-link density.

  1. Highly efficient copper(II) ion sorbents obtained by calcium carbonate mineralization on functionalized cross-linked copolymers.

    PubMed

    Mihai, Marcela; Bunia, Ion; Doroftei, Florica; Varganici, Cristian-Dragos; Simionescu, Bogdan C

    2015-03-23

    A new type of Cu(II) ion sorbents is presented. These are obtained by CaCO3 mineralization from supersaturated solutions on gel-like cross-linked polymeric beads as insoluble templates. A divinylbenzene-ethylacrylate-acrylonitrile cross-linked copolymer functionalized with weakly acidic, basic, or amphoteric functional groups has been used, as well as different initial inorganic concentrations and addition procedures for CaCO3 crystal growth. The morphology of the new composites was investigated by SEM and compared to that of the unmodified beads, and the polymorph content was established by X-ray diffraction. The beads, before and after CaCO3 mineralization, were tested as sorbents for Cu(II) ions. The newly formed patterns on the bead surface after Cu(II) sorption were observed by SEM, and the elemental distribution on the composites and the chemical structure of crystals after interaction with Cu(II) were investigated by EDAX elemental mapping and by FTIR-ATR spectroscopy, respectively. The sorption capacity increased significantly after CaCO3 crystals growth on the weak anionic bead surface (up to 1041.5 mg Cu(II) /g sample) compared to that of unmodified beads (491.5 mg Cu(II) /g sample). PMID:25675892

  2. Optimisation of the reaction conditions for the production of cross-linked starch with high resistant starch content.

    PubMed

    Kahraman, Kevser; Koksel, Hamit; Ng, Perry K W

    2015-05-01

    The optimum reaction conditions (temperature and pH) for the preparation of cross-linked (CL) corn and wheat starches with maximum resistant starch (RS) content were investigated by using response surface methodology (RSM). According to the preliminary results, five levels were selected for reaction temperature (38-70 °C) and pH (10-12) in the main study. RS contents of the CL corn and wheat starch samples increased with increasing temperature and pH, and pH had a greater influence on RS content than had temperature. The maximum RS content (with a maximum p value of 0.4%) was obtained in wheat starch cross-linked at 38 °C and pH 12. In the case of CL corn starch, the optimum condition was 70 °C and pH 12. CL corn and wheat starch samples were also produced separately under the optimum conditions and their RS contents were 80.4% and 83.9%, respectively. These results were also in agreement with the values predicted by RSM.

  3. The Centre of High-Performance Scientific Computing, Geoverbund, ABC/J - Geosciences enabled by HPSC

    NASA Astrophysics Data System (ADS)

    Kollet, Stefan; Görgen, Klaus; Vereecken, Harry; Gasper, Fabian; Hendricks-Franssen, Harrie-Jan; Keune, Jessica; Kulkarni, Ketan; Kurtz, Wolfgang; Sharples, Wendy; Shrestha, Prabhakar; Simmer, Clemens; Sulis, Mauro; Vanderborght, Jan

    2016-04-01

    The Centre of High-Performance Scientific Computing (HPSC TerrSys) was founded 2011 to establish a centre of competence in high-performance scientific computing in terrestrial systems and the geosciences enabling fundamental and applied geoscientific research in the Geoverbund ABC/J (geoscientfic research alliance of the Universities of Aachen, Cologne, Bonn and the Research Centre Jülich, Germany). The specific goals of HPSC TerrSys are to achieve relevance at the national and international level in (i) the development and application of HPSC technologies in the geoscientific community; (ii) student education; (iii) HPSC services and support also to the wider geoscientific community; and in (iv) the industry and public sectors via e.g., useful applications and data products. A key feature of HPSC TerrSys is the Simulation Laboratory Terrestrial Systems, which is located at the Jülich Supercomputing Centre (JSC) and provides extensive capabilities with respect to porting, profiling, tuning and performance monitoring of geoscientific software in JSC's supercomputing environment. We will present a summary of success stories of HPSC applications including integrated terrestrial model development, parallel profiling and its application from watersheds to the continent; massively parallel data assimilation using physics-based models and ensemble methods; quasi-operational terrestrial water and energy monitoring; and convection permitting climate simulations over Europe. The success stories stress the need for a formalized education of students in the application of HPSC technologies in future.

  4. Exceptionally large entropy contributions enable the high rates of GTP hydrolysis on the ribosome

    PubMed Central

    Åqvist, Johan; Kamerlin, Shina C.L.

    2015-01-01

    Protein synthesis on the ribosome involves hydrolysis of GTP in several key steps of the mRNA translation cycle. These steps are catalyzed by the translational GTPases of which elongation factor Tu (EF-Tu) is the fastest GTPase known. Here, we use extensive computer simulations to explore the origin of its remarkably high catalytic rate on the ribosome and show that it is made possible by a very large positive activation entropy. This entropy term (TΔS‡) amounts to more than 7 kcal/mol at 25 °C. It is further found to be characteristic of the reaction mechanism utilized by the translational, but not other, GTPases and it enables these enzymes to attain hydrolysis rates exceeding 500 s−1. This entropy driven mechanism likely reflects the very high selection pressure on the speed of protein synthesis, which drives the rate of each individual GTPase towards maximal turnover rate of the whole translation cycle. PMID:26497916

  5. Grid-Enabled High Energy Physics Research using a Beowulf Cluster

    NASA Astrophysics Data System (ADS)

    Mahmood, Akhtar

    2005-04-01

    At Edinboro University of Pennsylvania, we have built a 8-node 25 Gflops Beowulf Cluster with 2.5 TB of disk storage space to carry out grid-enabled, data-intensive high energy physics research for the ATLAS experiment via Grid3. We will describe how we built and configured our Cluster, which we have named the Sphinx Beowulf Cluster. We will describe the results of our cluster benchmark studies and the run-time plots of several parallel application codes. Once fully functional, the Cluster will be part of Grid3[www.ivdgl.org/grid3]. The current ATLAS simulation grid application, models the entire physical processes from the proton anti-proton collisions and detector's response to the collision debri through the complete reconstruction of the event from analyses of these responses. The end result is a detailed set of data that simulates the real physical collision event inside a particle detector. Grid is the new IT infrastructure for the 21^st century science -- a new computing paradigm that is poised to transform the practice of large-scale data-intensive research in science and engineering. The Grid will allow scientist worldwide to view and analyze huge amounts of data flowing from the large-scale experiments in High Energy Physics. The Grid is expected to bring together geographically and organizationally dispersed computational resources, such as CPUs, storage systems, communication systems, and data sources.

  6. Internet-enabled high-resolution brain mapping and virtual microscopy.

    PubMed

    Mikula, Shawn; Trotts, Issac; Stone, James M; Jones, Edward G

    2007-03-01

    Virtual microscopy involves the conversion of histological sections mounted on glass microscope slides to high-resolution digital images. Virtual microscopy offers several advantages over traditional microscopy, including remote viewing and data sharing, annotation, and various forms of data mining. We describe a method utilizing virtual microscopy for generation of internet-enabled, high-resolution brain maps and atlases. Virtual microscopy-based digital brain atlases have resolutions approaching 100,000 dpi, which exceeds by three or more orders of magnitude resolutions obtainable in conventional print atlases, MRI, and flat-bed scanning. Virtual microscopy-based digital brain atlases are superior to conventional print atlases in five respects: (1) resolution, (2) annotation, (3) interaction, (4) data integration, and (5) data mining. Implementation of virtual microscopy-based digital brain atlases is located at BrainMaps.org, which is based on more than 10 million megapixels (35 terabytes) of scanned images of serial sections of primate and non-primate brains with a resolution of 0.46 microm/pixel (55,000 dpi). The method can be replicated by labs seeking to increase accessibility and sharing of neuroanatomical data. Online tools offer the possibility of visualizing and exploring completely digitized sections of brains at a sub-neuronal level and can facilitate large-scale connectional tracing, histochemical, and stereological analyses. PMID:17229579

  7. A comparison of sugar indicators enables a universal high-throughput sugar-1-phosphate nucleotidyltransferase assay

    PubMed Central

    Moretti, Rocco; Thorson, Jon S.

    2008-01-01

    A systematic comparison of six sugar indicators for their sensitivity, specificity, cross reactivity and suitability in the context of crude lysates revealed para-hydroxybenzoic acid hydrazide (pHBH) to be best suited for application in a plate-based phosphatase-assisted universal sugar-1-phosphate nucleotidyltransferase assay. The addition of a general phosphatase to nucleotidyltransferase reaction aliquots enabled the conversion of remaining sugar-1-phosphate to free sugar, the concentration of which could be rapidly assessed via the pHBH assay. The assay was validated using the model glucose-1-phosphate thymidylyltransferase from Salmonella enterica (RmlA) and compared favorably to a previously reported HPLC assay. This coupled discontinuous assay is quantitative, high-throughput and robust; relies only on commercially available enzymes and reagents; does not require chromatography, specialized detectors (e.g. mass or evaporative light scattering detectors) or radioisotopes; and is capable of detecting less than 5 nmol of sugar-1-phosphate. It is anticipated this high throughput assay system will greatly facilitate nucleotidyltransferase mechanistic and directed evolution/engineering studies. PMID:18387352

  8. Exceptionally large entropy contributions enable the high rates of GTP hydrolysis on the ribosome.

    PubMed

    Åqvist, Johan; Kamerlin, Shina C L

    2015-10-26

    Protein synthesis on the ribosome involves hydrolysis of GTP in several key steps of the mRNA translation cycle. These steps are catalyzed by the translational GTPases of which elongation factor Tu (EF-Tu) is the fastest GTPase known. Here, we use extensive computer simulations to explore the origin of its remarkably high catalytic rate on the ribosome and show that it is made possible by a very large positive activation entropy. This entropy term (TΔS(‡)) amounts to more than 7 kcal/mol at 25 °C. It is further found to be characteristic of the reaction mechanism utilized by the translational, but not other, GTPases and it enables these enzymes to attain hydrolysis rates exceeding 500 s(-1). This entropy driven mechanism likely reflects the very high selection pressure on the speed of protein synthesis, which drives the rate of each individual GTPase towards maximal turnover rate of the whole translation cycle.

  9. Surface preparation for high purity alumina ceramics enabling direct brazing in hydrogen atmospheres

    DOEpatents

    Cadden, Charles H.; Yang, Nancy Yuan Chi; Hosking, Floyd M.

    2001-01-01

    The present invention relates to a method for preparing the surface of a high purity alumina ceramic or sapphire specimen that enables direct brazing in a hydrogen atmosphere using an active braze alloy. The present invention also relates to a method for directly brazing a high purity alumina ceramic or sapphire specimen to a ceramic or metal member using this method of surface preparation, and to articles produced by this brazing method. The presence of silicon, in the form of a SiO.sub.2 -containing surface layer, can more than double the tensile bond strength in alumina ceramic joints brazed in a hydrogen atmosphere using an active Au-16Ni-0.75 Mo-1.75V filler metal. A thin silicon coating applied by PVD processing can, after air firing, produce a semi-continuous coverage of the alumina surface with a SiO.sub.2 film. Room temperature tensile strength was found to be proportional to the fraction of air fired surface covered by silicon-containing films. Similarly, the ratio of substrate fracture versus interface separation was also related to the amount of surface silicon present prior to brazing. This process can replace the need to perform a "moly-manganese" metallization step.

  10. Soil-frost-enabled soil-moisture-precipitation feedback over northern high latitudes

    NASA Astrophysics Data System (ADS)

    Hagemann, Stefan; Blome, Tanja; Ekici, Altug; Beer, Christian

    2016-07-01

    Permafrost or perennially frozen ground is an important part of the terrestrial cryosphere; roughly one quarter of Earth's land surface is underlain by permafrost. The currently observed global warming is most pronounced in the Arctic region and is projected to persist during the coming decades due to anthropogenic CO2 input. This warming will certainly have effects on the ecosystems of the vast permafrost areas of the high northern latitudes. The quantification of such effects, however, is still an open question. This is partly due to the complexity of the system, including several feedback mechanisms between land and atmosphere. In this study we contribute to increasing our understanding of such land-atmosphere interactions using an Earth system model (ESM) which includes a representation of cold-region physical soil processes, especially the effects of freezing and thawing of soil water on thermal and hydrological states and processes. The coupled atmosphere-land models of the ESM of the Max Planck Institute for Meteorology, MPI-ESM, have been driven by prescribed observed SST and sea ice in an AMIP2-type setup with and without newly implemented cold-region soil processes. Results show a large improvement in the simulated discharge. On the one hand this is related to an improved snowmelt peak of runoff due to frozen soil in spring. On the other hand a subsequent reduction in soil moisture enables a positive feedback to precipitation over the high latitudes, which reduces the model's wet biases in precipitation and evapotranspiration during the summer. This is noteworthy as soil-moisture-atmosphere feedbacks have previously not been the focus of research on the high latitudes. These results point out the importance of high-latitude physical processes at the land surface for regional climate.

  11. Magnetically-Separable and Highly-Stable Enzyme System Based on Crosslinked Enzyme Aggregates Shipped in Magnetite-Coated Mesoporous Silica

    SciTech Connect

    Lee, Jinwoo; Na, Hyon Bin; Kim, Byoung Chan; Lee, Jin Hyung; Lee, Byoungsoo; Kwak, Ja Hun; Hwang, Yosun; Park, Je-Geun; Gu, Man Bock; Kim, Jaeyun; Joo, Jin; Shin, Chae-Ho; Grate, Jay W.; Hyeon, Taeghwan; Kim, Jungbae

    2009-10-15

    Magnetically-separable and highly-stable enzyme system was developed by adsorption of enzymes in superparamagnetic hierarchically ordered mesocellular mesoporous silica (M-HMMS) and subsequent enzyme crosslinking. Superparamagnetic nanoparticles were homogeneously incorporated into hierarchically-ordered mesocellular mesoporous silica (HMMS) by the decomposition of preformed iron propionate complex. The size of incorporated superparamagnetic 15 nanoparticles was around 5 nm, generating a magnetically separable host with high pore volumes and large pores (M-HMMS). α-chymotrypsin (CT) was adsorbed into M-HMMS with high loading (~30 wt%) in less than 30 minutes. Glutaraldehyde (GA) treatment of adsorbed CT resulted in nanometer scale crosslinked enzyme aggregates in M-HMMS (CLEA-M). The activity of these CT aggregates in M-HMMS (CLEA-M-CT) was 34 times than that of simply adsorbed CT in M20 HMMS, due to an effective prevention of enzyme leaching during washing via a ship-in-a-bottle approach. CLEA-M-CT maintained the intial activity not only under shaking (250 rpm) for 30 days, but also under recycled uses of 35 times. The same approach was employed for the synthesis of CLEA-M of lipase (CLEA-M-LP), and proven to be effective in improving the loading, activity, and stability of enzyme when compared to those of adsorbed LP in M-HMMS.

  12. Reduced-mode (REM) diodes enable high brightness fiber-coupled modules

    NASA Astrophysics Data System (ADS)

    Kanskar, M.; Bao, L.; Chen, Z.; Dawson, D.; DeVito, M.; Dong, W.; Grimshaw, M.; Guan, X.; Hemenway, M.; Kennedy, K.; Martinsen, R.; Urbanek, W.; Zhang, S.

    2016-03-01

    There is an increasing demand for high-power, high-brightness diode lasers from 8xx nm to 9xx nm for applications such as fiber laser pumping, materials processing, solid-state laser pumping, and consumer electronics manufacturing. The kilowatt CW fiber laser pumping (915 nm - 976 nm), in particular, requires the diode lasers to have both high power and high brightness in order to achieve high-performance and reduced manufacturing costs. This paper presents continued progress in the development of high brightness fiber-coupled product platform, elementTM. Further brightness improvement and power-scaling have been enabled by both the rise in chip brightness as well as the increase in number of chips used to couple into a given numerical aperture. We have developed a new generation of high power broad area laser known as reduced-mode diode (REM-diode) which suppresses many of the higher order modes in the slow axis and reduces divergence up to two times at the same operating conditions. To date, we have achieved slow-axis brightness as high as 4.3 W/mm-mrad for devices with thermal resistance of ~2.5 C/W. As a result, we have achieved >75 watts from a 1×6 elementTMin the 9xx nm spectral range; and 177 watts of peak power from a 2×6 elementTM. We have also improved our optics for fiber-coupling which accommodates 7 emitters per polarization in the same numerical aperture. Using this configuration, we project 200 watts of peak power from a 2×7 elementTM with a reliable product at 176 W of power from 105 μm and 0.15 NA fiber. REM-diodes can also be wavelength stabilized using VBGs. The reliability of REM-diodes are equal or better than broad area lasers (BALs). We present current status on ongoing reliability assessment of chip-on-submount.

  13. Materials-Enabled High-Efficiency (MEHE) Heavy-Duty Diesel Engines

    SciTech Connect

    Kass, M.; Veliz, M.

    2011-09-30

    The purpose of this Cooperative Research and Development Agreement (CRADA) between UTBattelle, Inc. and Caterpillar, Inc. was to improve diesel engine efficiency by incorporating advanced materials to enable higher combustion pressures and temperatures necessary for improved combustion. The project scope also included novel materials for use in advanced components and designs associated with waste-heat recovery and other concepts for improved thermal efficiency. Caterpillar initially provided ORNL with a 2004 Tier 2 C15 ACERT diesel engine (designed for on-highway use) and two 600 hp motoring dynamometers. The first year of the CRADA effort was focused on establishing a heavy-duty experimental engine research cell. First year activities included procuring, installing and commissioning the cell infrastructure. Infrastructure components consisted of intake air handling system, water tower, exhaust handling system, and cell air conditioning. Other necessary infrastructure items included the fuel delivery system and bottled gas handling to support the analytical instrumentation. The second year of the CRADA focused on commissioning the dynamometer system to enable engine experimentation. In addition to the requirements associated with the dynamometer controller, the electrical system needed a power factor correction system to maintain continuity with the electrical grid. During the second year the engine was instrumented and baseline operated to confirm performance and commission the dynamometer. The engine performance was mapped and modeled according to requirements provided by Caterpillar. This activity was further supported by a Work-for-Others project from Caterpillar to evaluate a proprietary modeling system. A second Work-for-Others activity was performed to evaluate a novel turbocharger design. This project was highly successful and may lead to new turbocharger designs for Caterpillar heavy-duty diesel engines. During the third (and final) year of the CRADA, a

  14. Biodegradable, hydrophobic coatings based on crosslinked polycaprolactone

    SciTech Connect

    Koenig, M.F.

    1993-12-31

    Crosslinked poly(caprolactone) (PCL) has been explored as a hydrophobic and biodegradable coating for hydrophilic substrates. Crosslinking of PCL is known to retard its degradation rate, but does not affect its biodegradability. The cross-linking efficiencies of several organic peroxides have been determined for PCL. This has been accomplished by calculating the crosslink density (M{sub c} from dynamic mechanical data) for a given molar concentration of organic peroxide. Various thicknesses of crosslinked PCL have been coated on several different hydrophilic substrates, including paper, MaterBi (regsign), and PCL/starch composites. The hydrophobicity of the coating has been measured by following the weight gain of the coated samples upon exposure to water and a high relative humidity for various lengths of time. Results show that a coating as thin as 10 {mu}m reduces water absorption of paper by a factor of five, and thicker coatings (0.25 mm) by more than two orders of magnitude.

  15. Wear and migration of highly cross-linked and conventional cemented polyethylene cups with cobalt chrome or Oxinium femoral heads: a randomized radiostereometric study of 150 patients.

    PubMed

    Kadar, Thomas; Hallan, Geir; Aamodt, Arild; Indrekvam, Kari; Badawy, Mona; Skredderstuen, Arne; Havelin, Leif Ivar; Stokke, Terje; Haugan, Kristin; Espehaug, Birgitte; Furnes, Ove

    2011-08-01

    This randomized study was performed to compare wear and migration of five different cemented total hip joint articulations in 150 patients. The patients received either a Charnley femoral stem with a 22.2 mm head or a Spectron EF femoral stem with a 28 mm head. The Charnley articulated with a γ-sterilized Charnley Ogee acetabular cup. The Spectron EF was used with either EtO-sterilized non-cross-linked polyethylene (Reflection All-Poly) or highly cross-linked (Reflection All-Poly XLPE) cups, combined with either cobalt chrome (CoCr) or Oxinium femoral heads. The patients were followed with repeated RSA measurements for 2 years. After 2 years, the EtO-sterilized non-cross-linked Reflection All-Poly cups had more than four times higher proximal penetration than its highly cross-linked counterpart. Use of Oxinium femoral heads did not affect penetration at 2 years compared to heads made of CoCr. Further follow-up is needed to evaluate the benefits, if any, of Oxinium femoral heads in the clinical setting. The Charnley Ogee was not outperformed by the more recently introduced implants in our study. We conclude that this prostheses still represents a standard against which new implants can be measured.

  16. Catalytic trimerization of aromatic nitriles and triaryl-s-triazine ring cross-linked high temperature resistant polymers and copolymers made thereby

    NASA Technical Reports Server (NTRS)

    Hsu, L. C. (Inventor)

    1979-01-01

    Triazine compounds and cross-linked polymer compositions are made by heating aromatic nitriles to a temperature in the range of from about 100 C to about 700 C, and preferably in the range of from about 200 C to about 350 C, in the presence of a catalyst or mixture of catalysts selected from one or more of the following groups: (1) organic sulfonic and sulfinic acids, (2) organic phosphonic and phosphinic acids, and (3)metallic acetylacetonates, at a pressure in the range of from about atmospheric pressure to about 10,000 psi and preferably in the range of from about 200 psi to about 750 psi. Aromatic nitrile-modified (terminated and/or appended) imide, benzimidazole, imidazopyrrolone, quinoxaline, and other condensation type prepolymers or their precopolymers are made which are trimerized with or without a filler by the aforementioned catalytic trimerization process into triaryl-s-triazine ring containing or cross-linked polymeric or copolymeric products useful in applications requiring high thermal-oxidative stability and high performance structural properties at elevated temperatures.

  17. Initiated Chemical Vapor Deposition (iCVD) of Highly Cross-Linked Polymer Films for Advanced Lithium-Ion Battery Separators.

    PubMed

    Yoo, Youngmin; Kim, Byung Gon; Pak, Kwanyong; Han, Sung Jae; Song, Heon-Sik; Choi, Jang Wook; Im, Sung Gap

    2015-08-26

    We report an initiated chemical vapor deposition (iCVD) process to coat polyethylene (PE) separators in Li-ion batteries with a highly cross-linked, mechanically strong polymer, namely, polyhexavinyldisiloxane (pHVDS). The highly cross-linked but ultrathin pHVDS films can only be obtained by a vapor-phase process, because the pHVDS is insoluble in most solvents and thus infeasible with conventional solution-based methods. Moreover, even after the pHVDS coating, the initial porous structure of the separator is well preserved owing to the conformal vapor-phase deposition. The coating thickness is delicately controlled by deposition time to the level that the pore size decreases to below 7% compared to the original dimension. The pHVDS-coated PE shows substantially improved thermal stability and electrolyte wettability. After incubation at 140 °C for 30 min, the pHVDS-coated PE causes only a 12% areal shrinkage (versus 90% of the pristine separator). The superior wettability results in increased electrolyte uptake and ionic conductivity, leading to significantly improved rate performance. The current approach is applicable to a wide range of porous polymeric separators that suffer from thermal shrinkage and poor electrolyte wetting.

  18. High-k Dielectric Passivation: Novel Considerations Enabling Cell Specific Lysis Induced by Electric Fields.

    PubMed

    Wassermann, Klemens J; Barth, Sven; Keplinger, Franz; Noehammer, Christa; Peham, Johannes R

    2016-08-24

    A better understanding of the electrodynamic behavior of cells interacting with electric fields would allow for novel scientific insights and would lead to the next generation of cell manipulation, diagnostics, and treatment. Here, we introduce a promising electrode design by using metal oxide high-k dielectric passivation. The thermally generated dielectric passivation layer enables efficient electric field coupling to the fluid sample comprising cells while simultaneously decoupling the electrode ohmically from the electrolyte, allowing for better control and adjustability of electric field effects due to reduced electrochemical reactions at the electrode surface. This approach demonstrates cell-size specific lysis with electric fields in a microfluidic flow-through design resulting in 99.8% blood cell lysis at 6 s exposure without affecting the viability of Gram-positive and Gram-negative bacterial spike-ins. The advantages of this new approach can support next-generation investigations of electrodynamics in biological systems and their exploitation for cell manipulation in multiple fields of medicine, life science, and industry. PMID:27466697

  19. Co-incident insertion enables high efficiency genome engineering in mouse embryonic stem cells

    PubMed Central

    Shy, Brian R.; MacDougall, Matthew S.; Clarke, Ryan; Merrill, Bradley J.

    2016-01-01

    CRISPR/Cas9 nucleases have enabled powerful, new genome editing capabilities; however, the preponderance of non-homologous end joining (NHEJ) mediated repair events over homology directed repair (HDR) in most cell types limits the ability to engineer precise changes in mammalian genomes. Here, we increase the efficiency of isolating precise HDR-mediated events in mouse embryonic stem (ES) cells by more than 20-fold through the use of co-incidental insertion (COIN) of independent donor DNA sequences. Analysis of on:off-target frequencies at the Lef1 gene revealed that bi-allelic insertion of a PGK-Neo cassette occurred more frequently than expected. Using various selection cassettes targeting multiple loci, we show that the insertion of a selectable marker at one control site frequently coincided with an insertion at an unlinked, independently targeted site, suggesting enrichment of a sub-population of HDR-proficient cells. When individual cell events were tracked using flow cytometry and fluorescent protein markers, individual cells frequently performed either a homology-dependent insertion event or a homology-independent event, but rarely both types of insertions in a single cell. Thus, when HDR-dependent selection donors are used, COIN enriches for HDR-proficient cells among heterogeneous cell populations. When combined with a self-excising selection cassette, COIN provides highly efficient and scarless genome editing. PMID:27484482

  20. Modified bases enable high-efficiency oligonucleotide-mediated allelic replacement via mismatch repair evasion.

    PubMed

    Wang, Harris H; Xu, George; Vonner, Ashley J; Church, George

    2011-09-01

    Genome engineering using single-stranded oligonucleotides is an efficient method for generating small chromosomal and episomal modifications in a variety of host organisms. The efficiency of this allelic replacement strategy is highly dependent on avoidance of the endogenous mismatch repair (MMR) machinery. However, global MMR inactivation generally results in significant accumulation of undesired background mutations. Here, we present a novel strategy using oligos containing chemically modified bases (2'-Fluoro-Uridine, 5-Methyl-deoxyCytidine, 2,6-Diaminopurine or Iso-deoxyGuanosine) in place of the standard T, C, A or G to avoid mismatch detection and repair, which we tested in Escherichia coli. This strategy increases transient allelic-replacement efficiencies by up to 20-fold, while maintaining a 100-fold lower background mutation level. We further show that the mismatched bases between the full length oligo and the chromosome are often not incorporated at the target site, probably due to nuclease activity at the 5' and 3' termini of the oligo. These results further elucidate the mechanism of oligo-mediated allelic replacement (OMAR) and enable improved methodologies for efficient, large-scale engineering of genomes.

  1. Highly sensitive microscale in vivo sensor enabled by electrophoretic assembly of nanoparticles for multiple biomarker detection.

    PubMed

    Malima, Asanterabi; Siavoshi, Salome; Musacchio, Tiziana; Upponi, Jaydev; Yilmaz, Cihan; Somu, Sivasubramanian; Hartner, William; Torchilin, Vladimir; Busnaina, Ahmed

    2012-11-21

    This paper describes a microscale in vivo sensor platform device for the simultaneous detection of multiple biomarkers. We designed the polymer-based biosensors incorporating multiple active isolated areas, as small as 70 μm × 70 μm, for antigen detection. The fabrication approach involved conventional micro- and nano-fabrication processes followed by site-specific electrophoretic directed assembly of antibody-functionalized nanoparticles. To ensure precise and large-scale manufacturing of these biosensors, we developed a semi-automated system for the attachment of the 250-μm biosensor to a 300-μm catheter probe. Our fabrication and post-processing procedures should enable large-scale production of such biosensor devices at lower manufacturing cost. The principle of detection with these biosensors involved a simple fluorescence-based enzyme-linked immunosorbent assay. These biosensors exhibit high selectivity (ability to selectively detect multiple biomarkers of different diseases), specificity (ability to target generic to specific disease biomarkers), rapid antigen uptake, and low detection limits (for carcinoembryonic antigen, 31.25 pg mL(-1); for nucleosomes, 62.5 pg mL(-1)), laying the foundation for potential early detection of various diseases. PMID:22983480

  2. ARTIFICIAL INCOHERENT SPECKLES ENABLE PRECISION ASTROMETRY AND PHOTOMETRY IN HIGH-CONTRAST IMAGING

    SciTech Connect

    Jovanovic, N.; Guyon, O.; Pathak, P.; Kudo, T.; Martinache, F.; Hagelberg, J.

    2015-11-10

    State-of-the-art coronagraphs employed on extreme adaptive optics enabled instruments are constantly improving the contrast detection limit for companions at ever-closer separations from the host star. In order to constrain their properties and, ultimately, compositions, it is important to precisely determine orbital parameters and contrasts with respect to the stars they orbit. This can be difficult in the post-coronagraphic image plane, as by definition the central star has been occulted by the coronagraph. We demonstrate the flexibility of utilizing the deformable mirror in the adaptive optics system of the Subaru Coronagraphic Extreme Adaptive Optics system to generate a field of speckles for the purposes of calibration. Speckles can be placed up to 22.5 λ/D from the star, with any position angle, brightness, and abundance required. Most importantly, we show that a fast modulation of the added speckle phase, between 0 and π, during a long science integration renders these speckles effectively incoherent with the underlying halo. We quantitatively show for the first time that this incoherence, in turn, increases the robustness and stability of the adaptive speckles, which will improve the precision of astrometric and photometric calibration procedures. This technique will be valuable for high-contrast imaging observations with imagers and integral field spectrographs alike.

  3. Designs and numerical calculations for echo-enabled harmonic generation at very high harmonics

    NASA Astrophysics Data System (ADS)

    Penn, G.; Reinsch, M.

    2011-09-01

    The echo-enabled harmonic generation (EEHG) scheme for driving an FEL using two seeded energy modulations at much longer wavelengths than the output wavelength is a promising concept for future seeded FELs. There are many competing requirements in the design of an EEHG beamline which need careful optimization. Furthermore, revised simulation tools and methods are necessary because of both the high harmonic numbers simulated and the complicated nature of the phase space manipulations which are intrinsic to the scheme. This paper explores the constraints on performance and the required tolerances for reaching wavelengths well below 1/100th of that of the seed lasers, and describes some of the methodology for designing such a beamline. Numerical tools, developed both for the GENESIS and GINGER FEL codes, are presented and used here for more accurate study of the scheme beyond a time-averaged model. In particular, the impact of the local structure in peak current and bunching, which is an inherent part of the EEHG scheme, is evaluated.

  4. Artificial Incoherent Speckles Enable Precision Astrometry and Photometry in High-contrast Imaging

    NASA Astrophysics Data System (ADS)

    Jovanovic, N.; Guyon, O.; Martinache, F.; Pathak, P.; Hagelberg, J.; Kudo, T.

    2015-11-01

    State-of-the-art coronagraphs employed on extreme adaptive optics enabled instruments are constantly improving the contrast detection limit for companions at ever-closer separations from the host star. In order to constrain their properties and, ultimately, compositions, it is important to precisely determine orbital parameters and contrasts with respect to the stars they orbit. This can be difficult in the post-coronagraphic image plane, as by definition the central star has been occulted by the coronagraph. We demonstrate the flexibility of utilizing the deformable mirror in the adaptive optics system of the Subaru Coronagraphic Extreme Adaptive Optics system to generate a field of speckles for the purposes of calibration. Speckles can be placed up to 22.5 λ/D from the star, with any position angle, brightness, and abundance required. Most importantly, we show that a fast modulation of the added speckle phase, between 0 and π, during a long science integration renders these speckles effectively incoherent with the underlying halo. We quantitatively show for the first time that this incoherence, in turn, increases the robustness and stability of the adaptive speckles, which will improve the precision of astrometric and photometric calibration procedures. This technique will be valuable for high-contrast imaging observations with imagers and integral field spectrographs alike.

  5. Accelerated ageing experiments with crosslinked and conventional ultra-high molecular weight polyethylene (UHMW-PE) stabilised with alpha-tocopherol for total joint arthroplasty.

    PubMed

    Wolf, C; Macho, C; Lederer, K

    2006-12-01

    Samples of untreated ultra-high molecular weight polyethylene (UHMW-PE), UHMW-PE sterilized with gamma-rays in nitrogen atmosphere (conventional UHMW-PE, widely used for articulating surfaces in endoprostheses) and UHMW-PE, which has been crosslinked by electron beam irradiation and annealed subsequently, were stabilized with alpha-tocopherol and aged in air at 120 degrees C as well as in 10% aqueous hydrogenperoxide with 0.04 mg/ml FeCl3 as catalyst at 50 degrees C. The oxidative degradation was monitored with the help of infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), solubility measurements and size exclusion chromatography (SEC) and were compared to unstabilized samples. When aged in air at 120 degrees C, the crosslinked UHMW-PE showed a slightly slower increase of the carbonyl (CO)-number (according to DIN 53383) in FTIR than conventional UHMW-PE. A stabilisation with 0.4% w/w alpha-tocopherol resulted in an increase of lifetime by a factor of approx. 40 for all samples. Ageing in 10% aqueous H2O2 at 50 degrees C yielded similar results for all three unstabilised samples. The addition of the natural antioxidant alpha-tocopherol led to a prolongation of lifetime by a factor of approx. 2.5. A linear loss of alpha-tocopherol was detected during ageing. An increase of crystallinity as well as lamella thickness during ageing was observed with the help of DSC. The two-phase structure of crosslinked UHMW-PE with two melting endotherms at 114 degrees C and 137 degrees C was replaced very quickly by a single melting point at 130 degrees C. This effect was delayed with the stabilized samples. In the solubility and SEC measurements, a severe molecular degradation and drop of molar mass of all materials could be observed after ageing in H2O2, leading to a complete destruction and, in case of crosslinked UHMW-PE, to a serious damage of the molecular network, respectively. PMID:17143765

  6. Ensembler: Enabling High-Throughput Molecular Simulations at the Superfamily Scale

    PubMed Central

    Parton, Daniel L.; Grinaway, Patrick B.; Hanson, Sonya M.; Beauchamp, Kyle A.; Chodera, John D.

    2016-01-01

    The rapidly expanding body of available genomic and protein structural data provides a rich resource for understanding protein dynamics with biomolecular simulation. While computational infrastructure has grown rapidly, simulations on an omics scale are not yet widespread, primarily because software infrastructure to enable simulations at this scale has not kept pace. It should now be possible to study protein dynamics across entire (super)families, exploiting both available structural biology data and conformational similarities across homologous proteins. Here, we present a new tool for enabling high-throughput simulation in the genomics era. Ensembler takes any set of sequences—from a single sequence to an entire superfamily—and shepherds them through various stages of modeling and refinement to produce simulation-ready structures. This includes comparative modeling to all relevant PDB structures (which may span multiple conformational states of interest), reconstruction of missing loops, addition of missing atoms, culling of nearly identical structures, assignment of appropriate protonation states, solvation in explicit solvent, and refinement and filtering with molecular simulation to ensure stable simulation. The output of this pipeline is an ensemble of structures ready for subsequent molecular simulations using computer clusters, supercomputers, or distributed computing projects like Folding@home. Ensembler thus automates much of the time-consuming process of preparing protein models suitable for simulation, while allowing scalability up to entire superfamilies. A particular advantage of this approach can be found in the construction of kinetic models of conformational dynamics—such as Markov state models (MSMs)—which benefit from a diverse array of initial configurations that span the accessible conformational states to aid sampling. We demonstrate the power of this approach by constructing models for all catalytic domains in the human tyrosine

  7. Ensembler: Enabling High-Throughput Molecular Simulations at the Superfamily Scale.

    PubMed

    Parton, Daniel L; Grinaway, Patrick B; Hanson, Sonya M; Beauchamp, Kyle A; Chodera, John D

    2016-06-01

    The rapidly expanding body of available genomic and protein structural data provides a rich resource for understanding protein dynamics with biomolecular simulation. While computational infrastructure has grown rapidly, simulations on an omics scale are not yet widespread, primarily because software infrastructure to enable simulations at this scale has not kept pace. It should now be possible to study protein dynamics across entire (super)families, exploiting both available structural biology data and conformational similarities across homologous proteins. Here, we present a new tool for enabling high-throughput simulation in the genomics era. Ensembler takes any set of sequences-from a single sequence to an entire superfamily-and shepherds them through various stages of modeling and refinement to produce simulation-ready structures. This includes comparative modeling to all relevant PDB structures (which may span multiple conformational states of interest), reconstruction of missing loops, addition of missing atoms, culling of nearly identical structures, assignment of appropriate protonation states, solvation in explicit solvent, and refinement and filtering with molecular simulation to ensure stable simulation. The output of this pipeline is an ensemble of structures ready for subsequent molecular simulations using computer clusters, supercomputers, or distributed computing projects like Folding@home. Ensembler thus automates much of the time-consuming process of preparing protein models suitable for simulation, while allowing scalability up to entire superfamilies. A particular advantage of this approach can be found in the construction of kinetic models of conformational dynamics-such as Markov state models (MSMs)-which benefit from a diverse array of initial configurations that span the accessible conformational states to aid sampling. We demonstrate the power of this approach by constructing models for all catalytic domains in the human tyrosine kinase

  8. Ensembler: Enabling High-Throughput Molecular Simulations at the Superfamily Scale.

    PubMed

    Parton, Daniel L; Grinaway, Patrick B; Hanson, Sonya M; Beauchamp, Kyle A; Chodera, John D

    2016-06-01

    The rapidly expanding body of available genomic and protein structural data provides a rich resource for understanding protein dynamics with biomolecular simulation. While computational infrastructure has grown rapidly, simulations on an omics scale are not yet widespread, primarily because software infrastructure to enable simulations at this scale has not kept pace. It should now be possible to study protein dynamics across entire (super)families, exploiting both available structural biology data and conformational similarities across homologous proteins. Here, we present a new tool for enabling high-throughput simulation in the genomics era. Ensembler takes any set of sequences-from a single sequence to an entire superfamily-and shepherds them through various stages of modeling and refinement to produce simulation-ready structures. This includes comparative modeling to all relevant PDB structures (which may span multiple conformational states of interest), reconstruction of missing loops, addition of missing atoms, culling of nearly identical structures, assignment of appropriate protonation states, solvation in explicit solvent, and refinement and filtering with molecular simulation to ensure stable simulation. The output of this pipeline is an ensemble of structures ready for subsequent molecular simulations using computer clusters, supercomputers, or distributed computing projects like Folding@home. Ensembler thus automates much of the time-consuming process of preparing protein models suitable for simulation, while allowing scalability up to entire superfamilies. A particular advantage of this approach can be found in the construction of kinetic models of conformational dynamics-such as Markov state models (MSMs)-which benefit from a diverse array of initial configurations that span the accessible conformational states to aid sampling. We demonstrate the power of this approach by constructing models for all catalytic domains in the human tyrosine kinase

  9. Remote high-definition rotating video enables fast spatial survey of marine underwater macrofauna and habitats.

    PubMed

    Pelletier, Dominique; Leleu, Kévin; Mallet, Delphine; Mou-Tham, Gérard; Hervé, Gilles; Boureau, Matthieu; Guilpart, Nicolas

    2012-01-01

    Observing spatial and temporal variations of marine biodiversity from non-destructive techniques is central for understanding ecosystem resilience, and for monitoring and assessing conservation strategies, e.g. Marine Protected Areas. Observations are generally obtained through Underwater Visual Censuses (UVC) conducted by divers. The problems inherent to the presence of divers have been discussed in several papers. Video techniques are increasingly used for observing underwater macrofauna and habitat. Most video techniques that do not need the presence of a diver use baited remote systems. In this paper, we present an original video technique which relies on a remote unbaited rotating remote system including a high definition camera. The system is set on the sea floor to record images. These are then analysed at the office to quantify biotic and abiotic sea bottom cover, and to identify and count fish species and other species like marine turtles. The technique was extensively tested in a highly diversified coral reef ecosystem in the South Lagoon of New Caledonia, based on a protocol covering both protected and unprotected areas in major lagoon habitats. The technique enabled to detect and identify a large number of species, and in particular fished species, which were not disturbed by the system. Habitat could easily be investigated through the images. A large number of observations could be carried out per day at sea. This study showed the strong potential of this non obtrusive technique for observing both macrofauna and habitat. It offers a unique spatial coverage and can be implemented at sea at a reasonable cost by non-expert staff. As such, this technique is particularly interesting for investigating and monitoring coastal biodiversity in the light of current conservation challenges and increasing monitoring needs.

  10. Remote high-definition rotating video enables fast spatial survey of marine underwater macrofauna and habitats.

    PubMed

    Pelletier, Dominique; Leleu, Kévin; Mallet, Delphine; Mou-Tham, Gérard; Hervé, Gilles; Boureau, Matthieu; Guilpart, Nicolas

    2012-01-01

    Observing spatial and temporal variations of marine biodiversity from non-destructive techniques is central for understanding ecosystem resilience, and for monitoring and assessing conservation strategies, e.g. Marine Protected Areas. Observations are generally obtained through Underwater Visual Censuses (UVC) conducted by divers. The problems inherent to the presence of divers have been discussed in several papers. Video techniques are increasingly used for observing underwater macrofauna and habitat. Most video techniques that do not need the presence of a diver use baited remote systems. In this paper, we present an original video technique which relies on a remote unbaited rotating remote system including a high definition camera. The system is set on the sea floor to record images. These are then analysed at the office to quantify biotic and abiotic sea bottom cover, and to identify and count fish species and other species like marine turtles. The technique was extensively tested in a highly diversified coral reef ecosystem in the South Lagoon of New Caledonia, based on a protocol covering both protected and unprotected areas in major lagoon habitats. The technique enabled to detect and identify a large number of species, and in particular fished species, which were not disturbed by the system. Habitat could easily be investigated through the images. A large number of observations could be carried out per day at sea. This study showed the strong potential of this non obtrusive technique for observing both macrofauna and habitat. It offers a unique spatial coverage and can be implemented at sea at a reasonable cost by non-expert staff. As such, this technique is particularly interesting for investigating and monitoring coastal biodiversity in the light of current conservation challenges and increasing monitoring needs. PMID:22383965

  11. A GRAPHICS PROCESSING UNIT-ENABLED, HIGH-RESOLUTION COSMOLOGICAL MICROLENSING PARAMETER SURVEY

    SciTech Connect

    Bate, N. F.; Fluke, C. J.

    2012-01-10

    In the era of synoptic surveys, the number of known gravitationally lensed quasars is set to increase by over an order of magnitude. These new discoveries will enable a move from single-quasar studies to investigations of statistical samples, presenting new opportunities to test theoretical models for the structure of quasar accretion disks and broad emission line regions (BELRs). As one crucial step in preparing for this influx of new lensed systems, a large-scale exploration of microlensing convergence-shear parameter space is warranted, requiring the computation of O(10{sup 5}) high-resolution magnification maps. Based on properties of known lensed quasars, and expectations from accretion disk/BELR modeling, we identify regions of convergence-shear parameter space, map sizes, smooth matter fractions, and pixel resolutions that should be covered. We describe how the computationally time-consuming task of producing {approx}290,000 magnification maps with sufficient resolution (10,000{sup 2} pixel map{sup -1}) to probe scales from the inner edge of the accretion disk to the BELR can be achieved in {approx}400 days on a 100 teraflop s{sup -1} high-performance computing facility, where the processing performance is achieved with graphics processing units. We illustrate a use-case for the parameter survey by investigating the effects of varying the lens macro-model on accretion disk constraints in the lensed quasar Q2237+0305. We find that although all constraints are consistent within their current error bars, models with more densely packed microlenses tend to predict shallower accretion disk radial temperature profiles. With a large parameter survey such as the one described here, such systematics on microlensing measurements could be fully explored.

  12. Modulation of orthogonal body waves enables high maneuverability in sidewinding locomotion

    PubMed Central

    Astley, Henry C.; Gong, Chaohui; Dai, Jin; Travers, Matthew; Serrano, Miguel M.; Vela, Patricio A.; Choset, Howie; Mendelson, Joseph R.; Hu, David L.; Goldman, Daniel I.

    2015-01-01

    Many organisms move using traveling waves of body undulation, and most work has focused on single-plane undulations in fluids. Less attention has been paid to multiplane undulations, which are particularly important in terrestrial environments where vertical undulations can regulate substrate contact. A seemingly complex mode of snake locomotion, sidewinding, can be described by the superposition of two waves: horizontal and vertical body waves with a phase difference of ±90°. We demonstrate that the high maneuverability displayed by sidewinder rattlesnakes (Crotalus cerastes) emerges from the animal’s ability to independently modulate these waves. Sidewinder rattlesnakes used two distinct turning methods, which we term differential turning (26° change in orientation per wave cycle) and reversal turning (89°). Observations of the snakes suggested that during differential turning the animals imposed an amplitude modulation in the horizontal wave whereas in reversal turning they shifted the phase of the vertical wave by 180°. We tested these mechanisms using a multimodule snake robot as a physical model, successfully generating differential and reversal turning with performance comparable to that of the organisms. Further manipulations of the two-wave system revealed a third turning mode, frequency turning, not observed in biological snakes, which produced large (127°) in-place turns. The two-wave system thus functions as a template (a targeted motor pattern) that enables complex behaviors in a high-degree-of-freedom system to emerge from relatively simple modulations to a basic pattern. Our study reveals the utility of templates in understanding the control of biological movement as well as in developing control schemes for limbless robots. PMID:25831489

  13. Enabling computer models of the heart for high-performance computers and the grid.

    PubMed

    Pitt-Francis, Joe; Garny, Alan; Gavaghan, David

    2006-06-15

    Although it is now feasible to compute multi-cellular models of the heart on a personal desktop or laptop computer, it is not feasible to undertake the detailed sweeps of high-dimensional parameter spaces required if we are to undertake in silico experimentation of the complex processes that constitute heart disease. For this research, modelling requirements move rapidly beyond the limit of commodity computers' resource both in terms of their memory footprint and the speed of calculation, so that multi-processor architectures must be considered. In addition, as such models have become more mature and have been validated against experimental data, there is increasing pressure for experimentalists to be able to make use of these models themselves as a key tool for hypothesis formulation and in planning future experimental studies to test those hypotheses. This paper discusses our initial experiences in a large-scale project (the Integrative Biology (IB) e-Science project) aimed at meeting these dual aims. We begin by putting the research in context by describing in outline the overall aims of the IB project, in particular focusing on the challenge of enabling novice users to make full use of high-performance resources without the need to gain detailed technical expertise in computing. We then discuss our experience of adapting one particular heart modelling package, Cellular Open Resource, and show how the solving engine of this code was dissected from the rest of the package, ported to C++ and parallelized using the Message-Passing Interface. We show that good parallel efficiency and realistic memory reduction can be achieved on simple geometries. We conclude by discussing lessons learnt in this process.

  14. OpenTopography: Enabling Online Access to High-Resolution Lidar Topography Data and Processing Tools

    NASA Astrophysics Data System (ADS)

    Crosby, Christopher; Nandigam, Viswanath; Baru, Chaitan; Arrowsmith, J. Ramon

    2013-04-01

    resources. Datasets hosted by other organizations, as well as lidar-specific software, can be registered into the OpenTopography catalog, providing users a "one-stop shop" for such information. With several thousand active users, OpenTopography is an excellent example of a mature Spatial Data Infrastructure system that is enabling access to challenging data for research, education and outreach. Ongoing OpenTopography design and development work includes the archive and publication of datasets using digital object identifiers (DOIs); creation of a more flexible and scalable high-performance environment for processing of large datasets; expanded support for satellite and terrestrial lidar; and creation of a "pluggable" infrastructure for third-party programs and algorithms. OpenTopography has successfully created a facility for sharing lidar data. In the project's next phase, we are working to enable equally easy and successful sharing of services for processing and analysis of these data.

  15. Demonstration of high current carbon nanotube enabled vertical organic field effect transistors at industrially relevant voltages

    NASA Astrophysics Data System (ADS)

    McCarthy, Mitchell

    The display market is presently dominated by the active matrix liquid crystal display (LCD). However, the active matrix organic light emitting diode (AMOLED) display is argued to become the successor to the LCD, and is already beginning its way into the market, mainly in small size displays. But, for AMOLED technology to become comparable in market share to LCD, larger size displays must become available at a competitive price with their LCD counterparts. A major issue preventing low-cost large AMOLED displays is the thin-film transistor (TFT) technology. Unlike the voltage driven LCD, the OLEDs in the AMOLED display are current driven. Because of this, the mature amorphous silicon TFT backplane technology used in the LCD must be upgraded to a material possessing a higher mobility. Polycrystalline silicon and transparent oxide TFT technologies are being considered to fill this need. But these technologies bring with them significant manufacturing complexity and cost concerns. Carbon nanotube enabled vertical organic field effect transistors (CN-VFETs) offer a unique solution to this problem (now known as the AMOLED backplane problem). The CN-VFET allows the use of organic semiconductors to be used for the semiconductor layer. Organics are known for their low-cost large area processing compatibility. Although the mobility of the best organics is only comparable to that of amorphous silicon, the CN-VFET makes up for this by orienting the channel vertically, as opposed to horizontally (like in conventional TFTs). This allows the CN-VFET to achieve sub-micron channel lengths without expensive high resolution patterning. Additionally, because the CN-VFET can be easily converted into a light emitting transistor (called the carbon nanotube enabled vertical organic light emitting transistor---CN-VOLET) by essentially stacking an OLED on top of the CN-VFET, more potential benefits can be realized. These potential benefits include, increased aperture ratio, increased OLED

  16. Highly crystalline lithium titanium oxide sheets coated with nitrogen-doped carbon enable high-rate lithium-ion batteries.

    PubMed

    Han, Cuiping; He, Yan-Bing; Li, Baohua; Li, Hongfei; Ma, Jun; Du, Hongda; Qin, Xianying; Yang, Quan-Hong; Kang, Feiyu

    2014-09-01

    Sheets of Li4Ti5O12 with high crystallinity are coated with nitrogen-doped carbon (NC-LTO) using a controlled process, comprising hydrothermal reaction followed by chemical vapor deposition (CVD). Acetonitrile (CH3 CN) vapor is used as carbon and nitrogen source to obtain a thin coating layer of nitrogen-doped carbon. The layer enables the NC-LTO material to maintain its sheet structure during the high-temperature CVD process and to achieve high crystallinity. Doping with nitrogen introduces defects into the carbon coating layer, and this increased degree of disorder allows fast transportation of lithium ions in the layer. An electrode of NC-LTO synthesized at 700 °C exhibits greatly improved rate and cycling performance due to a markedly decreased total cell resistance and enhanced Li-ion diffusion coefficient (D(Li)). Specific capacities of 159.2 and 145.8 mA h g(-1) are obtained using the NC-LTO sheets, at charge/discharge rates of 1 and 10 C, respectively. These values are much higher than values for LTO particles did not undergo the acetonitrile CVD treatment. A capacity retention value as high as 94.7% is achieved for the NC-LTO sheets after 400 cycles in a half-cell at 5 C discharge rate.

  17. Can Sequentially-irradiated and Annealed Highly Cross-linked Polyethylene Inserts Thinner than Eight-millimeters Be Utilized in Total Knee Arthroplasty?

    PubMed

    Sayeed, Siraj A; Jauregui, Julio J; Korduba, Laryssa A; Essner, Aaron; Harwin, Steven F; Delanois, Ronald E; Mont, Michael A

    2015-05-01

    The routine use of highly cross-linked ultra-high molecular weight polyethylene (UHMWPE) has remained controversial secondary to the possibility of decreased material properties when compared to conventional UHMWPE. The aim of the present study was to evaluate if thin, sequentially-irradiated, and annealed highly cross-linked UHMWPE tibial inserts would have improved wear properties, while maintaining mechanical integrity, compared to conventional UHMWPE during biomechanical testing under aligned and malaligned conditions. Polyethylene inserts (4.27 and 6.27 mm) manufactured from GUR 1020-UHMWPE were cyclically loaded to analyze for wear. All wear scars were visually examined after loading using scanning electron microscopy (SEM). Volume loss was plotted versus cycle count with linear regression analysis yielding wear rates. There was no statistical difference in wear between both thicknesses for all testing conditions. During aligned condition testing, the volumetric wear rate for sequentially-irradiated and annealed polyethylene thicknesses of 4.27 and 6.27 mm was 4.0 and 4.4 mm3/million cycles; and during malaligned conditions, it was 13.9 and 15.1 mm3/million cycles. For conventional polyethylene during aligned conditions, the volumetric wear rate was 33.0 and 22.8 mm3/million cycles; and during malaligned conditions it was 50.0 and 50.8 mm3/million cycles. By SEM evaluation, condylar wear surfaces for conventional and sequentially-irradiated and annealed polyethylene displayed surface ripples typical of adhesive wear. There were no observed visible differences between the wear scars for conventional compared to sequentially-irradiated and annealed polyethylene with no evidence of fatigue failure. This study demonstrated no differences between polyethylenes with thicknesses of 4.27 and 6.27 mm. This strengthens the conclusion that sequentially-irradiated and annealed highly cross-linked UHMWPE can be utilized in total knee arthroplasty. The successful wear

  18. Influence of cross-link structure, density and mechanical properties in the mesoscale deformation mechanisms of collagen fibrils.

    PubMed

    Depalle, Baptiste; Qin, Zhao; Shefelbine, Sandra J; Buehler, Markus J

    2015-12-01

    Collagen is a ubiquitous protein with remarkable mechanical properties. It is highly elastic, shows large fracture strength and enables substantial energy dissipation during deformation. Most of the connective tissue in humans consists of collagen fibrils composed of a staggered array of tropocollagen molecules, which are connected by intermolecular cross-links. In this study, we report a three-dimensional coarse-grained model of collagen and analyze the influence of enzymatic cross-links on the mechanics of collagen fibrils. Two representatives immature and mature cross-links are implemented in the mesoscale model using a bottom-up approach. By varying the number, type and mechanical properties of cross-links in the fibrils and performing tensile test on the models, we systematically investigate the deformation mechanisms of cross-linked collagen fibrils. We find that cross-linked fibrils exhibit a three phase behavior, which agrees closer with experimental results than what was obtained using previous models. The fibril mechanical response is characterized by: (i) an initial elastic deformation corresponding to the collagen molecule uncoiling, (ii) a linear regime dominated by molecule sliding and (iii) the second stiffer elastic regime related to the stretching of the backbone of the tropocollagen molecules until the fibril ruptures. Our results suggest that both cross-link density and type dictate the stiffness of large deformation regime by increasing the number of interconnected molecules while cross-links mechanical properties determine the failure strain and strength of the fibril. These findings reveal that cross-links play an essential role in creating an interconnected fibrillar material of tunable toughness and strength.

  19. Influence of cross-link structure, density and mechanical properties in the mesoscale deformation mechanisms of collagen fibrils

    PubMed Central

    Depalle, Baptiste; Qin, Zhao; Shefelbine, Sandra J.; Buehler, Markus J.

    2015-01-01

    Collagen is a ubiquitous protein with remarkable mechanical properties. It is highly elastic, shows large fracture strength and enables substantial energy dissipation during deformation. Most of the connective tissue in humans consists of collagen fibrils composed of a staggered array of tropocollagen molecules, which are connected by intermolecular cross-links. In this study, we report a three-dimensional coarse-grained model of collagen and analyze the influence of enzymatic cross-links on the mechanics of collagen fibrils. Two representatives immature and mature cross-links are implemented in the mesoscale model using a bottom-up approach. By varying the number, type and mechanical properties of cross-links in the fibrils and performing tensile test on the models, we systematically investigate the deformation mechanisms of cross-linked collagen fibrils. We find that cross-linked fibrils exhibit a three phase behavior, which agrees closer with experimental results than what was obtained using previous models. The fibril mechanical response is characterized by: (i) an initial elastic deformation corresponding to the collagen molecule uncoiling, (ii) a linear regime dominated by molecule sliding and (iii) the second stiffer elastic regime related to the stretching of the backbone of the tropocollagen molecules until the fibril ruptures. Our results suggest that both cross-link density and type dictate the stiffness of large deformation regime by increasing the number of interconnected molecules while cross-links mechanical properties determine the failure strain and strength of the fibril. These findings reveal that cross-links play an essential role in creating an interconnected fibrillar material of tunable toughness and strength. PMID:25153614

  20. The radiation crosslinking process and new products

    NASA Astrophysics Data System (ADS)

    Ueno, Keiji

    In 1988 there were over 90 EB accelerators for industrial use in Japan. The number one industrial application was Wire and Cable, the 2nd was PE foam and Curing, and the 3rd was Precure of tyre. R & D has a very high ration of EB accelerator use. Low energy industrial applications were coated steel (white board), plaster slab, coated paper, magnetic tape and floppy disks. As a new application of the radiation crosslinking process, we have studied radiation crosslinking of engineering plastics and succeeded in improving the hea tresistivity without using glass fibers. Many kinds of polyfunctional monomers used as crosslinking reagents of irradiated Nylon and PBT were studied.

  1. New in situ crosslinking chemistries for hydrogelation

    NASA Astrophysics Data System (ADS)

    Roberts, Meredith Colleen

    Over the last half century, hydrogels have found immense value as biomaterials in a vast number of biomedical and pharmaceutical applications. One subset of hydrogels receiving increased attention is in situ forming gels. Gelling by either bioresponsive self-assembly or mixing of binary crosslinking systems, these technologies are useful in minimally invasive applications as well as drug delivery systems in which the sol-to-gel transition aids the formulation's performance. Thus far, the field of in situ crosslinking hydrogels has received limited attention in the development of new crosslinking chemistries. Moreover, not only does the chemical nature of the crosslinking moieties allow these systems to perform in situ, but they contribute dramatically to the mechanical properties of the hydrogel networks. For example, reversible crosslinks with finite lifetimes generate dynamic viscoelastic gels with time-dependent properties, whereas irreversible crosslinks form highly elastic networks. The aim of this dissertation is to explore two new covalent chemistries for their ability to crosslink hydrogels in situ under physiological conditions. First, reversible phenylboronate-salicylhydroxamate crosslinking was implemented in a binary, multivalent polymeric system. These gels formed rapidly and generated hydrogel networks with frequency-dependent dynamic rheological properties. Analysis of the composition-structure-property relationships of these hydrogels---specifically considering the effects of pH, degree of polymer functionality, charge of the polymer backbone and polymer concentration on dynamic theological properties---was performed. These gels demonstrate diverse mechanical properties, due to adjustments in the binding equilibrium of the pH-sensitive crosslinks, and thus have the potential to perform in a range of dynamic or bioresponsive applications. Second, irreversible catalyst-free "click" chemistry was employed in the hydrogelation of multivalent azide

  2. Long-Term Results of Total Hip Arthroplasty with 28-Millimeter Cobalt-Chromium Femoral Heads on Highly Cross-Linked Polyethylene in Patients 50 Years and Less.

    PubMed

    Stambough, Jeffrey B; Pashos, Gail; Bohnenkamp, Frank C; Maloney, William J; Martell, John M; Clohisy, John C

    2016-01-01

    Highly cross-linked polyethylene (HXLPE) is the most commonly used bearing surface in total hip arthroplasty (THA) because of its superior wear properties, but long-term results in young patients are limited. We report on the clinical outcome, radiographic wear patterns and survivorship of 72 patients ≤50 years old who had a 28-millimeter cobalt-chromium femoral head on HXLPE acetabular liner. Mean and median true linear wear rates at average ten-year follow-up were 0.0104 and 0.01 mm per year ± 0.07 mm. Mean and median two-dimensional volumetric wear rates were 12.79 mm(3) and 5.834 mm(3) per year ± 26.1mm(3) as determined by Martell analysis. As a result of the minimal wear profile, there was no evidence of radiographic osteolysis and no wear-related revisions.

  3. Highly cross-linked ultrahigh molecular weight polyethylene with improved fatigue resistance for total joint arthroplasty: recipient of the 2006 Hap Paul Award.

    PubMed

    Oral, Ebru; Malhi, Arnaz S; Wannomae, Keith K; Muratoglu, Orhun K

    2008-10-01

    Eliminating postirradiation melting and stabilizing the residual free radicals of radiation cross-linked ultrahigh molecular weight polyethylene (UHMWPE) with vitamin E resulted in improved fatigue crack propagation resistance without compromising wear resistance. We designed a cantilever postbending test to determine the bending fatigue resistance of alpha-tocopherol-doped, irradiated UHMWPE (alpha-TPE) in comparison to conventional UHMWPE. The bending fatigue behavior of alpha-TPE was comparable to conventional UHMWPE. Upon accelerated aging, the fatigue resistance of alpha-TPE was substantially better than that of conventional UHMWPE. alpha-TPE has shown improved wear and oxidation resistance, migration stability of vitamin E, and improved mechanical properties. The use of this material may be beneficial in total knee arthroplasty where its improved fatigue properties may be an advantage under high stresses.

  4. Long-Term Results of Total Hip Arthroplasty with 28-Millimeter Cobalt-Chromium Femoral Heads on Highly Cross-Linked Polyethylene in Patients 50 Years and Less.

    PubMed

    Stambough, Jeffrey B; Pashos, Gail; Bohnenkamp, Frank C; Maloney, William J; Martell, John M; Clohisy, John C

    2016-01-01

    Highly cross-linked polyethylene (HXLPE) is the most commonly used bearing surface in total hip arthroplasty (THA) because of its superior wear properties, but long-term results in young patients are limited. We report on the clinical outcome, radiographic wear patterns and survivorship of 72 patients ≤50 years old who had a 28-millimeter cobalt-chromium femoral head on HXLPE acetabular liner. Mean and median true linear wear rates at average ten-year follow-up were 0.0104 and 0.01 mm per year ± 0.07 mm. Mean and median two-dimensional volumetric wear rates were 12.79 mm(3) and 5.834 mm(3) per year ± 26.1mm(3) as determined by Martell analysis. As a result of the minimal wear profile, there was no evidence of radiographic osteolysis and no wear-related revisions. PMID:26260785

  5. Evaluation of Pressure Stable Chip-to-Tube Fittings Enabling High-Speed Chip-HPLC with Mass Spectrometric Detection.

    PubMed

    Lotter, Carsten; Heiland, Josef J; Stein, Volkmar; Klimkait, Michael; Queisser, Marco; Belder, Detlev

    2016-08-01

    Appropriate chip-to-tube interfacing is an enabling technology for high-pressure and high-speed liquid chromatography on chip. For this purpose, various approaches, to connect pressure resistant glass chips with HPLC pumps working at pressures of up to 500 bar, were examined. Three side-port and one top-port connection approach were evaluated with regard to pressure stability and extra column band broadening. A clamp-based top-port approach enabled chip-HPLC-MS analysis of herbicides at the highest pressure and speed. PMID:27397738

  6. Evaluation of Pressure Stable Chip-to-Tube Fittings Enabling High-Speed Chip-HPLC with Mass Spectrometric Detection.

    PubMed

    Lotter, Carsten; Heiland, Josef J; Stein, Volkmar; Klimkait, Michael; Queisser, Marco; Belder, Detlev

    2016-08-01

    Appropriate chip-to-tube interfacing is an enabling technology for high-pressure and high-speed liquid chromatography on chip. For this purpose, various approaches, to connect pressure resistant glass chips with HPLC pumps working at pressures of up to 500 bar, were examined. Three side-port and one top-port connection approach were evaluated with regard to pressure stability and extra column band broadening. A clamp-based top-port approach enabled chip-HPLC-MS analysis of herbicides at the highest pressure and speed.

  7. The rates of wear of X3 highly cross-linked polyethylene at five years when coupled with a 36 mm diameter ceramic femoral head in young patients.

    PubMed

    Selvarajah, E; Hooper, G; Grabowski, K; Frampton, C; Woodfield, T B F; Inglis, G

    2015-11-01

    Polyethylene wear debris can cause osteolysis and the failure of total hip arthroplasty. We present the five-year wear rates of a highly cross-linked polyethylene (X3) bearing surface when used in conjunction with a 36 mm ceramic femoral head. This was a prospective study of a cohort of 100 THAs in 93 patients. Pain and activity scores were measured pre- and post-operatively. Femoral head penetration was measured at two months, one year, two years and at five years using validated edge-detecting software (PolyWare Auto). At a mean of 5.08 years (3.93 to 6.01), 85 hips in 78 patients were available for study. The mean age of these patients was 59.08 years (42 to 73, the mean age of males (n = 34) was 59.15 years, and females (n = 44) was 59.02 years). All patients had significant improvement in their functional scores (p < 0.001). The steady state two-dimensional linear wear rate was 0.109 mm/year. The steady state volumetric wear rate was 29.61 mm(3)/year. No significant correlation was found between rate of wear and age (p = 0.34), acetabular component size (p = 0.12) or clinical score (p = 0.74). Our study shows low steady state wear rates at five years in X3 highly cross-linked polyethylene in conjunction with a 36 mm ceramic femoral head. The linear wear rate was almost identical to the osteolysis threshold of 0.1 mm/year recommended in the literature.

  8. Stereocomplexation of low molecular weight poly(L-lactic acid) and high molecular weight poly(D-lactic acid), radiation crosslinking PLLA/PDLA stereocomplexes and their characterization

    NASA Astrophysics Data System (ADS)

    Quynh, Tran Minh; Mai, Hoang Hoa; Lan, Pham Ngoc

    2013-02-01

    Poly(L-lactic acid)s (PLLAx) were synthesized from L-lactic acid by polycondensation. Different stereocomplexes were also obtained with equimolar mixtures of synthesized PLLAx and a commercial PDLA. The stereocomplexes were crosslinked with triallyl isocyanurate (TAIC) by gamma irradiation. Crosslinking density increased with radiation doses, the heavier the crosslinking network, the lower its swelling degree. The crosslinking structures were introduced in the stereocomplexes inhibiting the mobility for crystallization of PLLA molecules. Thermal and mechanical properties of PLA stereocomplexes were remarkably enhanced by radiation induced crosslinking. PLA stereocomplex does not seem to be degraded by PLLA degrading microorganisms existing in compost at room temperature, but the synthesized PLLA was significantly degraded.

  9. RFID-enabled traceability system for consignment and high value products: a case study in the healthcare sector.

    PubMed

    Bendavid, Ygal; Boeck, Harold; Philippe, Richard

    2012-12-01

    This paper presents a case study of a hospital operating room that evaluated a Radio-Frequency Identification (RFID)-enabled traceability system for the management of consignment and high value products requiring item level traceability. Results indicate that the traceability system in conjunction with the redesign of replenishment processes facilitates item level traceability, improves financial controls and case costing, upgrades service levels and reduces inventory shrinkage. Other benefits include time saved from non-value-added activities that can be transferred to patient care activities. The solution can be considered (i) as an alternative to RFID-enabled cabinets used in the replenishment of consignment and high value supplies in certain operating rooms, cardiac catheterization laboratories and interventional radiology departments, or (ii) as a complementary solution facilitating the tracking of medical devices removed from RFID-enabled cabinets. In short, the end-to-end traceability of medical products in the healthcare supply chain can be significantly enhanced. PMID:22105627

  10. RFID-enabled traceability system for consignment and high value products: a case study in the healthcare sector.

    PubMed

    Bendavid, Ygal; Boeck, Harold; Philippe, Richard

    2012-12-01

    This paper presents a case study of a hospital operating room that evaluated a Radio-Frequency Identification (RFID)-enabled traceability system for the management of consignment and high value products requiring item level traceability. Results indicate that the traceability system in conjunction with the redesign of replenishment processes facilitates item level traceability, improves financial controls and case costing, upgrades service levels and reduces inventory shrinkage. Other benefits include time saved from non-value-added activities that can be transferred to patient care activities. The solution can be considered (i) as an alternative to RFID-enabled cabinets used in the replenishment of consignment and high value supplies in certain operating rooms, cardiac catheterization laboratories and interventional radiology departments, or (ii) as a complementary solution facilitating the tracking of medical devices removed from RFID-enabled cabinets. In short, the end-to-end traceability of medical products in the healthcare supply chain can be significantly enhanced.

  11. ULTRACOATINGS: Enabling Energy and Power Solutions in High Contact Stress Environments through Next-Generation Nanocoatings

    SciTech Connect

    Blau, P.; Qu, J.; Higdon, C. III

    2011-09-30

    This industry-driven project was the result of a successful response by Eaton Corporation to a DOE/ITP Program, Grand Challenge, industry call. It consisted of a one-year effort in which ORNL participated in the area of friction and wear testing. In addition to Eaton Corporation and ORNL (CRADA), the project team included: Ames Laboratory, who developed the underlying concept for titanium- zirconium-boron (TZB) based nanocomposite coatings; Borg-Warner Morse TEC, an automotive engine timing chain manufacturer in Ithaca, New York, with its own proprietary hard coating; and Pratt & Whitney Rocketdyne, Inc., a dry-solids pump manufacturer in San Fernando Valley, California. This report focuses only on the portion of work that was conducted by ORNL, in a CRADA with Eaton Corporation. A comprehensive final report for the entire effort, which ended in September 2010, has been prepared for DOE by the team. The term 'ultracoatings' derives from the ambitious technical target for the new generation of nanocoatings. As applications, Eaton was specifically considering a fuel pump and a gear application in which the product of the contact pressure and slip velocity during operation of mating surfaces, commonly called the 'PV value', was equal to or greater than 70,000 MPa-m/s. This ambitious target challenges the developers of coatings to produce material capable of strong bonding to the substrate, as well as high wear resistance and the ability to maintain sliding friction at low, energy-saving levels. The partners in this effort were responsible for the selection and preparation of such candidate ultracoatings, and ORNL used established tribology testing capabilities to help screen these candidates for performance. This final report summarizes ORNL's portion of the nanocomposite coatings development effort and presents both generated data and the analyses that were used in the course of this effort. Initial contact stress and speed calculations showed that laboratory tests

  12. Disorder by Random Crosslinking in Smectic Elastomers

    NASA Astrophysics Data System (ADS)

    Lambreva, Denitza M.; Ostrovskii, Boris I.; Finkelmann, Heino; de Jeu, Wim H.

    2004-10-01

    We present a high-resolution x-ray study of the effects of disorder due to random crosslinking on the one-dimensional translational ordering in smectic elastomers. At a small crosslink density of about 5%, the elastomer network stabilizes the smectic structure against layer-displacement fluctuations, and the algebraically decaying layer ordering extends up to several micrometers. With increasing concentration of crosslinks, the finite size of these domains is strongly reduced, indicating that disordering takes over. Finally, at a crosslink concentration of 20%, the structure factor can be described by a Lorentzian, which signals extended short-range correlations. The findings are discussed in terms of recent theories of randomly quenched disorder.

  13. Abstract for Session IN016. Enabling Science Through Reuse of Data and Free and Open Source Software How Elsevier is supporting the value and usefulness of data with Cross-linking and Digital Content

    NASA Astrophysics Data System (ADS)

    Keall, B. S.; Koers, H.

    2013-12-01

    Thanks to decades of technological advances to improve the collection, organization, storage, and sharing of data, experimental research data has become an increasingly important element of the research process. And one can only expect that the relevance of research data will continue to grow, given the recent push from funding bodies to make research data better available, the emergence of trusted, domain-specific data repositories, and the support from journal publishers. Elsevier is excited by the prospect of accelerating the pace of research by creating proper solutions for research data, including bidirectional links between articles and data to enable discovery and proper re-use. Connecting articles and data is an integral part of Elsevier's 'Article of the Future', an ongoing program to improve the article format to meet the needs of modern-day researchers. As part of this effort, we have set up bi-directional linking between online articles and data repositories so that researchers can easily find the data that is relevant for a paper and vice versa. Recently, we have set up such links with some of the leading data repositories in Earth Sciences, including the British Geological Survey, IEDA's Marine Geoscience Data System, and the Oak Ridge National Laboratory DAAC. Building on these links, Elsevier has also developed a number of data integration and visualization tools, such as our long-standing collaboration with PANGAEA. Another dimension of the Article of the Future is to provide authors with the capabilities to embed digital research output to their publication, thus breaking away from the limitations of the traditional ink-on-paper format. Supported digital content types include interactive (Google) maps, videos, and 3D models. Recently, we have also published a Special Issue with Executable Papers that combines the narrative of the article with data and code elements, all connected in such a way that researchers can perform computations while

  14. Evidence of high harmonics from echo-enabled harmonic generation for seeding x-ray free electron lasers.

    PubMed

    Xiang, D; Colby, E; Dunning, M; Gilevich, S; Hast, C; Jobe, K; McCormick, D; Nelson, J; Raubenheimer, T O; Soong, K; Stupakov, G; Szalata, Z; Walz, D; Weathersby, S; Woodley, M

    2012-01-13

    Echo-enabled harmonic generation free electron lasers hold great promise for the generation of fully coherent radiation in x-ray wavelengths. Here we report the first evidence of high harmonics from the echo-enabled harmonic generation technique in the realistic scenario where the laser energy modulation is comparable to the beam slice energy spread. In this experiment, coherent radiation at the seventh harmonic of the second seed laser is generated when the energy modulation amplitude is about 2-3 times the slice energy spread. The experiment confirms the underlying physics of echo-enabled harmonic generation and may have a strong impact on emerging seeded x-ray free electron lasers that are capable of generating laserlike x rays which will advance many areas of science.

  15. Evidence of High Harmonics from Echo-Enabled Harmonic Generation for Seeding X-ray Free Electron Lasers

    SciTech Connect

    Xiang, D.; Colby, E.; Dunning, M.; Gilevich, S.; Hast, C.; Jobe, K.; McCormick, D.; Nelson, J.; Raubenheimer, T.O.; Soong, K.; Stupakov, G.; Szalata, Z.; Walz, D.; Weathersby, S.; Woodle, M.; /SLAC

    2012-02-15

    Echo-enabled harmonic generation free electron lasers hold great promise for the generation of fully coherent radiation in x-ray wavelengths. Here we report the first evidence of high harmonics from the echo-enabled harmonic generation technique in the realistic scenario where the laser energy modulation is comparable to the beam slice energy spread. In this experiment, coherent radiation at the seventh harmonic of the second seed laser is generated when the energy modulation amplitude is about 2-3 times the slice energy spread. The experiment confirms the underlying physics of echo-enabled harmonic generation and may have a strong impact on emerging seeded x-ray free electron lasers that are capable of generating laserlike x rays which will advance many areas of science.

  16. High strength polymer post insulators enable economical transmission lines with low environmental impact

    SciTech Connect

    Burnham, J.T.; Givens, P.S.; Grisham, T.M.

    1994-12-31

    In today`s operational environment, utility transmission engineers are being challenged with a new set of design parameters. In addition to the traditional objective of system reliability, new issues of paramount importance heave evolved. These include the reduction of construction costs, addressing transmission line aesthetics, and optimizing power delivery within restricted right of way. This document describes a design approach which enables the engineer to maximize these criteria without sacrificing system reliability. A laboratory test method for polymer post insulators is also presented which effectively simulates combined mechanical load conditions expected in application, thus allowing the utility engineer to optimize span lengths, conductor size, and insulator selection. Polymer history and benefits associated with compact line design are also reviewed.

  17. A poly(dimethylsiloxane)-based device enabling time-lapse imaging with high spatial resolution

    SciTech Connect

    Hirano, Masahiko; Hoshida, Tetsushi; Sakaue-Sawano, Asako; Miyawaki, Atsushi

    2010-02-12

    We have developed a regulator-free device that enables long-term incubation of mammalian cells for epi-fluorescence imaging, based on a concept that the size of sample to be gassed and heated is reduced to observation scale. A poly(dimethylsiloxane) block stamped on a coverslip works as a long-lasting supplier of CO{sub 2}-rich gas to adjust bicarbonate-containing medium in a tiny chamber at physiological pH, and an oil-immersion objective warms cells across the coverslip. A time-lapse imaging experiment using HeLa cells stably expressing fluorescent cell-cycle indicators showed that the cells in the chamber proliferated with normal cell-cycle period over 2 days.

  18. Micropatterned comet assay enables high throughput and sensitive DNA damage quantification.

    PubMed

    Ge, Jing; Chow, Danielle N; Fessler, Jessica L; Weingeist, David M; Wood, David K; Engelward, Bevin P

    2015-01-01

    The single cell gel electrophoresis assay, also known as the comet assay, is a versatile method for measuring many classes of DNA damage, including base damage, abasic sites, single strand breaks and double strand breaks. However, limited throughput and difficulties with reproducibility have limited its utility, particularly for clinical and epidemiological studies. To address these limitations, we created a microarray comet assay. The use of a micrometer scale array of cells increases the number of analysable comets per square centimetre and enables automated imaging and analysis. In addition, the platform is compatible with standard 24- and 96-well plate formats. Here, we have assessed the consistency and sensitivity of the microarray comet assay. We showed that the linear detection range for H2O2-induced DNA damage in human lymphoblastoid cells is between 30 and 100 μM, and that within this range, inter-sample coefficient of variance was between 5 and 10%. Importantly, only 20 comets were required to detect a statistically significant induction of DNA damage for doses within the linear range. We also evaluated sample-to-sample and experiment-to-experiment variation and found that for both conditions, the coefficient of variation was lower than what has been reported for the traditional comet assay. Finally, we also show that the assay can be performed using a 4× objective (rather than the standard 10× objective for the traditional assay). This adjustment combined with the microarray format makes it possible to capture more than 50 analysable comets in a single image, which can then be automatically analysed using in-house software. Overall, throughput is increased more than 100-fold compared to the traditional assay. Together, the results presented here demonstrate key advances in comet assay technology that improve the throughput, sensitivity, and robustness, thus enabling larger scale clinical and epidemiological studies. PMID:25527723

  19. Micropatterned comet assay enables high throughput and sensitive DNA damage quantification

    PubMed Central

    Ge, Jing; Chow, Danielle N.; Fessler, Jessica L.; Weingeist, David M.; Wood, David K.; Engelward, Bevin P.

    2015-01-01

    The single cell gel electrophoresis assay, also known as the comet assay, is a versatile method for measuring many classes of DNA damage, including base damage, abasic sites, single strand breaks and double strand breaks. However, limited throughput and difficulties with reproducibility have limited its utility, particularly for clinical and epidemiological studies. To address these limitations, we created a microarray comet assay. The use of a micrometer scale array of cells increases the number of analysable comets per square centimetre and enables automated imaging and analysis. In addition, the platform is compatible with standard 24- and 96-well plate formats. Here, we have assessed the consistency and sensitivity of the microarray comet assay. We showed that the linear detection range for H2O2-induced DNA damage in human lymphoblastoid cells is between 30 and 100 μM, and that within this range, inter-sample coefficient of variance was between 5 and 10%. Importantly, only 20 comets were required to detect a statistically significant induction of DNA damage for doses within the linear range. We also evaluated sample-to-sample and experiment-to-experiment variation and found that for both conditions, the coefficient of variation was lower than what has been reported for the traditional comet assay. Finally, we also show that the assay can be performed using a 4× objective (rather than the standard 10× objective for the traditional assay). This adjustment combined with the microarray format makes it possible to capture more than 50 analysable comets in a single image, which can then be automatically analysed using in-house software. Overall, throughput is increased more than 100-fold compared to the traditional assay. Together, the results presented here demonstrate key advances in comet assay technology that improve the throughput, sensitivity, and robustness, thus enabling larger scale clinical and epidemiological studies. PMID:25527723

  20. Multimodal confocal mosaics enable high sensitivity and specificity in screening of in situ squamous cell carcinoma

    NASA Astrophysics Data System (ADS)

    Grados Luyando, Maria del Carmen; Bar, Anna; Snavely, Nicholas; Jacques, Steven; Gareau, Daniel S.

    2014-02-01

    Screening cancer in excision margins with confocal microscopy may potentially save time and cost over the gold standard histopathology (H and E). However, diagnostic accuracy requires sufficient contrast and resolution to reveal pathological traits in a growing set of tumor types. Reflectance mode images structural details due to microscopic refractive index variation. Nuclear contrast with acridine orange fluorescence provides enhanced diagnostic value, but fails for in situ squamous cell carcinoma (SCC), where the cytoplasm is important to visualize. Combination of three modes [eosin (Eo) fluorescence, reflectance (R) and acridine orange (AO) fluorescence] enable imaging of cytoplasm, collagen and nuclei respectively. Toward rapid intra-operative pathological margin assessment to guide staged cancer excisions, multimodal confocal mosaics can image wide surgical margins (~1cm) with sub-cellular resolution and mimic the appearance of conventional H and E. Absorption contrast is achieved by alternating the excitation wavelength: 488nm (AO fluorescence) and 532nm (Eo fluorescence). Superposition and false-coloring of these modes mimics H and E, enabling detection of the carcinoma in situ in the epidermal layer The sum mosaic Eo+R is false-colored pink to mimic eosins' appearance in H and E, while the AO mosaic is false-colored purple to mimic hematoxylins' appearance in H and E. In this study, mosaics of 10 Mohs surgical excisions containing SCC in situ and 5 containing only normal tissue were subdivided for digital presentation equivalent to 4X histology. Of the total 16 SCC in situ multimodal mosaics and 16 normal cases presented, two reviewers made 1 and 2 (respectively) type-2 errors (false positives) but otherwise scored perfectly when using the confocal images to screen for the presence of SCC in situ as compared to the gold standard histopathology. Limitations to precisely mimic H and E included occasional elastin staining by AO. These results suggest that

  1. Micropatterned comet assay enables high throughput and sensitive DNA damage quantification.

    PubMed

    Ge, Jing; Chow, Danielle N; Fessler, Jessica L; Weingeist, David M; Wood, David K; Engelward, Bevin P

    2015-01-01

    The single cell gel electrophoresis assay, also known as the comet assay, is a versatile method for measuring many classes of DNA damage, including base damage, abasic sites, single strand breaks and double strand breaks. However, limited throughput and difficulties with reproducibility have limited its utility, particularly for clinical and epidemiological studies. To address these limitations, we created a microarray comet assay. The use of a micrometer scale array of cells increases the number of analysable comets per square centimetre and enables automated imaging and analysis. In addition, the platform is compatible with standard 24- and 96-well plate formats. Here, we have assessed the consistency and sensitivity of the microarray comet assay. We showed that the linear detection range for H2O2-induced DNA damage in human lymphoblastoid cells is between 30 and 100 μM, and that within this range, inter-sample coefficient of variance was between 5 and 10%. Importantly, only 20 comets were required to detect a statistically significant induction of DNA damage for doses within the linear range. We also evaluated sample-to-sample and experiment-to-experiment variation and found that for both conditions, the coefficient of variation was lower than what has been reported for the traditional comet assay. Finally, we also show that the assay can be performed using a 4× objective (rather than the standard 10× objective for the traditional assay). This adjustment combined with the microarray format makes it possible to capture more than 50 analysable comets in a single image, which can then be automatically analysed using in-house software. Overall, throughput is increased more than 100-fold compared to the traditional assay. Together, the results presented here demonstrate key advances in comet assay technology that improve the throughput, sensitivity, and robustness, thus enabling larger scale clinical and epidemiological studies.

  2. Analysis of the conformation of the 3' major domain of Escherichia coli16S ribosomal RNA using site-directed photoaffinity crosslinking.

    PubMed Central

    Montpetit, A; Payant, C; Nolan, J M; Brakier-Gingras, L

    1998-01-01

    The 3' major domain of Escherichia coli 16S rRNA, which occupies the head of the small ribosomal subunit, is involved in several functions of the ribosome. We have used a site-specific crosslinking procedure to gain further insights into the higher-order structure of this domain. Circularly permuted RNAs were used to introduce an azidophenacyl group at specific positions within the 3' major domain. Crosslinks were generated in a high-ionic strength buffer that has been used for ribosome reconstitution studies and so enables the RNA to adopt a structure recognized by ribosomal proteins. The crosslinking sites were identified by primer extension and confirmed by assessing the mobility of the crosslinked RNA lariats in denaturing polyacrylamide gels. Eight crosslinks were characterized. Among them, one crosslink demonstrates that helix 28 is proximal to the top of helix 34, and two others show that the 1337 region, located in an internal loop at the junction of helices 29, 30, 41, and 42, is proximal to the center of helix 30 and to a segment connecting helix 28 to helix 29. These relationships of vicinity have previously been observed in native 30S subunits, which suggests that the free domain adopts a conformation similar to that within the 30S subunit. Furthermore, crosslinks were obtained in helix 34, which suggest that the upper and lower portions of this helix are in close proximity. PMID:9814765

  3. A New Advanced Backcross Tomato Population Enables High Resolution Leaf QTL Mapping and Gene Identification

    PubMed Central

    Fulop, Daniel; Ranjan, Aashish; Ofner, Itai; Covington, Michael F.; Chitwood, Daniel H.; West, Donelly; Ichihashi, Yasunori; Headland, Lauren; Zamir, Daniel; Maloof, Julin N.; Sinha, Neelima R.

    2016-01-01

    Quantitative Trait Loci (QTL) mapping is a powerful technique for dissecting the genetic basis of traits and species differences. Established tomato mapping populations between domesticated tomato (Solanum lycopersicum) and its more distant interfertile relatives typically follow a near isogenic line (NIL) design, such as the S. pennellii Introgression Line (IL) population, with a single wild introgression per line in an otherwise domesticated genetic background. Here, we report on a new advanced backcross QTL mapping resource for tomato, derived from a cross between the M82 tomato cultivar and S. pennellii. This so-called Backcrossed Inbred Line (BIL) population is comprised of a mix of BC2 and BC3 lines, with domesticated tomato as the recurrent parent. The BIL population is complementary to the existing S. pennellii IL population, with which it shares parents. Using the BILs, we mapped traits for leaf complexity, leaflet shape, and flowering time. We demonstrate the utility of the BILs for fine-mapping QTL, particularly QTL initially mapped in the ILs, by fine-mapping several QTL to single or few candidate genes. Moreover, we confirm the value of a backcrossed population with multiple introgressions per line, such as the BILs, for epistatic QTL mapping. Our work was further enabled by the development of our own statistical inference and visualization tools, namely a heterogeneous hidden Markov model for genotyping the lines, and by using state-of-the-art sparse regression techniques for QTL mapping. PMID:27510891

  4. A Structural Approach to Establishing a Platform Chemistry for the Tunable, Bulk Electron Beam Cross-Linking of Shape Memory Polymer Systems

    PubMed Central

    Hearon, Keith; Besset, Celine J.; Lonnecker, Alexander T.; Ware, Taylor; Voit, Walter E.; Wilson, Thomas S.; Wooley, Karen L.; Maitland, Duncan J.

    2014-01-01

    The synthetic design and thermomechanical characterization of shape memory polymers (SMPs) built from a new polyurethane chemistry that enables facile, bulk and tunable cross-linking of low-molecular weight thermoplastics by electron beam irradiation is reported in this study. SMPs exhibit stimuli-induced geometry changes and are being proposed for applications in numerous fields. We have previously reported a polyurethane SMP system that exhibits the complex processing capabilities of thermoplastic polymers and the mechanical robustness and tunability of thermomechanical properties that are often characteristic of thermoset materials. These previously reported polyurethanes suffer practically because the thermoplastic molecular weights needed to achieve target cross-link densities severely limit high-throughput thermoplastic processing and because thermally unstable radiation-sensitizing additives must be used to achieve high enough cross-link densities to enable desired tunable shape memory behavior. In this study, we demonstrate the ability to manipulate cross-link density in low-molecular weight aliphatic thermoplastic polyurethane SMPs (Mw as low as ~1.5 kDa) without radiation-sensitizing additives by incorporating specific structural motifs into the thermoplastic polymer side chains that we hypothesized would significantly enhance susceptibility to e-beam cross-linking. A custom diol monomer was first synthesized and then implemented in the synthesis of neat thermoplastic polyurethane SMPs that were irradiated at doses ranging from 1 to 500 kGy. Dynamic mechanical analysis (DMA) demonstrated rubbery moduli to be tailorable between 0.1 and 55 MPa, and both DMA and sol/gel analysis results provided fundamental insight into our hypothesized mechanism of electron beam cross-linking, which enables controllable bulk cross-linking to be achieved in highly processable, low-molecular weight thermoplastic shape memory polymers without sensitizing additives. PMID

  5. Cross-linking of Thy-1 glycoproteins or high-affinity IgE receptors induces mast cell activation via different mechanisms.

    PubMed Central

    Dráberová, L; Dráber, P

    1993-01-01

    Rat peritoneal and pleural mast cells and rat basophilic leukemia cells, RBL-2H3, have been previously shown to be activated by Thy-1-specific monoclonal antibodies (mAb). In the present study we investigated the mechanism of Thy-1-mediated activation and compared it with activation induced by cross-linking of the high-affinity IgE receptor. Binding of an IgG Thy-1 x 1-specific mAb, MRCOX7 (OX7), to RBL-2H3 cells and mast cells, and activation of RBL-2H3 by the OX7 were abrogated by pretreatment of the cells with phosphatidyl inositol-specific phospholipase C (PI-PLC). The F(ab')2 fragment of OX7, in contrast to the Fab' fragment, induced cell activation as well as intact OX7 mAb. Cells sensitized with IgE exhibited an increased responsiveness to anti-Thy-1 antibodies suggesting formation of functional complexes of IgE receptor/IgE/Thy-1/anti-Thy-1. Pretreatment of RBL-2H3 cells with cholera toxin potentiated activation induced by IgE+antigen (Ag) and IgE+OX7, but had no effect on activation induced by OX7 antibody alone. Similarly, dexamethasone had no effect on OX7-induced activation but inhibited IgE+Ag- and IgE+OX7-induced activation. Analysis of phosphotyrosine-containing proteins in RBL-2H3 cell lysates revealed that IgE+Ag and IgE+OX7 induced a marked increase in tyrosine phosphorylation of several proteins that were not tyrosine phosphorylated in cells exposed to OX7 mAb alone. Similar results were obtained when RBL-2H3-derived cells, expressing transfected mouse Thy-1.2, were activated with Thy-1.2-specific IgM antibody. The combined data suggest that Thy-1-specific antibodies activate cells by a mechanism that is different from activation induced by cross-linking of high-affinity IgE receptor. Images Figure 5 Figure 6 PMID:7902332

  6. Broadly available imaging devices enable high-quality low-cost photometry.

    PubMed

    Christodouleas, Dionysios C; Nemiroski, Alex; Kumar, Ashok A; Whitesides, George M

    2015-09-15

    This paper demonstrates that, for applications in resource-limited environments, expensive microplate spectrophotometers that are used in many central laboratories for parallel measurement of absorbance of samples can be replaced by photometers based on inexpensive and ubiquitous, consumer electronic devices (e.g., scanners and cell-phone cameras). Two devices, (i) a flatbed scanner operating in transmittance mode and (ii) a camera-based photometer (constructed from a cell phone camera, a planar light source, and a cardboard box), demonstrate the concept. These devices illuminate samples in microtiter plates from one side and use the RGB-based imaging sensors of the scanner/camera to measure the light transmitted to the other side. The broadband absorbance of samples (RGB-resolved absorbance) can be calculated using the RGB color values of only three pixels per microwell. Rigorous theoretical analysis establishes a well-defined relationship between the absorbance spectrum of a sample and its corresponding RGB-resolved absorbance. The linearity and precision of measurements performed with these low-cost photometers on different dyes, which absorb across the range of the visible spectrum, and chromogenic products of assays (e.g., enzymatic, ELISA) demonstrate that these low-cost photometers can be used reliably in a broad range of chemical and biochemical analyses. The ability to perform accurate measurements of absorbance on liquid samples, in parallel and at low cost, would enable testing, typically reserved for well-equipped clinics and laboratories, to be performed in circumstances where resources and expertise are limited.

  7. Broadly available imaging devices enable high-quality low-cost photometry.

    PubMed

    Christodouleas, Dionysios C; Nemiroski, Alex; Kumar, Ashok A; Whitesides, George M

    2015-09-15

    This paper demonstrates that, for applications in resource-limited environments, expensive microplate spectrophotometers that are used in many central laboratories for parallel measurement of absorbance of samples can be replaced by photometers based on inexpensive and ubiquitous, consumer electronic devices (e.g., scanners and cell-phone cameras). Two devices, (i) a flatbed scanner operating in transmittance mode and (ii) a camera-based photometer (constructed from a cell phone camera, a planar light source, and a cardboard box), demonstrate the concept. These devices illuminate samples in microtiter plates from one side and use the RGB-based imaging sensors of the scanner/camera to measure the light transmitted to the other side. The broadband absorbance of samples (RGB-resolved absorbance) can be calculated using the RGB color values of only three pixels per microwell. Rigorous theoretical analysis establishes a well-defined relationship between the absorbance spectrum of a sample and its corresponding RGB-resolved absorbance. The linearity and precision of measurements performed with these low-cost photometers on different dyes, which absorb across the range of the visible spectrum, and chromogenic products of assays (e.g., enzymatic, ELISA) demonstrate that these low-cost photometers can be used reliably in a broad range of chemical and biochemical analyses. The ability to perform accurate measurements of absorbance on liquid samples, in parallel and at low cost, would enable testing, typically reserved for well-equipped clinics and laboratories, to be performed in circumstances where resources and expertise are limited. PMID:26241835

  8. Cross-linked branching nanohybrid polymer electrolyte with monodispersed TiO2 nanoparticles for high performance lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Ma, Cheng; Zhang, Jinfang; Xu, Mingquan; Xia, Qingbing; Liu, Jiatu; Zhao, Shuai; Chen, Libao; Pan, Anqiang; Ivey, Douglas G.; Wei, Weifeng

    2016-06-01

    Nanohybrid polymer electrolytes (NHPE) with ceramic particles have attracted significant attention owing to their improvement in electrochemical performance. However, particle aggregation and weak nanoparticle/polymer matrix interaction restrict their further application in lithium-ion batteries (LIBs). We demonstrate a facile in-situ polymerization/crystallization method to synthesize a homogeneous TiO2-grafted NHPE with a cross-linked branching structure, comprised of ion-conducting poly(ethylene glycol) methyl ether methacrylate (PEGMEM) and non-polar stearyl methacrylate (SMA). This technique is different from existing methods of blending functionalized ceramic particles into the polymer matrix. Highly monodispersed TiO2 nanocrystals enhance the effective interfacial interactions between particles and polymer matrix, which suppress the crystallization of ethylene oxide (EO) groups and facilitate forming continuously interconnected ion-conducting channels. Moreover, an increased dissociation degree of Li salt can also be achieved. The TiO2-grafted NHPE exhibits superior electrochemical properties with an ionic conductivity of 1.1 × 10-4 S cm-1 at 30 °C, a high lithium ion transference number and excellent interfacial compatibility with the lithium electrode. In particular, a lithium-ion battery based on TiO2-grafted NHPE demonstrates good C-rate performance, as well as excellent cycling stability with an initial discharge capacity of 153.5 mAh g-1 and a capacity retention of 96% after 300 cycles at 1 C (80 °C).

  9. Plasma Doping - Enabling Technology for High Dose Logic and Memory Applications

    SciTech Connect

    Miller, T.; Godet, L.; Papasouliotis, G. D.; Singh, V.

    2008-11-03

    As logic and memory device dimensions shrink with each generation, there are more high dose implants at lower energies. Examples include dual poly gate (also referred to as counter-doped poly), elevated source drain and contact plug implants. Plasma Doping technology throughput and dopant profile benefits at these ultra high dose and lower energy conditions have been well established [1,2,3]. For the first time a production-worthy plasma doping implanter, the VIISta PLAD tool, has been developed with unique architecture suited for precise and repeatable dopant placement. Critical elements of the architecture include pulsed DC wafer bias, closed-loop dosimetry and a uniform low energy, high density plasma source. In this paper key performance metrics such as dose uniformity, dose repeatability and dopant profile control will be presented that demonstrate the production-worthiness of the VIISta PLAD tool for several high dose applications.

  10. A Robust Highly Aligned DNA Nanowire Array-Enabled Lithography for Graphene Nanoribbon Transistors.

    PubMed

    Kang, Seok Hee; Hwang, Wan Sik; Lin, Zhiqun; Kwon, Se Hun; Hong, Suck Won

    2015-12-01

    Because of its excellent charge carrier mobility at the Dirac point, graphene possesses exceptional properties for high-performance devices. Of particular interest is the potential use of graphene nanoribbons or graphene nanomesh for field-effect transistors. Herein, highly aligned DNA nanowire arrays were crafted by flow-assisted self-assembly of a drop of DNA aqueous solution on a flat polymer substrate. Subsequently, they were exploited as "ink" and transfer-printed on chemical vapor deposited (CVD)-grown graphene substrate. The oriented DNA nanowires served as the lithographic resist for selective removal of graphene, forming highly aligned graphene nanoribbons. Intriguingly, these graphene nanoribbons can be readily produced over a large area (i.e., millimeter scale) with a high degree of feature-size controllability and a low level of defects, rendering the fabrication of flexible two terminal devices and field-effect transistors.

  11. High performance Li-ion sulfur batteries enabled by intercalation chemistry.

    PubMed

    Lv, Dongping; Yan, Pengfei; Shao, Yuyan; Li, Qiuyan; Ferrara, Seth; Pan, Huilin; Graff, Gordon L; Polzin, Bryant; Wang, Chongmin; Zhang, Ji-Guang; Liu, Jun; Xiao, Jie

    2015-09-11

    The unstable interface of lithium metal in high energy density Li sulfur (Li-S) batteries raises concerns of poor cycling, low efficiency and safety issues, which may be addressed by using intercalation types of anode. Herein, a new prototype of Li-ion sulfur battery with high performance has been demonstrated by coupling a graphite anode with a sulfur cathode (2 mA h cm(-2)) after successfully addressing the interface issue of graphite in an ether based electrolyte. PMID:26214797

  12. High performance Li-ion sulfur batteries enabled by intercalation chemistry.

    PubMed

    Lv, Dongping; Yan, Pengfei; Shao, Yuyan; Li, Qiuyan; Ferrara, Seth; Pan, Huilin; Graff, Gordon L; Polzin, Bryant; Wang, Chongmin; Zhang, Ji-Guang; Liu, Jun; Xiao, Jie

    2015-09-11

    The unstable interface of lithium metal in high energy density Li sulfur (Li-S) batteries raises concerns of poor cycling, low efficiency and safety issues, which may be addressed by using intercalation types of anode. Herein, a new prototype of Li-ion sulfur battery with high performance has been demonstrated by coupling a graphite anode with a sulfur cathode (2 mA h cm(-2)) after successfully addressing the interface issue of graphite in an ether based electrolyte.

  13. Cross-Linking Aromatic Polymers With Ionizing Radiation

    NASA Technical Reports Server (NTRS)

    Bell, Vernon L.; Havens, Stephen J.

    1987-01-01

    Resistance to heat and solvents increased. Certain aromatic polymers containing radiation-sensitive methylene groups cross-linked through methylene groups upon exposure to ionizing radiation. Cross-linked polymers resistant to most organic solvents and generally more resistant to high temperatures, with less tendency to creep under load. No significant embrittlement of parts fabricated from these polymers when degree of cross-linking, as controlled by irradiation dose, kept at moderate level.

  14. Hybrid Microscopy: Enabling Inexpensive High-Performance Imaging through Combined Physical and Optical Magnifications.

    PubMed

    Zhang, Yu Shrike; Chang, Jae-Byum; Alvarez, Mario Moisés; Trujillo-de Santiago, Grissel; Aleman, Julio; Batzaya, Byambaa; Krishnadoss, Vaishali; Ramanujam, Aishwarya Aravamudhan; Kazemzadeh-Narbat, Mehdi; Chen, Fei; Tillberg, Paul W; Dokmeci, Mehmet Remzi; Boyden, Edward S; Khademhosseini, Ali

    2016-01-01

    To date, much effort has been expended on making high-performance microscopes through better instrumentation. Recently, it was discovered that physical magnification of specimens was possible, through a technique called expansion microscopy (ExM), raising the question of whether physical magnification, coupled to inexpensive optics, could together match the performance of high-end optical equipment, at a tiny fraction of the price. Here we show that such "hybrid microscopy" methods--combining physical and optical magnifications--can indeed achieve high performance at low cost. By physically magnifying objects, then imaging them on cheap miniature fluorescence microscopes ("mini-microscopes"), it is possible to image at a resolution comparable to that previously attainable only with benchtop microscopes that present costs orders of magnitude higher. We believe that this unprecedented hybrid technology that combines expansion microscopy, based on physical magnification, and mini-microscopy, relying on conventional optics--a process we refer to as Expansion Mini-Microscopy (ExMM)--is a highly promising alternative method for performing cost-effective, high-resolution imaging of biological samples. With further advancement of the technology, we believe that ExMM will find widespread applications for high-resolution imaging particularly in research and healthcare scenarios in undeveloped countries or remote places. PMID:26975883

  15. Hybrid Microscopy: Enabling Inexpensive High-Performance Imaging through Combined Physical and Optical Magnifications

    PubMed Central

    Zhang, Yu Shrike; Chang, Jae-Byum; Alvarez, Mario Moisés; Trujillo-de Santiago, Grissel; Aleman, Julio; Batzaya, Byambaa; Krishnadoss, Vaishali; Ramanujam, Aishwarya Aravamudhan; Kazemzadeh-Narbat, Mehdi; Chen, Fei; Tillberg, Paul W.; Dokmeci, Mehmet Remzi; Boyden, Edward S.; Khademhosseini, Ali

    2016-01-01

    To date, much effort has been expended on making high-performance microscopes through better instrumentation. Recently, it was discovered that physical magnification of specimens was possible, through a technique called expansion microscopy (ExM), raising the question of whether physical magnification, coupled to inexpensive optics, could together match the performance of high-end optical equipment, at a tiny fraction of the price. Here we show that such “hybrid microscopy” methods—combining physical and optical magnifications—can indeed achieve high performance at low cost. By physically magnifying objects, then imaging them on cheap miniature fluorescence microscopes (“mini-microscopes”), it is possible to image at a resolution comparable to that previously attainable only with benchtop microscopes that present costs orders of magnitude higher. We believe that this unprecedented hybrid technology that combines expansion microscopy, based on physical magnification, and mini-microscopy, relying on conventional optics—a process we refer to as Expansion Mini-Microscopy (ExMM)—is a highly promising alternative method for performing cost-effective, high-resolution imaging of biological samples. With further advancement of the technology, we believe that ExMM will find widespread applications for high-resolution imaging particularly in research and healthcare scenarios in undeveloped countries or remote places. PMID:26975883

  16. Microfluidic-Enabled Print-to-Screen Platform for High-Throughput Screening of Combinatorial Chemotherapy.

    PubMed

    Ding, Yuzhe; Li, Jiannan; Xiao, Wenwu; Xiao, Kai; Lee, Joyce; Bhardwaj, Urvashi; Zhu, Zijie; Digiglio, Philip; Yang, Gaomai; Lam, Kit S; Pan, Tingrui

    2015-10-20

    Since the 1960s, combination chemotherapy has been widely utilized as a standard method to treat cancer. However, because of the potentially enormous number of drug candidates and combinations, conventional identification methods of the effective drug combinations are usually associated with significantly high operational costs, low throughput screening, laborious and time-consuming procedures, and ethical concerns. In this paper, we present a low-cost, high-efficiency microfluidic print-to-screen (P2S) platform, which integrates combinatorial screening with biomolecular printing for high-throughput screening of anticancer drug combinations. This P2S platform provides several distinct advantages and features, including automatic combinatorial printing, high-throughput parallel drug screening, modular disposable cartridge, and biocompatibility, which can potentially speed up the entire discovery cycle of potent drug combinations. Microfluidic impact printing utilizing plug-and-play microfluidic cartridges is experimentally characterized with controllable droplet volume and accurate positioning. Furthermore, the combinatorial print-to-screen assay is demonstrated in a proof-of-concept biological experiment which can identify the positive hits among the entire drug combination library in a parallel and rapid manner. Overall, this microfluidic print-to-screen platform offers a simple, low-cost, high-efficiency solution for high-throughput large-scale combinatorial screening and can be applicable for various emerging applications in drug cocktail discovery. PMID:26334956

  17. Hybrid Microscopy: Enabling Inexpensive High-Performance Imaging through Combined Physical and Optical Magnifications.

    PubMed

    Zhang, Yu Shrike; Chang, Jae-Byum; Alvarez, Mario Moisés; Trujillo-de Santiago, Grissel; Aleman, Julio; Batzaya, Byambaa; Krishnadoss, Vaishali; Ramanujam, Aishwarya Aravamudhan; Kazemzadeh-Narbat, Mehdi; Chen, Fei; Tillberg, Paul W; Dokmeci, Mehmet Remzi; Boyden, Edward S; Khademhosseini, Ali

    2016-01-01

    To date, much effort has been expended on making high-performance microscopes through better instrumentation. Recently, it was discovered that physical magnification of specimens was possible, through a technique called expansion microscopy (ExM), raising the question of whether physical magnification, coupled to inexpensive optics, could together match the performance of high-end optical equipment, at a tiny fraction of the price. Here we show that such "hybrid microscopy" methods--combining physical and optical magnifications--can indeed achieve high performance at low cost. By physically magnifying objects, then imaging them on cheap miniature fluorescence microscopes ("mini-microscopes"), it is possible to image at a resolution comparable to that previously attainable only with benchtop microscopes that present costs orders of magnitude higher. We believe that this unprecedented hybrid technology that combines expansion microscopy, based on physical magnification, and mini-microscopy, relying on conventional optics--a process we refer to as Expansion Mini-Microscopy (ExMM)--is a highly promising alternative method for performing cost-effective, high-resolution imaging of biological samples. With further advancement of the technology, we believe that ExMM will find widespread applications for high-resolution imaging particularly in research and healthcare scenarios in undeveloped countries or remote places.

  18. Hybrid Microscopy: Enabling Inexpensive High-Performance Imaging through Combined Physical and Optical Magnifications

    NASA Astrophysics Data System (ADS)

    Zhang, Yu Shrike; Chang, Jae-Byum; Alvarez, Mario Moisés; Trujillo-de Santiago, Grissel; Aleman, Julio; Batzaya, Byambaa; Krishnadoss, Vaishali; Ramanujam, Aishwarya Aravamudhan; Kazemzadeh-Narbat, Mehdi; Chen, Fei; Tillberg, Paul W.; Dokmeci, Mehmet Remzi; Boyden, Edward S.; Khademhosseini, Ali

    2016-03-01

    To date, much effort has been expended on making high-performance microscopes through better instrumentation. Recently, it was discovered that physical magnification of specimens was possible, through a technique called expansion microscopy (ExM), raising the question of whether physical magnification, coupled to inexpensive optics, could together match the performance of high-end optical equipment, at a tiny fraction of the price. Here we show that such “hybrid microscopy” methods—combining physical and optical magnifications—can indeed achieve high performance at low cost. By physically magnifying objects, then imaging them on cheap miniature fluorescence microscopes (“mini-microscopes”), it is possible to image at a resolution comparable to that previously attainable only with benchtop microscopes that present costs orders of magnitude higher. We believe that this unprecedented hybrid technology that combines expansion microscopy, based on physical magnification, and mini-microscopy, relying on conventional optics—a process we refer to as Expansion Mini-Microscopy (ExMM)—is a highly promising alternative method for performing cost-effective, high-resolution imaging of biological samples. With further advancement of the technology, we believe that ExMM will find widespread applications for high-resolution imaging particularly in research and healthcare scenarios in undeveloped countries or remote places.

  19. Cross-linked polyelectrolyte for direct methanol fuel cells applications based on a novel sulfonated cross-linker

    NASA Astrophysics Data System (ADS)

    Li, Mingyu; Zhang, Gang; Xu, Shuai; Zhao, Chengji; Han, Miaomiao; Zhang, Liyuan; Jiang, Hao; Liu, Zhongguo; Na, Hui

    2014-06-01

    A novel type of cross-linked proton exchange membrane of lower methanol permeation and high proton conductivity is prepared, based on a newly synthesized sulfonated cross-linker: carboxyl terminated benzimidazole trimer bearing sulfonic acid groups (s-BI). Compared to membranes cross-linked with non-sulfonated cross-linker (BI), SPEEK/s-BI-n membranes show higher IEC values and proton conductivities. Meanwhile, oxidative stability and mechanical property of SPEEK/s-BI-n membranes are obviously improved. Among SPEEK/s-BI-n membranes, SPEEK/s-BI-2 exhibits high proton conductivity, low swelling ratio (0.122 S cm-1 and 15.2% at 60 °C, respectively) and low methanol permeability coefficient. These results imply that the cross-linked membranes prepared with the newly sulfonated cross-linker are promising for the direct methanol fuel cells (DMFCs) application.

  20. High-Performance Silicon Battery Anodes Enabled by Engineering Graphene Assemblies.

    PubMed

    Zhou, Min; Li, Xianglong; Wang, Bin; Zhang, Yunbo; Ning, Jing; Xiao, Zhichang; Zhang, Xinghao; Chang, Yanhong; Zhi, Linjie

    2015-09-01

    We propose a novel material/electrode design formula and develop an engineered self-supporting electrode configuration, namely, silicon nanoparticle impregnated assemblies of templated carbon-bridged oriented graphene. We have demonstrated their use as binder-free lithium-ion battery anodes with exceptional lithium storage performances, simultaneously attaining high gravimetric capacity (1390 mAh g(-1) at 2 A g(-1) with respect to the total electrode weight), high volumetric capacity (1807 mAh cm(-3) that is more than three times that of graphite anodes), remarkable rate capability (900 mAh g(-1) at 8 A g(-1)), excellent cyclic stability (0.025% decay per cycle over 200 cycles), and competing areal capacity (as high as 4 and 6 mAh cm(-2) at 15 and 3 mA cm(-2), respectively). Such combined level of performance is attributed to the templated carbon bridged oriented graphene assemblies involved. This engineered graphene bulk assemblies not only create a robust bicontinuous network for rapid transport of both electrons and lithium ions throughout the electrode even at high material mass loading but also allow achieving a substantially high material tap density (1.3 g cm(-3)). Coupled with a simple and flexible fabrication protocol as well as practically scalable raw materials (e.g., silicon nanoparticles and graphene oxide), the material/electrode design developed would propagate new and viable battery material/electrode design principles and opportunities for energy storage systems with high-energy and high-power characteristics.

  1. High rate lithium-sulfur battery enabled by sandwiched single ion conducting polymer electrolyte

    PubMed Central

    Sun, Yubao; Li, Gai; Lai, Yuanchu; Zeng, Danli; Cheng, Hansong

    2016-01-01

    Lithium-sulfur batteries are highly promising for electric energy storage with high energy density, abundant resources and low cost. However, the battery technologies have often suffered from a short cycle life and poor rate stability arising from the well-known “polysulfide shuttle” effect. Here, we report a novel cell design by sandwiching a sp3 boron based single ion conducting polymer electrolyte film between two carbon films to fabricate a composite separator for lithium-sulfur batteries. The dense negative charges uniformly distributed in the electrolyte membrane inherently prohibit transport of polysulfide anions formed in the cathode inside the polymer matrix and effectively blocks polysulfide shuttling. A battery assembled with the composite separator exhibits a remarkably long cycle life at high charge/discharge rates. PMID:26898772

  2. High rate lithium-sulfur battery enabled by sandwiched single ion conducting polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Sun, Yubao; Li, Gai; Lai, Yuanchu; Zeng, Danli; Cheng, Hansong

    2016-02-01

    Lithium-sulfur batteries are highly promising for electric energy storage with high energy density, abundant resources and low cost. However, the battery technologies have often suffered from a short cycle life and poor rate stability arising from the well-known “polysulfide shuttle” effect. Here, we report a novel cell design by sandwiching a sp3 boron based single ion conducting polymer electrolyte film between two carbon films to fabricate a composite separator for lithium-sulfur batteries. The dense negative charges uniformly distributed in the electrolyte membrane inherently prohibit transport of polysulfide anions formed in the cathode inside the polymer matrix and effectively blocks polysulfide shuttling. A battery assembled with the composite separator exhibits a remarkably long cycle life at high charge/discharge rates.

  3. High rate lithium-sulfur battery enabled by sandwiched single ion conducting polymer electrolyte.

    PubMed

    Sun, Yubao; Li, Gai; Lai, Yuanchu; Zeng, Danli; Cheng, Hansong

    2016-02-22

    Lithium-sulfur batteries are highly promising for electric energy storage with high energy density, abundant resources and low cost. However, the battery technologies have often suffered from a short cycle life and poor rate stability arising from the well-known "polysulfide shuttle" effect. Here, we report a novel cell design by sandwiching a sp(3) boron based single ion conducting polymer electrolyte film between two carbon films to fabricate a composite separator for lithium-sulfur batteries. The dense negative charges uniformly distributed in the electrolyte membrane inherently prohibit transport of polysulfide anions formed in the cathode inside the polymer matrix and effectively blocks polysulfide shuttling. A battery assembled with the composite separator exhibits a remarkably long cycle life at high charge/discharge rates.

  4. Click Reaction on Solid Phase Enables High Fidelity Synthesis of Nucleobase-Modified DNA.

    PubMed

    Tolle, Fabian; Rosenthal, Malte; Pfeiffer, Franziska; Mayer, Günter

    2016-03-16

    The post-synthetic functionalization of nucleic acids via click chemistry (CuAAC) has seen tremendous implementation, extending the applicability of nucleobase-modified nucleic acids in fields like fluorescent labeling, nanotechnology, and in vitro selection. However, the production of large quantities of high-density functionalized material via solid phase synthesis has been hampered by oxidative by-product formation associated with the alkaline workup conditions. Herein, we describe a rapid and cost-effective protocol for the high fidelity large-scale production of nucleobase-modified nucleic acids, exemplified with a recently described nucleobase-modified aptamer.

  5. Click Reaction on Solid Phase Enables High Fidelity Synthesis of Nucleobase-Modified DNA.

    PubMed

    Tolle, Fabian; Rosenthal, Malte; Pfeiffer, Franziska; Mayer, Günter

    2016-03-16

    The post-synthetic functionalization of nucleic acids via click chemistry (CuAAC) has seen tremendous implementation, extending the applicability of nucleobase-modified nucleic acids in fields like fluorescent labeling, nanotechnology, and in vitro selection. However, the production of large quantities of high-density functionalized material via solid phase synthesis has been hampered by oxidative by-product formation associated with the alkaline workup conditions. Herein, we describe a rapid and cost-effective protocol for the high fidelity large-scale production of nucleobase-modified nucleic acids, exemplified with a recently described nucleobase-modified aptamer. PMID:26850226

  6. Microbes encapsulated within crosslinkable polymers

    DOEpatents

    Chidambaram, Devicharan; Liu, Ying; Rafailovich, Miriam H

    2013-02-05

    The invention relates to porous films comprising crosslinked electrospun hydrogel fibers. Viable microbes are encapsulated within the crosslinked electrospun hydrogel fibers. The crosslinked electrospun hydrogel fibers are water insoluble and permeable. The invention also relates to methods of making and using such porous films.

  7. Enabling High-Dimensional Hierarchical Uncertainty Quantification by ANOVA and Tensor-Train Decomposition

    SciTech Connect

    Zhang, Zheng; Yang, Xiu; Oseledets, Ivan; Karniadakis, George E.; Daniel, Luca

    2015-01-31

    Hierarchical uncertainty quantification can reduce the computational cost of stochastic circuit simulation by employing spectral methods at different levels. This paper presents an efficient framework to simulate hierarchically some challenging stochastic circuits/systems that include high-dimensional subsystems. Due to the high parameter dimensionality, it is challenging to both extract surrogate models at the low level of the design hierarchy and to handle them in the high-level simulation. In this paper, we develop an efficient analysis of variance-based stochastic circuit/microelectromechanical systems simulator to efficiently extract the surrogate models at the low level. In order to avoid the curse of dimensionality, we employ tensor-train decomposition at the high level to construct the basis functions and Gauss quadrature points. As a demonstration, we verify our algorithm on a stochastic oscillator with four MEMS capacitors and 184 random parameters. This challenging example is efficiently simulated by our simulator at the cost of only 10min in MATLAB on a regular personal computer.

  8. Sulphur-impregnated flow cathode to enable high-energy-density lithium flow batteries

    NASA Astrophysics Data System (ADS)

    Chen, Hongning; Zou, Qingli; Liang, Zhuojian; Liu, Hao; Li, Quan; Lu, Yi-Chun

    2015-01-01

    Redox flow batteries are promising technologies for large-scale electricity storage, but have been suffering from low energy density and low volumetric capacity. Here we report a flow cathode that exploits highly concentrated sulphur-impregnated carbon composite, to achieve a catholyte volumetric capacity 294 Ah l-1 with long cycle life (>100 cycles), high columbic efficiency (>90%, 100 cycles) and high energy efficiency (>80%, 100 cycles). The demonstrated catholyte volumetric capacity is five times higher than the all-vanadium flow batteries (60 Ah l-1) and 3-6 times higher than the demonstrated lithium-polysulphide approaches (50-117 Ah l-1). Pseudo-in situ impedance and microscopy characterizations reveal superior electrochemical and morphological reversibility of the sulphur redox reactions. Our approach of exploiting sulphur-impregnated carbon composite in the flow cathode creates effective interfaces between the insulating sulphur and conductive carbon-percolating network and offers a promising direction to develop high-energy-density flow batteries.

  9. Towards enabling femtosecond helicity-dependent spectroscopy with high-harmonic sources.

    PubMed

    Lambert, G; Vodungbo, B; Gautier, J; Mahieu, B; Malka, V; Sebban, S; Zeitoun, P; Luning, J; Perron, J; Andreev, A; Stremoukhov, S; Ardana-Lamas, F; Dax, A; Hauri, C P; Sardinha, A; Fajardo, M

    2015-01-01

    Recent advances in high-harmonic generation gave rise to soft X-ray pulses with higher intensity, shorter duration and higher photon energy. One of the remaining shortages of this source is its restriction to linear polarization, since the yield of generation of elliptically polarized high harmonics has been low so far. We here show how this limitation is overcome by using a cross-polarized two-colour laser field. With this simple technique, we reach high degrees of ellipticity (up to 75%) with efficiencies similar to classically generated linearly polarized harmonics. To demonstrate these features and to prove the capacity of our source for applications, we measure the X-ray magnetic circular dichroism (XMCD) effect of nickel at the M2,3 absorption edge around 67 eV. There results open up the way towards femtosecond time-resolved experiments using high harmonics exploiting the powerful element-sensitive XMCD effect and resolving the ultrafast magnetization dynamics of individual components in complex materials. PMID:25649329

  10. Chlorine resistant glutaraldehyde crosslinked polyelectrolyte multilayer membranes for desalination.

    PubMed

    Cho, Kwun Lun; Hill, Anita J; Caruso, Frank; Kentish, Sandra E

    2015-05-01

    Crosslinked polyelectrolyte multilayer membranes are synthesized with salt rejection values approaching those of commercial desalination membranes, but with increased chlorine resistance. The membranes are fabricated directly onto porous commercial substrates. Subsequent crosslinking of the polycation layers with glutaraldehyde leads to NaCl rejections of up to 97%, while the incorporation of a highly sulfonated polysulfone polyanion leads to high chlorine resistance.

  11. Collagen cross-linking and resorption: effect of glutaraldehyde concentration.

    PubMed

    Roe, S C; Milthorpe, B K; Schindhelm, K

    1990-12-01

    Cross-linked collagen bioprostheses usually are designed to be inert and nonresorbable, resulting in fatigue and wear failure in high-stress environments. Eventual replacement of the implant, although minimizing strength loss during resorption, would result in a graft with reparative ability. Kangaroo tail tendon (KTT) partially cross-linked with glutaraldehyde (GA) was evaluated in vitro for resistance to bacterial collagenase digestion and in vivo for biocompatibility and resorbability in an intramuscular implant assay. Cross-linking was quantified by thermal denaturation studies. Incomplete cross-linking was achieved with concentrations of GA less than 0.1% (w/v). KTT cross-linked in greater than or equal to 0.05% GA were collagenase resistant being incompletely digested after 240 h. Cross-linking of KTT with low concentrations of GA resulted in partial collagenase resistance and slowed resorption. PMID:2126427

  12. Synthesis and characterization of poly(maleic acid)-grafted crosslinked chitosan nanomaterial with high uptake and selectivity for Hg(II) sorption.

    PubMed

    Ge, Huacai; Hua, Tingting

    2016-11-20

    Chitosan-poly(maleic acid) nanomaterial (PMACS) with the size of 400-900nm was synthesized by grafting poly(maleic acid) onto chitosan and then crosslinking with glutaraldehyde. The synthesis conditions were optimized. The structure and morphology of PMACS were characterized by FT-IR, XRD, SEM and TGA. PMACS was used to adsorb some heavy metal ions such as Hg(II), Pb(II), Cu(II), Cd(II), Co(II), and Zn(II). The results indicated that PMACS had selectivity for Hg(II) sorption. The effects of various variables for sorption of Hg(II) were further explored. The maximum capacity for Hg(II) sorption was found to be 1044mgg(-1) at pH 6.0, which could compare with the maximal value of the recently reported other sorbents. The sorption followed the pseudo-second-order kinetics and Langmuir isotherm models. The rising of temperature benefited the uptake and the sorption was a spontaneous chemical process. The sorbent could be reused with EDTA. Hence, the nanomaterial would be used as a selective and high uptake sorbent in the removal of Hg(II) from effluents.

  13. Cross-linked enzyme aggregates of Mung bean epoxide hydrolases: a highly active, stable and recyclable biocatalyst for asymmetric hydrolysis of epoxides.

    PubMed

    Yu, Chun-Yang; Li, Xiao-Feng; Lou, Wen-Yong; Zong, Min-Hua

    2013-06-20

    A highly active and stable cross-linked enzyme aggregates (CLEAs) of epoxide hydrolases (EHs) from Mung bean, which plays a crucial role in synthesis of valuable enantiopure diols, were successfully prepared and characterized. Under the optimum preparation conditions, the activity recovery of CLEAs recorded 92%. The CLEAs were more efficient than the free enzyme in catalyzing asymmetric hydrolysis of styrene oxide to (R)-1-phenyl-1,2-ethanediol in organic solvent-containing biphasic system. The biocatalytic reaction performed in n-hexane/buffer biphasic system had a clearly faster initial reaction rate, much higher product yield and product e.e. value than that in aqueous medium. Moreover, the optimal volume ratio of n-hexane to buffer, reaction temperature, buffer pH value and substrate concentration for the enzymatic hydrolysis were found to be 1:1, 40 °C, 7.5 and 30 mM, respectively, under which the initial reaction rate, product yield and product e.e. value were 13.26 mM/h, 46% and 93.5%, respectively. The CLEAs retained more than 50% of their initial activity after 8 batches of re-use in phosphate buffer and maintained 53% of their original activity after 8 reaction cycle in biphasic system. The efficient biocatalytic process with CLEAs proved to be feasible on a 250-mL preparative scale, exhibiting great potential for asymmetric synthesis of chiral diols.

  14. Combinatorial and high-throughput screening of the effect of siloxane composition on the surface properties of crosslinked siloxane-polyurethane coatings.

    PubMed

    Ekin, Abdullah; Webster, Dean C

    2007-01-01

    Libraries of siloxane-polyurethane coatings were designed, formulated, and screened using high-throughput experimentation. Four independent variables that were analyzed were the molecular weight of poly(dimethylsiloxane) (PDMS), presence or absence of poly(epsilon-caprolactone) (PCL) blocks attached to the PDMS backbone, the length of the PCL blocks, and the siloxane polymer level in the coating formulations. In addition to the siloxane libraries (3-aminopropyl-terminated PDMS and poly(epsilon-caprolactone)-poly(dimethylsiloxane)-poly(epsilon-caprolactone) (PCL-PDMS-PCL) triblock copolymers), the coating formulation included a trifunctional isocyanate crosslinker, trifunctional poly(epsilon-caprolactone) polyol, 2,4-pentanedione (pot-life extender), dibutyltin diacetate (catalyst), and a blend of solvents. The resulting coatings were analyzed for their surface energy and pseudobarnacle adhesion both before and after aging the coatings for 30 days in water. The water and methylene iodide contact angle averages increase with increasing molecular weight of PDMS. Coatings prepared from PCL-PDMS-PCL triblock copolymers have lower surface energies than coatings prepared from 3-aminopropyl-terminated PDMS; however, lower pseudobarnacle adhesion results were obtained for the coatings prepared from 3-aminopropyl-terminated PDMS than coatings prepared from PCL-PDMS-PCL triblock copolymers. The siloxane polymer level in the coating formulations does not have a significant effect on the surface energy of the coatings, but it resulted in higher pseudobarnacle adhesion. PMID:17206846

  15. Preparation of porous polymer monolithic column using functionalized graphene oxide as a functional crosslinker for high performance liquid chromatography separation of small molecules.

    PubMed

    Li, Yaping; Qi, Li; Ma, Huimin

    2013-09-21

    A newly developed porous polymer monolith was prepared through copolymerization of 3-(trimethoxysilyl)propylmethacrylate modified graphene oxide with glycidyl methacrylate and ethylene dimethacrylate as a functional crosslinker, which was synthesized through silanization reaction of graphene oxide prepared by Hummers method with 3-(trimethoxysilyl)propylmethacrylate. The monolith was characterized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, scanning electron microscopy, mercury intrusion porosimetry and nitrogen adsorption measurement. The monolith column was applied as the stationary phase of high performance liquid chromatography and its chromatographic performance was evaluated by separation of small molecules in the isocratic reversed-phase mode. The chromatograms of hydrophobic steroids and polar aromatic amines on the prepared monolith displayed the enhanced separation performance over those on the parent monolith. The reproducibility of the column was less than 3.5% in terms of relative standard deviation of retention time. The results demonstrate that copolymerization of functionalized graphene oxide into porous polymer monolith was an effective tool for chromatography separation enhancement of small molecules in an isocratic mode. PMID:23884304

  16. Effects of vitamin E blending on plastic deformation mechanisms of highly crosslinked ultrahigh molecular weight polyethylene (HXL-UHMWPE) in total hip arthroplasty.

    PubMed

    Takahashi, Yasuhito; Yamamoto, Kengo; Pezzotti, Giuseppe

    2015-03-01

    The molecular mobility and crystalline texture development in highly crosslinked ultrahigh molecular weight polyethylene (HXL-UHMWPE) blended with antioxidant vitamin E (VE, dl-α-tocopherol) were studied via uniaxial compression at room temperature by means of confocal/polarized Raman spectroscopy. The results were compared to morphological analyses under the same compression conditions performed on HXL-UHMWPE prepared in exactly the same way but blending VE into the polyethylene resin (VE-free HXL-UHMWPE). These comparative analyses allow us to evaluate the physical role of VE in morphological alterations of HXL-UHMWPE induced by compression deformation, which can greatly affect its micromechanical behavior. Molecular rearrangement and phase transitions in crystalline and non-crystalline phase, i.e. amorphous and intermediate (third) phase, were found to be part of a reconstruction process after plastic deformation in the samples. Although VE-blended HXL-UHMWPE exhibited more pronounced molecular mobility, as evidenced by its significant deformation-induced texturing, crystallinity change was totally inhibited by the presence of VE during deformation. On the other hand, amorphous-to-intermediate phase transition was confirmed. VE-free HXL-UHMWPE also presented significant crystallization after deformation, but its surface texture evolution occurred to a much lesser extent. This study suggests that the addition of VE induced earlier activation of compression deformation modes in crystalline and non-crystalline phases (e.g. chain slip, interlamellar shear and rotation) due to an increase in polyethylene chain mobility.

  17. Synthesis and characterization of poly(maleic acid)-grafted crosslinked chitosan nanomaterial with high uptake and selectivity for Hg(II) sorption.

    PubMed

    Ge, Huacai; Hua, Tingting

    2016-11-20

    Chitosan-poly(maleic acid) nanomaterial (PMACS) with the size of 400-900nm was synthesized by grafting poly(maleic acid) onto chitosan and then crosslinking with glutaraldehyde. The synthesis conditions were optimized. The structure and morphology of PMACS were characterized by FT-IR, XRD, SEM and TGA. PMACS was used to adsorb some heavy metal ions such as Hg(II), Pb(II), Cu(II), Cd(II), Co(II), and Zn(II). The results indicated that PMACS had selectivity for Hg(II) sorption. The effects of various variables for sorption of Hg(II) were further explored. The maximum capacity for Hg(II) sorption was found to be 1044mgg(-1) at pH 6.0, which could compare with the maximal value of the recently reported other sorbents. The sorption followed the pseudo-second-order kinetics and Langmuir isotherm models. The rising of temperature benefited the uptake and the sorption was a spontaneous chemical process. The sorbent could be reused with EDTA. Hence, the nanomaterial would be used as a selective and high uptake sorbent in the removal of Hg(II) from effluents. PMID:27561493

  18. "Water-in-salt" electrolyte enables high-voltage aqueous lithium-ion chemistries.

    PubMed

    Suo, Liumin; Borodin, Oleg; Gao, Tao; Olguin, Marco; Ho, Janet; Fan, Xiulin; Luo, Chao; Wang, Chunsheng; Xu, Kang

    2015-11-20

    Lithium-ion batteries raise safety, environmental, and cost concerns, which mostly arise from their nonaqueous electrolytes. The use of aqueous alternatives is limited by their narrow electrochemical stability window (1.23 volts), which sets an intrinsic limit on the practical voltage and energy output. We report a highly concentrated aqueous electrolyte whose window was expanded to ~3.0 volts with the formation of an electrode-electrolyte interphase. A full lithium-ion battery of 2.3 volts using such an aqueous electrolyte was demonstrated to cycle up to 1000 times, with nearly 100% coulombic efficiency at both low (0.15 coulomb) and high (4.5 coulombs) discharge and charge rates.

  19. Using High-Speed WANs and Network Data Caches to Enable Remote and Distributed Visualization

    SciTech Connect

    Bethel, Wes; Lau, Stephen; Tierney, Brian; Lee, Jason; Gunter, Dan

    2000-04-18

    Visapult is a prototype application and framework for remote visualization of large scientific datasets. We approach the technical challenges of tera-scale visualization with a unique architecture that employs high speed WANs and network data caches for data staging and transmission. This architecture allows for the use of available cache and compute resources at arbitrary locations on the network. High data throughput rates and network utilization are achieved by parallelizing I/O at each stage in the application, and by pipe-lining the visualization process. On the desktop, the graphics interactivity is effectively decoupled from the latency inherent in network applications. We present a detailed performance analysis of the application, and improvements resulting from field-test analysis conducted as part of the DOE Combustion Corridor project.

  20. High-throughput automated image analysis of neuroinflammation and neurodegeneration enables quantitative assessment of virus neurovirulence

    PubMed Central

    Maximova, Olga A.; Murphy, Brian R.; Pletnev, Alexander G.

    2010-01-01

    Historically, the safety of live attenuated vaccine candidates against neurotropic viruses was assessed by semi-quantitative analysis of virus-induced histopathology in the central nervous system of monkeys. We have developed a high-throughput automated image analysis (AIA) for the quantitative assessment of virus-induced neuroinflammation and neurodegeneration. Evaluation of the results generated by AIA showed that quantitative estimates of lymphocytic infiltration, microglial activation, and neurodegeneration strongly and significantly correlated with results of traditional histopathological scoring. In addition, we show that AIA is a targeted, objective, accurate, and time-efficient approach that provides reliable differentiation of virus neurovirulence. As such, it may become a useful tool in establishing consistent analytical standards across research and development laboratories and regulatory agencies, and may improve the safety evaluation of live virus vaccines. The implementation of this high-throughput AIA will markedly advance many fields of research including virology, neuroinflammation, neuroscience, and vaccinology. PMID:20688036

  1. Solar Forecasting Challenges and Opportunities for Enabling High Penetration of Solar Energy

    NASA Astrophysics Data System (ADS)

    Mishra, S.

    2015-12-01

    In 2011, DOE launched the SunShot Initiative to reduce the total cost of solar energy systems by about 75% to make them cost competitive with other forms of energy (without subsidies) by 2020. This translates to a total cost of installed solar energy at 1/Watt or 0.06/kWh, incentivizing high penetration of solar on the utility grid. In the past four years, the SunShot Initiative has catalyzed revolutionary advancements in solar technologies, stimulating significant growth and accelerating deployment of solar energy systems. However, as solar deployment increases, integrating solar energy into the utility grid poses difficult challenges due to the variability in solar resource and the impact of clouds and aerosols on surface irradiance. Accurate forecasting of solar resource and its variability at high temporal and spatial resolution at least a day ahead is crucial to large scale integration of solar energy into the utility grid. However, this is limited by current errors in forecasting that are as high as 25% for clear sky forecasts of Global Horizontal Irradiance (GHI), and as large as 40-80% for cloudy conditions. Forecasting errors are even higher for the direct normal irradiance (DNI). For solar energy to be seamlessly integrated into the utility grid under the scenarios of high penetration of solar, significant improvements in surface solar irradiance modeling and observations of both Global Horizontal Irradiance (GHI) and Direct Normal Irradiance (DNI) are essential to accurately predict power outputs from photovoltaic (PV) and concentrating solar power (CSP) systems. Furthermore, forecasting improvements have to be closely tied to utility needs and operation timelines. Details about the ongoing research efforts supported through the SunShot initiative and the challenges and needs for solar forecasting improvements in regards to the SunShot Initiative will be presented at the conference.

  2. High-rate lithium-sulfur batteries enabled by hierarchical porous carbons synthesized via ice templation

    NASA Astrophysics Data System (ADS)

    Sahore, Ritu; Estevez, Luis P.; Ramanujapuram, Anirudh; DiSalvo, Francis J.; Giannelis, Emmanuel P.

    2015-11-01

    We report the performance of a series of hierarchical porous carbons (HPCs) with extremely high surface areas of up to 2340 m2 g-1 with total pore volume of up to 3.8 cm3 g-1 as supports for sulfur for Li-S batteries. The hierarchical structure of the carbon originating from interconnected large mesopores (10-50 nm), small mesopores (2-10 nm) and micropores (<2 nm) makes the total available surface area highly accessible, resulting in excellent electrode kinetics. At high C-rates of 2 C and 5 C, large specific capacities of 647 mA h g-1 and 503 mA h g-1, respectively, were obtained after 200 cycles. In addition, we also systematically show that the cyclic stability is independent of the size of the pores sulfur is initially confined in, when LiNO3 is used as the electrolyte additive, indicating that capacity fade due to polysulfide shuttle is effectively eliminated and that it is not related to pore size anymore.

  3. High-resolution enabled 12-plex DiLeu isobaric tags for quantitative proteomics.

    PubMed

    Frost, Dustin C; Greer, Tyler; Li, Lingjun

    2015-02-01

    Multiplex isobaric tags (e.g., tandem mass tags (TMT) and isobaric tags for relative and absolute quantification (iTRAQ)) are a valuable tool for high-throughput mass spectrometry based quantitative proteomics. We have developed our own multiplex isobaric tags, DiLeu, that feature quantitative performance on par with commercial offerings but can be readily synthesized in-house as a cost-effective alternative. In this work, we achieve a 3-fold increase in the multiplexing capacity of the DiLeu reagent without increasing structural complexity by exploiting mass defects that arise from selective incorporation of (13)C, (15)N, and (2)H stable isotopes in the reporter group. The inclusion of eight new reporter isotopologues that differ in mass from the existing four reporters by intervals of 6 mDa yields a 12-plex isobaric set that preserves the synthetic simplicity and quantitative performance of the original implementation. We show that the new reporter variants can be baseline-resolved in high-resolution higher-energy C-trap dissociation (HCD) spectra, and we demonstrate accurate 12-plex quantitation of a DiLeu-labeled Saccharomyces cerevisiae lysate digest via high-resolution nano liquid chromatography-tandem mass spectrometry (nanoLC-MS(2)) analysis on an Orbitrap Elite mass spectrometer. PMID:25405479

  4. Controllable Edge Oxidation and Bubbling Exfoliation Enable the Fabrication of High Quality Water Dispersible Graphene

    PubMed Central

    Tian, Suyun; Sun, Jing; Yang, Siwei; He, Peng; Wang, Gang; Di, Zengfeng; Ding, Guqiao; Xie, Xiaoming; Jiang, Mianheng

    2016-01-01

    Despite significant progresses made on mass production of chemically exfoliated graphene, the quality, cost and environmental friendliness remain major challenges for its market penetration. Here, we present a fast and green exfoliation strategy for large scale production of high quality water dispersible few layer graphene through a controllable edge oxidation and localized gas bubbling process. Mild edge oxidation guarantees that the pristine sp2 lattice is largely intact and the edges are functionalized with hydrophilic groups, giving rise to high conductivity and good water dispersibility at the same time. The aqueous concentration can be as high as 5.0 mg mL−1, which is an order of magnitude higher than previously reports. The water soluble graphene can be directly spray-coated on various substrates, and the back-gated field effect transistor give hole and electron mobility of ~496 and ~676 cm2 V−1 s−1, respectively. These results achieved are expected to expedite various applications of graphene. PMID:27666869

  5. High-Resolution Enabled 12-Plex DiLeu Isobaric Tags for Quantitative Proteomics

    PubMed Central

    2015-01-01

    Multiplex isobaric tags (e.g., tandem mass tags (TMT) and isobaric tags for relative and absolute quantification (iTRAQ)) are a valuable tool for high-throughput mass spectrometry based quantitative proteomics. We have developed our own multiplex isobaric tags, DiLeu, that feature quantitative performance on par with commercial offerings but can be readily synthesized in-house as a cost-effective alternative. In this work, we achieve a 3-fold increase in the multiplexing capacity of the DiLeu reagent without increasing structural complexity by exploiting mass defects that arise from selective incorporation of 13C, 15N, and 2H stable isotopes in the reporter group. The inclusion of eight new reporter isotopologues that differ in mass from the existing four reporters by intervals of 6 mDa yields a 12-plex isobaric set that preserves the synthetic simplicity and quantitative performance of the original implementation. We show that the new reporter variants can be baseline-resolved in high-resolution higher-energy C-trap dissociation (HCD) spectra, and we demonstrate accurate 12-plex quantitation of a DiLeu-labeled Saccharomyces cerevisiae lysate digest via high-resolution nano liquid chromatography–tandem mass spectrometry (nanoLC–MS2) analysis on an Orbitrap Elite mass spectrometer. PMID:25405479

  6. Controllable Edge Oxidation and Bubbling Exfoliation Enable the Fabrication of High Quality Water Dispersible Graphene

    NASA Astrophysics Data System (ADS)

    Tian, Suyun; Sun, Jing; Yang, Siwei; He, Peng; Wang, Gang; di, Zengfeng; Ding, Guqiao; Xie, Xiaoming; Jiang, Mianheng

    2016-09-01

    Despite significant progresses made on mass production of chemically exfoliated graphene, the quality, cost and environmental friendliness remain major challenges for its market penetration. Here, we present a fast and green exfoliation strategy for large scale production of high quality water dispersible few layer graphene through a controllable edge oxidation and localized gas bubbling process. Mild edge oxidation guarantees that the pristine sp2 lattice is largely intact and the edges are functionalized with hydrophilic groups, giving rise to high conductivity and good water dispersibility at the same time. The aqueous concentration can be as high as 5.0 mg mL‑1, which is an order of magnitude higher than previously reports. The water soluble graphene can be directly spray-coated on various substrates, and the back-gated field effect transistor give hole and electron mobility of ~496 and ~676 cm2 V‑1 s‑1, respectively. These results achieved are expected to expedite various applications of graphene.

  7. Crosslinking of aromatic polyamides via pendant propargyl groups

    NASA Technical Reports Server (NTRS)

    St.clair, A. K.; St.clair, T. L.; Barrick, J. D.; Campbell, F. J.

    1980-01-01

    Methods for crosslinking N-methyl substituted aromatic polyamides were investigated in an effort to improve the applicability of these polymers as matrix resins for Kavlar trademark fiber composites. High molecular weight polymers were prepared from isophthaloyl dichloride and 4,4'- bis(methylamino)diphenylmethane with varying proportions of the N,N'bispropargyl diamine incorporated as a crosslinking agent. The propargylcontaining diamines were crosslinked thermally and characterized by infrared spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. Attempts were also made to crosslink polyamide films by exposure to ultraviolet light, electron beam, and gamma radiation.

  8. Hyper-crosslinked resins filled with multiwalled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Castaldo, R.; Ambrogi, V.; Avolio, R.; Cocca, C.; Errico, M. E.; Gentile, G.; Avella, M.; Carfagna, C.

    2016-05-01

    Hyper-crosslinked styrenic resins are tipically prepared by suspension polymerization of a gel-type precursor and successive crosslinking by Friedel-Crafts reaction. This kind of polymers displays high specific surface area and excellent sorption properties. Hyper-crosslinked resins and nanocomposites containing multiwalled carbon nanotubes (MWCNT) were prepared in this study. Structure and properties of hyper-crosslinked resins containing MWCNT were investigated. Moreover, a new synthetic process of the nanocomposites was developed, based on the bulk polymerization of the precursor resin. The effect of the synthetic procedure and the addition of nanofillers on the material specific surface area, porosity and adsorption properties were explored.

  9. Modular pathway rewiring of Saccharomyces cerevisiae enables high-level production of L-ornithine.

    PubMed

    Qin, Jiufu; Zhou, Yongjin J; Krivoruchko, Anastasia; Huang, Mingtao; Liu, Lifang; Khoomrung, Sakda; Siewers, Verena; Jiang, Bo; Nielsen, Jens

    2015-01-01

    Baker's yeast Saccharomyces cerevisiae is an attractive cell factory for production of chemicals and biofuels. Many different products have been produced in this cell factory by reconstruction of heterologous biosynthetic pathways; however, endogenous metabolism by itself involves many metabolites of industrial interest, and de-regulation of endogenous pathways to ensure efficient carbon channelling to such metabolites is therefore of high interest. Furthermore, many of these may serve as precursors for the biosynthesis of complex natural products, and hence strains overproducing certain pathway intermediates can serve as platform cell factories for production of such products. Here we implement a modular pathway rewiring (MPR) strategy and demonstrate its use for pathway optimization resulting in high-level production of L-ornithine, an intermediate of L-arginine biosynthesis and a precursor metabolite for a range of different natural products. The MPR strategy involves rewiring of the urea cycle, subcellular trafficking engineering and pathway re-localization, and improving precursor supply either through attenuation of the Crabtree effect or through the use of controlled fed-batch fermentations, leading to an L-ornithine titre of 1,041±47 mg l(-1) with a yield of 67 mg (g glucose)(-1) in shake-flask cultures and a titre of 5.1 g l(-1) in fed-batch cultivations. Our study represents the first comprehensive study on overproducing an amino-acid intermediate in yeast, and our results demonstrate the potential to use yeast more extensively for low-cost production of many high-value amino-acid-derived chemicals. PMID:26345617

  10. Modular pathway rewiring of Saccharomyces cerevisiae enables high-level production of L-ornithine

    PubMed Central

    Qin, Jiufu; Zhou, Yongjin J.; Krivoruchko, Anastasia; Huang, Mingtao; Liu, Lifang; Khoomrung, Sakda; Siewers, Verena; Jiang, Bo; Nielsen, Jens

    2015-01-01

    Baker's yeast Saccharomyces cerevisiae is an attractive cell factory for production of chemicals and biofuels. Many different products have been produced in this cell factory by reconstruction of heterologous biosynthetic pathways; however, endogenous metabolism by itself involves many metabolites of industrial interest, and de-regulation of endogenous pathways to ensure efficient carbon channelling to such metabolites is therefore of high interest. Furthermore, many of these may serve as precursors for the biosynthesis of complex natural products, and hence strains overproducing certain pathway intermediates can serve as platform cell factories for production of such products. Here we implement a modular pathway rewiring (MPR) strategy and demonstrate its use for pathway optimization resulting in high-level production of L-ornithine, an intermediate of L-arginine biosynthesis and a precursor metabolite for a range of different natural products. The MPR strategy involves rewiring of the urea cycle, subcellular trafficking engineering and pathway re-localization, and improving precursor supply either through attenuation of the Crabtree effect or through the use of controlled fed-batch fermentations, leading to an L-ornithine titre of 1,041±47 mg l−1 with a yield of 67 mg (g glucose)−1 in shake-flask cultures and a titre of 5.1 g l−1 in fed-batch cultivations. Our study represents the first comprehensive study on overproducing an amino-acid intermediate in yeast, and our results demonstrate the potential to use yeast more extensively for low-cost production of many high-value amino-acid-derived chemicals. PMID:26345617

  11. High performance superconducting devices enabled by three dimensionally ordered nanodots and/or nanorods

    SciTech Connect

    Goyal, Amit

    2013-09-17

    Novel articles and methods to fabricate same with self-assembled nanodots and/or nanorods of a single or multicomponent material within another single or multicomponent material for use in electrical, electronic, magnetic, electromagnetic and electrooptical devices is disclosed. Self-assembled nanodots and/or nanorods are ordered arrays wherein ordering occurs due to strain minimization during growth of the materials. A simple method to accomplish this when depositing in-situ films is also disclosed. Device applications of resulting materials are in areas of superconductivity, photovoltaics, ferroelectrics, magnetoresistance, high density storage, solid state lighting, non-volatile memory, photoluminescence, thermoelectrics and in quantum dot lasers.

  12. High performance devices enabled by epitaxial, preferentially oriented, nanodots and/or nanorods

    DOEpatents

    Goyal, Amit

    2011-10-11

    Novel articles and methods to fabricate same with self-assembled nanodots and/or nanorods of a single or multicomponent material within another single or multicomponent material for use in electrical, electronic, magnetic, electromagnetic, superconducting and electrooptical devices is disclosed. Self-assembled nanodots and/or nanorods are ordered arrays wherein ordering occurs due to strain minimization during growth of the materials. A simple method to accomplish this when depositing in-situ films is also disclosed. Device applications of resulting materials are in areas of superconductivity, photovoltaics, ferroelectrics, magnetoresistance, high density storage, solid state lighting, non-volatile memory, photoluminescence, thermoelectrics and in quantum dot lasers.

  13. High performance electrical, magnetic, electromagnetic and electrooptical devices enabled by three dimensionally ordered nanodots and nanorods

    DOEpatents

    Goyal, Amit , Kang; Sukill

    2012-02-21

    Novel articles and methods to fabricate same with self-assembled nanodots and/or nanorods of a single or multicomponent material within another single or multicomponent material for use in electrical, electronic, magnetic, electromagnetic and electrooptical devices is disclosed. Self-assembled nanodots and/or nanorods are ordered arrays wherein ordering occurs due to strain minimization during growth of the materials. A simple method to accomplish this when depositing in-situ films is also disclosed. Device applications of resulting materials are in areas of superconductivity, photovoltaics, ferroelectrics, magnetoresistance, high density storage, solid state lighting, non-volatile memory, photoluminescence, thermoelectrics and in quantum dot lasers.

  14. Microfluidic Impedance Flow Cytometry Enabling High-Throughput Single-Cell Electrical Property Characterization

    PubMed Central

    Chen, Jian; Xue, Chengcheng; Zhao, Yang; Chen, Deyong; Wu, Min-Hsien; Wang, Junbo

    2015-01-01

    This article reviews recent developments in microfluidic impedance flow cytometry for high-throughput electrical property characterization of single cells. Four major perspectives of microfluidic impedance flow cytometry for single-cell characterization are included in this review: (1) early developments of microfluidic impedance flow cytometry for single-cell electrical property characterization; (2) microfluidic impedance flow cytometry with enhanced sensitivity; (3) microfluidic impedance and optical flow cytometry for single-cell analysis and (4) integrated point of care system based on microfluidic impedance flow cytometry. We examine the advantages and limitations of each technique and discuss future research opportunities from the perspectives of both technical innovation and clinical applications. PMID:25938973

  15. Analysis of Distribution Circuits with High Penetrations of Photo-Voltaic Generation and Progressive Steps to Enable Higher Penetrations

    NASA Astrophysics Data System (ADS)

    Payne, Joshua Daniel

    Concern for anthropogenic climate change has instigated an increase in renewable generation capacity, including photo-voltaic (PV) power generation in distribution circuits. Distribution circuits with relatively high penetrations of PV generation (High-Pen PV) exist today, but how much more generation can distribution systems handle? This research aims to approach this question by 1) analyzing and quantifying High-Pen PV limitations on the primary circuits of distribution systems and 2) propose and analyze progressive steps to enable higher penetrations of PV on distribution circuits. Utilizing connectivity and load demand measurements provided by Pacific Gas & Electric (PG&E), time-resolved three-phase balanced feeder models of a commercial and a residential circuit featuring High-Pen PV were developed and calibrated to the point of the sub-station. Once calibrated, the circuit performance was simulated with varying PV penetrations and spatial distributions for typical seasonal high and seasonal low load demand days. Circuit scenarios with the Generation Center located downstream of the Load Center and with high impedance distribution line in-between lead to high voltage conditions. High-Pen PV interacting with the sub-station Load Drop Compensation (LDC) resulted an increased number of equipment operations and low voltage conditions on the circuit. As PV penetration increased, sub-station power factor and line loss decreased until reverse power flow became dominant. These were observed characteristics of High-Pen PV circuits. To overcome the limitations stated above, practical steps, such as line re-conductoring, and progressive control and operation changes were introduced. The progressive changes included using a Voltage Rise Siting (VRS) score for planning and LDC Current Compensation control to enable higher penetrations of PV. It was shown that limitations of High-Pen PV on the primary side of distribution circuits may be overcome via these practical and

  16. Training in High-Throughput Sequencing: Common Guidelines to Enable Material Sharing, Dissemination, and Reusability

    PubMed Central

    Schiffthaler, Bastian

    2016-01-01

    The advancement of high-throughput sequencing (HTS) technologies and the rapid development of numerous analysis algorithms and pipelines in this field has resulted in an unprecedentedly high demand for training scientists in HTS data analysis. Embarking on developing new training materials is challenging for many reasons. Trainers often do not have prior experience in preparing or delivering such materials and struggle to keep them up to date. A repository of curated HTS training materials would support trainers in materials preparation, reduce the duplication of effort by increasing the usage of existing materials, and allow for the sharing of teaching experience among the HTS trainers’ community. To achieve this, we have developed a strategy for materials’ curation and dissemination. Standards for describing training materials have been proposed and applied to the curation of existing materials. A Git repository has been set up for sharing annotated materials that can now be reused, modified, or incorporated into new courses. This repository uses Git; hence, it is decentralized and self-managed by the community and can be forked/built-upon by all users. The repository is accessible at http://bioinformatics.upsc.se/htmr. PMID:27309738

  17. High strength-of-ties and low mobility enable the evolution of third-party punishment.

    PubMed

    Roos, Patrick; Gelfand, Michele; Nau, Dana; Carr, Ryan

    2014-02-01

    As punishment can be essential to cooperation and norm maintenance but costly to the punisher, many evolutionary game-theoretic studies have explored how direct punishment can evolve in populations. Compared to direct punishment, in which an agent acts to punish another for an interaction in which both parties were involved, the evolution of third-party punishment (3PP) is even more puzzling, because the punishing agent itself was not involved in the original interaction. Despite significant empirical studies of 3PP, little is known about the conditions under which it can evolve. We find that punishment reputation is not, by itself, sufficient for the evolution of 3PP. Drawing on research streams in sociology and psychology, we implement a structured population model and show that high strength-of-ties and low mobility are critical for the evolution of responsible 3PP. Only in such settings of high social-structural constraint are punishers able to induce self-interested agents toward cooperation, making responsible 3PP ultimately beneficial to individuals as well as the collective. Our results illuminate the conditions under which 3PP is evolutionarily adaptive in populations. Responsible 3PP can evolve and induce cooperation in cases where other mechanisms alone fail to do so. PMID:24335985

  18. Target dependent femtosecond laser plasma implantation dynamics in enabling silica for high density erbium doping

    PubMed Central

    Chandrappan, Jayakrishnan; Murray, Matthew; Kakkar, Tarun; Petrik, Peter; Agocs, Emil; Zolnai, Zsolt; Steenson, D.P.; Jha, Animesh; Jose, Gin

    2015-01-01

    Chemical dissimilarity of tellurium oxide with silica glass increases phase separation and crystallization tendency when mixed and melted for making a glass. We report a novel technique for incorporating an Er3+-doped tellurite glass composition into silica substrates through a femtosecond (fs) laser generated plasma assisted process. The engineered material consequently exhibits the spectroscopic properties of Er3+-ions, which are unachievable in pure silica and implies this as an ideal material for integrated photonics platforms. Formation of a well-defined metastable and homogeneous glass structure with Er3+-ions in a silica network, modified with tellurite has been characterized using high-resolution cross-sectional transmission electron microscopy (HRTEM). The chemical and structural analyses using HRTEM, Rutherford backscattering spectrometry (RBS) and laser excitation techniques, confirm that such fs-laser plasma implanted glasses may be engineered for significantly higher concentration of Er3+-ions without clustering, validated by the record high lifetime-density product 0.96 × 1019 s.cm−3. Characterization of planar optical layers and photoluminescence emission spectra were undertaken to determine their thickness, refractive indices and photoluminescence properties, as a function of Er3+ concentration via different target glasses. The increased Er3+ content in the target glass enhance the refractive index and photoluminescence intensity of the modified silica layer whilst the lifetime and thickness decrease. PMID:26370060

  19. Advanced High-Voltage Aqueous Lithium-Ion Battery Enabled by "Water-in-Bisalt" Electrolyte.

    PubMed

    Suo, Liumin; Borodin, Oleg; Sun, Wei; Fan, Xiulin; Yang, Chongyin; Wang, Fei; Gao, Tao; Ma, Zhaohui; Schroeder, Marshall; von Cresce, Arthur; Russell, Selena M; Armand, Michel; Angell, Austen; Xu, Kang; Wang, Chunsheng

    2016-06-13

    A new super-concentrated aqueous electrolyte is proposed by introducing a second lithium salt. The resultant ultra-high concentration of 28 m led to more effective formation of a protective interphase on the anode along with further suppression of water activities at both anode and cathode surfaces. The improved electrochemical stability allows the use of TiO2 as the anode material, and a 2.5 V aqueous Li-ion cell based on LiMn2 O4 and carbon-coated TiO2 delivered the unprecedented energy density of 100 Wh kg(-1) for rechargeable aqueous Li-ion cells, along with excellent cycling stability and high coulombic efficiency. It has been demonstrated that the introduction of a second salts into the "water-in-salt" electrolyte further pushed the energy densities of aqueous Li-ion cells closer to those of the state-of-the-art Li-ion batteries. PMID:27120336

  20. Protein deimmunization via structure-based design enables efficient epitope deletion at high mutational loads.

    PubMed

    Salvat, Regina S; Choi, Yoonjoo; Bishop, Alexandra; Bailey-Kellogg, Chris; Griswold, Karl E

    2015-07-01

    Anti-drug immune responses are a unique risk factor for biotherapeutics, and undesired immunogenicity can alter pharmacokinetics, compromise drug efficacy, and in some cases even threaten patient safety. To fully capitalize on the promise of biotherapeutics, more efficient and generally applicable protein deimmunization tools are needed. Mutagenic deletion of a protein's T cell epitopes is one powerful strategy to engineer immunotolerance, but deimmunizing mutations must maintain protein structure and function. Here, EpiSweep, a structure-based protein design and deimmunization algorithm, has been used to produce a panel of seven beta-lactamase drug candidates having 27-47% reductions in predicted epitope content. Despite bearing eight mutations each, all seven engineered enzymes maintained good stability and activity. At the same time, the variants exhibited dramatically reduced interaction with human class II major histocompatibility complex proteins, key regulators of anti-drug immune responses. When compared to 8-mutation designs generated with a sequence-based deimmunization algorithm, the structure-based designs retained greater thermostability and possessed fewer high affinity epitopes, the dominant drivers of anti-biotherapeutic immune responses. These experimental results validate the first structure-based deimmunization algorithm capable of mapping optimal biotherapeutic design space. By designing optimal mutations that reduce immunogenic potential while imparting favorable intramolecular interactions, broadly distributed epitopes may be simultaneously targeted using high mutational loads.

  1. Protein deimmunization via structure-based design enables efficient epitope deletion at high mutational loads

    PubMed Central

    Salvat, Regina S.; Choi, Yoonjoo; Bishop, Alexandra; Bailey-Kellogg, Chris; Griswold, Karl E.

    2015-01-01

    Anti-drug immune responses are a unique risk factor for biotherapeutics, and undesired immunogenicity can alter pharmacokinetics, compromise drug efficacy, and in some cases even threaten patient safety. To fully capitalize on the promise of biotherapeutics, more efficient and generally applicable protein deimmunization tools are needed. Mutagenic deletion of a protein’s T cell epitopes is one powerful strategy to engineer immunotolerance, but deimmunizing mutations must maintain protein structure and function. Here, EpiSweep, a structure-based protein design and deimmunization algorithm, has been used to produce a panel of seven beta-lactamase drug candidates having 27–47% reductions in predicted epitope content. Despite bearing eight mutations each, all seven engineered enzymes maintained good stability and activity. At the same time, the variants exhibited dramatically reduced interaction with human class II major histocompatibility complex proteins, key regulators of anti-drug immune responses. When compared to 8-mutation designs generated with a sequence-based deimmunization algorithm, the structure-based designs retained greater thermostability and possessed fewer high affinity epitopes, the dominant drivers of anti-biotherapeutic immune responses. These experimental results validate the first structure-based deimmunization algorithm capable of mapping optimal biotherapeutic design space. By designing optimal mutations that reduce immunogenic potential while imparting favorable intramolecular interactions, broadly distributed epitopes may be simultaneously targeted using high mutational loads. PMID:25655032

  2. Conformal surface coatings to enable high volume expansion Li-ion anode materials.

    PubMed

    Riley, Leah A; Cavanagh, Andrew S; George, Steven M; Jung, Yoon Seok; Yan, Yanfa; Lee, Se-Hee; Dillon, Anne C

    2010-07-12

    An alumina surface coating is demonstrated to improve electrochemical performance of MoO(3) nanoparticles as high capacity/high-volume expansion anodes for Li-ion batteries. Thin, conformal surface coatings were grown using atomic layer deposition (ALD) that relies on self-limiting surface reactions. ALD coatings were tested on both individual nanoparticles and prefabricated electrodes containing conductive additive and binder. The coated and non-coated materials were characterized using transmission electron microscopy, energy-dispersive X-ray spectroscopy, electrochemical impedance spectroscopy, and galvanostatic charge/discharge cycling. Importantly, increased stability and capacity retention was only observed when the fully fabricated electrode was coated. The alumina layer both improves the adhesion of the entire electrode, during volume expansion/contraction and protects the nanoparticle surfaces. Coating the entire electrode also allows for an important carbothermal reduction process that occurs during electrode pre-heat treatment. ALD is thus demonstrated as a novel and necessary method that may be employed to coat the tortuous network of a battery electrode.

  3. Advanced High-Voltage Aqueous Lithium-Ion Battery Enabled by "Water-in-Bisalt" Electrolyte.

    PubMed

    Suo, Liumin; Borodin, Oleg; Sun, Wei; Fan, Xiulin; Yang, Chongyin; Wang, Fei; Gao, Tao; Ma, Zhaohui; Schroeder, Marshall; von Cresce, Arthur; Russell, Selena M; Armand, Michel; Angell, Austen; Xu, Kang; Wang, Chunsheng

    2016-06-13

    A new super-concentrated aqueous electrolyte is proposed by introducing a second lithium salt. The resultant ultra-high concentration of 28 m led to more effective formation of a protective interphase on the anode along with further suppression of water activities at both anode and cathode surfaces. The improved electrochemical stability allows the use of TiO2 as the anode material, and a 2.5 V aqueous Li-ion cell based on LiMn2 O4 and carbon-coated TiO2 delivered the unprecedented energy density of 100 Wh kg(-1) for rechargeable aqueous Li-ion cells, along with excellent cycling stability and high coulombic efficiency. It has been demonstrated that the introduction of a second salts into the "water-in-salt" electrolyte further pushed the energy densities of aqueous Li-ion cells closer to those of the state-of-the-art Li-ion batteries.

  4. High strength-of-ties and low mobility enable the evolution of third-party punishment.

    PubMed

    Roos, Patrick; Gelfand, Michele; Nau, Dana; Carr, Ryan

    2014-02-01

    As punishment can be essential to cooperation and norm maintenance but costly to the punisher, many evolutionary game-theoretic studies have explored how direct punishment can evolve in populations. Compared to direct punishment, in which an agent acts to punish another for an interaction in which both parties were involved, the evolution of third-party punishment (3PP) is even more puzzling, because the punishing agent itself was not involved in the original interaction. Despite significant empirical studies of 3PP, little is known about the conditions under which it can evolve. We find that punishment reputation is not, by itself, sufficient for the evolution of 3PP. Drawing on research streams in sociology and psychology, we implement a structured population model and show that high strength-of-ties and low mobility are critical for the evolution of responsible 3PP. Only in such settings of high social-structural constraint are punishers able to induce self-interested agents toward cooperation, making responsible 3PP ultimately beneficial to individuals as well as the collective. Our results illuminate the conditions under which 3PP is evolutionarily adaptive in populations. Responsible 3PP can evolve and induce cooperation in cases where other mechanisms alone fail to do so.

  5. Can Nanofluidic Chemical Release Enable Fast, High Resolution Neurotransmitter-Based Neurostimulation?

    PubMed Central

    Jones, Peter D.; Stelzle, Martin

    2016-01-01

    Artificial chemical stimulation could provide improvements over electrical neurostimulation. Physiological neurotransmission between neurons relies on the nanoscale release and propagation of specific chemical signals to spatially-localized receptors. Current knowledge of nanoscale fluid dynamics and nanofluidic technology allows us to envision artificial mechanisms to achieve fast, high resolution neurotransmitter release. Substantial technological development is required to reach this goal. Nanofluidic technology—rather than microfluidic—will be necessary; this should come as no surprise given the nanofluidic nature of neurotransmission. This perspective reviews the state of the art of high resolution electrical neuroprostheses and their anticipated limitations. Chemical release rates from nanopores are compared to rates achieved at synapses and with iontophoresis. A review of microfluidic technology justifies the analysis that microfluidic control of chemical release would be insufficient. Novel nanofluidic mechanisms are discussed, and we propose that hydrophobic gating may allow control of chemical release suitable for mimicking neurotransmission. The limited understanding of hydrophobic gating in artificial nanopores and the challenges of fabrication and large-scale integration of nanofluidic components are emphasized. Development of suitable nanofluidic technology will require dedicated, long-term efforts over many years. PMID:27065794

  6. Highly Flexible Self-Assembled V2O5 Cathodes Enabled by Conducting Diblock Copolymers

    NASA Astrophysics Data System (ADS)

    An, Hyosung; Mike, Jared; Smith, Kendall; Swank, Lisa; Lin, Yen-Hao; Pesek, Stacy; Verduzco, Rafael; Lutkenhaus, Jodie

    Structural energy storage materials combining load-bearing mechanical properties and high energy storage performance are desired for applications in wearable devices or flexible displays. Vanadium pentoxide (V2O5) is a promising cathode material for possible use in flexible battery electrodes, but it remains limited by low Li+ diffusion coefficient and electronic conductivity, severe volumetric changes upon cycling, and limited mechanical flexibility. Here, we demonstrate a route to address these challenges by blending a diblock copolymer bearing electron- and ion-conducting blocks, poly(3-hexylthiophene)-block-poly(ethyleneoxide) (P3HT- b-PEO), with V2O5 to form a mechanically flexible, electro-mechanically stable hybrid electrode. V2O5 layers were arranged parallel in brick-and-mortar-like fashion held together by the P3HT- b-PEO binder. This unique structure significantly enhances mechanical flexibility, toughness and cyclability without sacrificing capacity. Electrodes comprised of 10 wt% polymer have unusually high toughness (293 kJ/m3) and specific energy (530 Wh/kg), both higher than reduced graphene oxide paper electrodes.

  7. Enabling high-quality observations of surface imperviousness for water runoff modelling from unmanned aerial vehicles

    NASA Astrophysics Data System (ADS)

    Tokarczyk, Piotr; Leitao, Joao Paulo; Rieckermann, Jörg; Schindler, Konrad; Blumensaat, Frank

    2015-04-01

    Modelling rainfall-runoff in urban areas is increasingly applied to support flood risk assessment particularly against the background of a changing climate and an increasing urbanization. These models typically rely on high-quality data for rainfall and surface characteristics of the area. While recent research in urban drainage has been focusing on providing spatially detailed rainfall data, the technological advances in remote sensing that ease the acquisition of detailed land-use information are less prominently discussed within the community. The relevance of such methods increase as in many parts of the globe, accurate land-use information is generally lacking, because detailed image data is unavailable. Modern unmanned air vehicles (UAVs) allow acquiring high-resolution images on a local level at comparably lower cost, performing on-demand repetitive measurements, and obtaining a degree of detail tailored for the purpose of the study. In this study, we investigate for the first time the possibility to derive high-resolution imperviousness maps for urban areas from UAV imagery and to use this information as input for urban drainage models. To do so, an automatic processing pipeline with a modern classification method is tested and applied in a state-of-the-art urban drainage modelling exercise. In a real-life case study in the area of Lucerne, Switzerland, we compare imperviousness maps generated from a consumer micro-UAV and standard large-format aerial images acquired by the Swiss national mapping agency (swisstopo). After assessing their correctness, we perform an end-to-end comparison, in which they are used as an input for an urban drainage model. Then, we evaluate the influence which different image data sources and their processing methods have on hydrological and hydraulic model performance. We analyze the surface runoff of the 307 individual sub-catchments regarding relevant attributes, such as peak runoff and volume. Finally, we evaluate the model

  8. The Wide-Field Imaging Interferometry Testbed: Enabling Techniques for High Angular Resolution Astronomy

    NASA Technical Reports Server (NTRS)

    Rinehart, S. A.; Armstrong, T.; Frey, Bradley J.; Jung, J.; Kirk, J.; Leisawitz, David T.; Leviton, Douglas B.; Lyon, R.; Maher, Stephen; Martino, Anthony J.; Pauls, T.

    2007-01-01

    The Wide-Field Imaging Interferometry Testbed (WIIT) was designed to develop techniques for wide-field of view imaging interferometry, using "double-Fourier" methods. These techniques will be important for a wide range of future spacebased interferometry missions. We have provided simple demonstrations of the methodology already, and continuing development of the testbed will lead to higher data rates, improved data quality, and refined algorithms for image reconstruction. At present, the testbed effort includes five lines of development; automation of the testbed, operation in an improved environment, acquisition of large high-quality datasets, development of image reconstruction algorithms, and analytical modeling of the testbed. We discuss the progress made towards the first four of these goals; the analytical modeling is discussed in a separate paper within this conference.

  9. High-frequency chaotic dynamics enabled by optical phase-conjugation

    PubMed Central

    Mercier, Émeric; Wolfersberger, Delphine; Sciamanna, Marc

    2016-01-01

    Wideband chaos is of interest for applications such as random number generation or encrypted communications, which typically use optical feedback in a semiconductor laser. Here, we show that replacing conventional optical feedback with phase-conjugate feedback improves the chaos bandwidth. In the range of achievable phase-conjugate mirror reflectivities, the bandwidth increase reaches 27% when compared with feedback from a conventional mirror. Experimental measurements of the time-resolved frequency dynamics on nanosecond time-scales show that the bandwidth enhancement is related to the onset of self-pulsing solutions at harmonics of the external-cavity frequency. In the observed regime, the system follows a chaotic itinerancy among these destabilized high-frequency external-cavity modes. The recorded features are unique to phase-conjugate feedback and distinguish it from the long-standing problem of time-delayed feedback dynamics. PMID:26739806

  10. Elongation of fibers from highly viscous dextran solutions enables fabrication of rapidly dissolving drug carrying fabrics.

    PubMed

    Frampton, John P; Lai, David; Lounds, Maxwell; Chung, Kyeongwoon; Kim, Jinsang; Mansfield, John F; Takayama, Shuichi

    2015-01-28

    A simple method is presented for forming thread-like fibers from highly viscous dextran solutions. Based on the cohesive and adhesive forces between a dextran solution and the substrate to which it is applied, multiple fibers of approximately 10 μm in diameter can be elongated simultaneously. These fibers can be woven into multiple layers to produce fabrics of varying fiber orientations and mechanical properties. Various bioactive agents can be incorporated into the dextran solution prior to fiber formation, including hemostatic and antibiotic agents. Fabrics containing thrombin are capable of coagulating human platelet poor plasma in vitro. Fabrics containing antibiotics are capable of suppressing bacterial growth in a disk diffusion assay. These data suggest that this new material composed entirely of dextran has promise as a drug delivery component in wound dressings.

  11. Diffractive intermediate layer enables broadband light trapping for high efficiency ultrathin c-Si tandem cells

    SciTech Connect

    Li, Guijun Ho, Jacob Y. L.; Li, He; Kwok, Hoi-Sing

    2014-06-09

    Light management through the intermediate reflector in the tandem cell configuration is of great practical importance for achieving high stable efficiency and also low cost production. So far, however, the intermediate reflectors employed currently are mainly focused on the light absorption enhancement of the top cell. Here, we present a diffractive intermediate layer that allows for light trapping over a broadband wavelength for the ultrathin c-Si tandem solar cell. Compared with the standard intermediate reflector, this nanoscale architectural intermediate layer results in a 35% and 21% remarkable enhancement of the light absorption in the top (400–800 nm) and bottom (800–1100 nm) cells simultaneously, and ultrathin c-Si tandem cells with impressive conversion efficiency of 13.3% are made on the glass substrate.

  12. Image reconstruction enables high resolution imaging at large penetration depths in fluorescence microscopy

    NASA Astrophysics Data System (ADS)

    Dilipkumar, Shilpa; Montalescot, Sandra; Mondal, Partha Pratim

    2013-10-01

    Imaging thick specimen at a large penetration depth is a challenge in biophysics and material science. Refractive index mismatch results in spherical aberration that is responsible for streaking artifacts, while Poissonian nature of photon emission and scattering introduces noise in the acquired three-dimensional image. To overcome these unwanted artifacts, we introduced a two-fold approach: first, point-spread function modeling with correction for spherical aberration and second, employing maximum-likelihood reconstruction technique to eliminate noise. Experimental results on fluorescent nano-beads and fluorescently coated yeast cells (encaged in Agarose gel) shows substantial minimization of artifacts. The noise is substantially suppressed, whereas the side-lobes (generated by streaking effect) drops by 48.6% as compared to raw data at a depth of 150 μm. Proposed imaging technique can be integrated to sophisticated fluorescence imaging techniques for rendering high resolution beyond 150 μm mark.

  13. Enabling Requirements-Based Programming for Highly-Dependable Complex Parallel and Distributed Systems

    NASA Technical Reports Server (NTRS)

    Hinchey, Michael G.; Rash, James L.; Rouff, Christopher A.

    2005-01-01

    The manual application of formal methods in system specification has produced successes, but in the end, despite any claims and assertions by practitioners, there is no provable relationship between a manually derived system specification or formal model and the customer's original requirements. Complex parallel and distributed system present the worst case implications for today s dearth of viable approaches for achieving system dependability. No avenue other than formal methods constitutes a serious contender for resolving the problem, and so recognition of requirements-based programming has come at a critical juncture. We describe a new, NASA-developed automated requirement-based programming method that can be applied to certain classes of systems, including complex parallel and distributed systems, to achieve a high degree of dependability.

  14. High temperature nitrogen oxides sensing enabled by indium oxide thin films

    NASA Astrophysics Data System (ADS)

    Kannan, Srinivasan

    Generation of power using fossil fuel combustion invariably results in formation of undesirable gas species (NOx, SOx, CO, CO2, etc.) at high-temperatures which are harmful to the environment. Thus, there is a continual need to develop sensitive, responsive, stable, selective, robust and low-cost sensor systems and sensor materials for combustion monitoring. This work investigates the viability of microfabricated NO x sensors based on sputtered indium oxide (In2O3) utilizing microhotplate structures. The material becomes resistive when exposed to oxidizing gases like NOx, with its conductivity dependent upon the temperature, partial pressure of the test gas and morphological structure. We believe this device would help increase efficiency and decrease emissions through improved combustion process control, leading to a comparably economic and responsive sensor. In this work, more than 600 sensors were fabricated and tested, including RF and pulsed-DC sputtered films. About 50 unique sensor conditions were characterized and related to the gas sensor response. The sensor conditions included deposition parameters (power, pressure, time, etc.) and postdeposition processes (anneals, promoter layers, etc.). In2O3 thin films were RF sputter deposited on microhotplate structures with different thickness (40 to 300 nm) in pure Ar. Additionally, a combination of reactive and RF sputtering of In2O3 material was-deposited in Ar and O2 (10% and 25%) mixture. In2O3 films without promoter layers and with gold or TiOx promoter layers (~ 3 nm) were investigated for NOx sensing. Selectivity, stability and repeatability of indium oxide (In2O3) thin film sensor to detect NOx (25 ppm) in presence of other exhaust gas pollutants including H2, NH3 and CO2 at high operating temperatures (greater than 350 °C) was investigated in N2 carrier gas. In2O 3 films (150nm thick) deposited in Ar and O2 (25% O 2) presented the highest response (S ~ 50) to 25 ppm NOx at 500 °C when compared to films

  15. The impact of computer science in molecular medicine: enabling high-throughput research.

    PubMed

    de la Iglesia, Diana; García-Remesal, Miguel; de la Calle, Guillermo; Kulikowski, Casimir; Sanz, Ferran; Maojo, Víctor

    2013-01-01

    The Human Genome Project and the explosion of high-throughput data have transformed the areas of molecular and personalized medicine, which are producing a wide range of studies and experimental results and providing new insights for developing medical applications. Research in many interdisciplinary fields is resulting in data repositories and computational tools that support a wide diversity of tasks: genome sequencing, genome-wide association studies, analysis of genotype-phenotype interactions, drug toxicity and side effects assessment, prediction of protein interactions and diseases, development of computational models, biomarker discovery, and many others. The authors of the present paper have developed several inventories covering tools, initiatives and studies in different computational fields related to molecular medicine: medical informatics, bioinformatics, clinical informatics and nanoinformatics. With these inventories, created by mining the scientific literature, we have carried out several reviews of these fields, providing researchers with a useful framework to locate, discover, search and integrate resources. In this paper we present an analysis of the state-of-the-art as it relates to computational resources for molecular medicine, based on results compiled in our inventories, as well as results extracted from a systematic review of the literature and other scientific media. The present review is based on the impact of their related publications and the available data and software resources for molecular medicine. It aims to provide information that can be useful to support ongoing research and work to improve diagnostics and therapeutics based on molecular-level insights.

  16. Two-dimensional Layered MoS2 Biosensors Enable Highly Sensitive Detection of Biomolecules

    NASA Astrophysics Data System (ADS)

    Lee, Joonhyung; Dak, Piyush; Lee, Yeonsung; Park, Heekyeong; Choi, Woong; Alam, Muhammad A.; Kim, Sunkook

    2014-12-01

    We present a MoS2 biosensor to electrically detect prostate specific antigen (PSA) in a highly sensitive and label-free manner. Unlike previous MoS2-FET-based biosensors, the device configuration of our biosensors does not require a dielectric layer such as HfO2 due to the hydrophobicity of MoS2. Such an oxide-free operation improves sensitivity and simplifies sensor design. For a quantitative and selective detection of PSA antigen, anti-PSA antibody was immobilized on the sensor surface. Then, introduction of PSA antigen, into the anti-PSA immobilized sensor surface resulted in a lable-free immunoassary format. Measured off-state current of the device showed a significant decrease as the applied PSA concentration was increased. The minimum detectable concentration of PSA is 1 pg/mL, which is several orders of magnitude below the clinical cut-off level of ~4 ng/mL. In addition, we also provide a systematic theoretical analysis of the sensor platform - including the charge state of protein at the specific pH level, and self-consistent channel transport. Taken together, the experimental demonstration and the theoretical framework provide a comprehensive description of the performance potential of dielectric-free MoS2-based biosensor technology.

  17. Structured nucleosome fingerprints enable high-resolution mapping of chromatin architecture within regulatory regions.

    PubMed

    Schep, Alicia N; Buenrostro, Jason D; Denny, Sarah K; Schwartz, Katja; Sherlock, Gavin; Greenleaf, William J

    2015-11-01

    Transcription factors canonically bind nucleosome-free DNA, making the positioning of nucleosomes within regulatory regions crucial to the regulation of gene expression. Using the assay of transposase accessible chromatin (ATAC-seq), we observe a highly structured pattern of DNA fragment lengths and positions around nucleosomes in Saccharomyces cerevisiae, and use this distinctive two-dimensional nucleosomal "fingerprint" as the basis for a new nucleosome-positioning algorithm called NucleoATAC. We show that NucleoATAC can identify the rotational and translational positions of nucleosomes with up to base-pair resolution and provide quantitative measures of nucleosome occupancy in S. cerevisiae, Schizosaccharomyces pombe, and human cells. We demonstrate the application of NucleoATAC to a number of outstanding problems in chromatin biology, including analysis of sequence features underlying nucleosome positioning, promoter chromatin architecture across species, identification of transient changes in nucleosome occupancy and positioning during a dynamic cellular response, and integrated analysis of nucleosome occupancy and transcription factor binding.

  18. A high-performance keyboard neural prosthesis enabled by task optimization

    PubMed Central

    Nuyujukian, Paul; Fan, Joline M.; Kao, Jonathan C.; Ryu, Stephen I.; Shenoy, Krishna V.

    2015-01-01

    Communication neural prostheses are an emerging class of medical devices that aim to restore efficient communication to people suffering from paralysis. These systems rely on an interface with the user, either via the use of a continuously-moving cursor (e.g., mouse) or the discrete selection of symbols (e.g., keyboard). In developing these interfaces, many design choices have a significant impact on the performance of the system. The objective of this study was to explore the design choices of a continuously-moving cursor neural prosthesis and optimize the interface to maximize information theoretic performance. We swept interface parameters of two keyboard-like tasks to find task and subject specific optimal parameters as measured by achieved bitrate using two rhesus macaques implanted with multielectrode arrays. In this report, we present the highest performing free-paced neural prosthesis under any recording modality with sustainable communication rates of up to 3.5 bits per second (bps). These findings demonstrate that meaningful high performance can be achieved using an intracortical neural prosthesis, and that, when optimized, these systems may be appropriate for use as communication devices for those with physical disabilities. PMID:25203982

  19. Highly sampled tetranucleotide and tetraloop motifs enable evaluation of common RNA force fields.

    PubMed

    Bergonzo, Christina; Henriksen, Niel M; Roe, Daniel R; Cheatham, Thomas E

    2015-09-01

    Recent modifications and improvements to standard nucleic acid force fields have attempted to fix problems and issues that have been observed as longer timescale simulations have become routine. Although previous work has shown the ability to fold the UUCG stem-loop structure, until now no group has attempted to quantify the performance of current force fields using highly converged structural populations of the tetraloop conformational ensemble. In this study, we report the use of multiple independent sets of multidimensional replica exchange molecular dynamics (M-REMD) simulations with different initial conditions to generate well-converged conformational ensembles for the tetranucleotides r(GACC) and r(CCCC), as well as the larger UUCG tetraloop motif. By generating what is to our knowledge the most complete RNA structure ensembles reported to date for these systems, we remove the coupling between force field errors and errors due to incomplete sampling, providing a comprehensive comparison between current top-performing MD force fields for RNA. Of the RNA force fields tested in this study, none demonstrate the ability to correctly identify the most thermodynamically stable structure for all three systems. We discuss the deficiencies present in each potential function and suggest areas where improvements can be made. The results imply that although "short" (nsec-μsec timescale) simulations may stay close to their respective experimental structures and may well reproduce experimental observables, inevitably the current force fields will populate alternative incorrect structures that are more stable than those observed via experiment.

  20. Two-dimensional layered MoS₂ biosensors enable highly sensitive detection of biomolecules.

    PubMed

    Lee, Joonhyung; Dak, Piyush; Lee, Yeonsung; Park, Heekyeong; Choi, Woong; Alam, Muhammad A; Kim, Sunkook

    2014-01-01

    We present a MoS2 biosensor to electrically detect prostate specific antigen (PSA) in a highly sensitive and label-free manner. Unlike previous MoS2-FET-based biosensors, the device configuration of our biosensors does not require a dielectric layer such as HfO2 due to the hydrophobicity of MoS2. Such an oxide-free operation improves sensitivity and simplifies sensor design. For a quantitative and selective detection of PSA antigen, anti-PSA antibody was immobilized on the sensor surface. Then, introduction of PSA antigen, into the anti-PSA immobilized sensor surface resulted in a lable-free immunoassary format. Measured off-state current of the device showed a significant decrease as the applied PSA concentration was increased. The minimum detectable concentration of PSA is 1 pg/mL, which is several orders of magnitude below the clinical cut-off level of ~4 ng/mL. In addition, we also provide a systematic theoretical analysis of the sensor platform - including the charge state of protein at the specific pH level, and self-consistent channel transport. Taken together, the experimental demonstration and the theoretical framework provide a comprehensive description of the performance potential of dielectric-free MoS2-based biosensor technology.

  1. Highly Flexible Self-Assembled V2O5 Cathodes Enabled by Conducting Diblock Copolymers

    NASA Astrophysics Data System (ADS)

    An, Hyosung; Mike, Jared; Smith, Kendall A.; Swank, Lisa; Lin, Yen-Hao; L. Pesek, Stacy; Verduzco, Rafael; Lutkenhaus, Jodie L.

    2015-09-01

    Mechanically robust battery electrodes are desired for applications in wearable devices, flexible displays, and structural energy and power. In this regard, the challenge is to balance mechanical and electrochemical properties in materials that are inherently brittle. Here, we demonstrate a unique water-based self-assembly approach that incorporates a diblock copolymer bearing electron- and ion-conducting blocks, poly(3-hexylthiophene)-block-poly(ethyleneoxide) (P3HT-b-PEO), with V2O5 to form a flexible, tough, carbon-free hybrid battery cathode. V2O5 is a promising lithium intercalation material, but it remains limited by its poor conductivity and mechanical properties. Our approach leads to a unique electrode structure consisting of interlocking V2O5 layers glued together with micellar aggregates of P3HT-b-PEO, which results in robust mechanical properties, far exceeding the those obtained from conventional fluoropolymer binders. Only 5 wt % polymer is required to triple the flexibility of V2O5, and electrodes comprised of 10 wt % polymer have unusually high toughness (293 kJ/m3) and specific energy (530 Wh/kg), both higher than reduced graphene oxide paper electrodes. Furthermore, addition of P3HT-b-PEO enhances lithium-ion diffusion, eliminates cracking during cycling, and boosts cyclability relative to V2O5 alone. These results highlight the importance of tradeoffs between mechanical and electrochemical performance, where polymer content can be used to tune both aspects.

  2. Light enables a very high efficiency of carbon storage in developing embryos of rapeseed.

    PubMed

    Goffman, Fernando D; Alonso, Ana P; Schwender, Jörg; Shachar-Hill, Yair; Ohlrogge, John B

    2005-08-01

    The conversion of photosynthate to seed storage reserves is crucial to plant fitness and agricultural production, yet quantitative information about the efficiency of this process is lacking. To measure metabolic efficiency in developing seeds, rapeseed (Brassica napus) embryos were cultured in media in which all carbon sources were [U-14C]-labeled and their conversion into CO2, oil, protein, and other biomass was determined. The conversion efficiency of the supplied carbon into seed storage reserves was very high. When provided with 0, 50, or 150 micromol m(-2) s(-1) light, the proportion of carbon taken up by embryos that was recovered in biomass was 60% to 64%, 77% to 86%, and 85% to 95%, respectively. Light not only improved the efficiency of carbon storage, but also increased the growth rate, the proportion of 14C recovered in oil relative to protein, and the fixation of external 14CO2 into biomass. Embryos grown at 50 micromol m(-2) s(-1) in the presence of 5 microM 1,1-dimethyl-3-(3,4-dichlorophenyl) urea (an inhibitor of photosystem II) were reduced in total biomass and oil synthesis by 3.2-fold and 2.8-fold, respectively, to the levels observed in the dark. To explore if the reduced growth and carbon conversion efficiency in dark were related to oxygen supplied by photosystem II, embryos and siliques were cultured with increased oxygen. The carbon conversion efficiency of embryos remained unchanged when oxygen levels were increased 3-fold. Increasing the O2 levels surrounding siliques from 21% to 60% did not increase oil synthesis rates either at 1,000 micromol m(-2) s(-1) or in the dark. We conclude that light increases the growth, efficiency of carbon storage, and oil synthesis in developing rapeseed embryos primarily by providing reductant and/or ATP.

  3. High-Throughput Excipient Discovery Enables Oral Delivery of Poorly Soluble Pharmaceuticals

    PubMed Central

    2016-01-01

    Polymeric excipients are crucial ingredients in modern pills, increasing the therapeutic bioavailability, safety, stability, and accessibility of lifesaving products to combat diseases in developed and developing countries worldwide. Because many early-pipeline drugs are clinically intractable due to hydrophobicity and crystallinity, new solubilizing excipients can reposition successful and even failed compounds to more effective and inexpensive oral formulations. With assistance from high-throughput controlled polymerization and screening tools, we employed a strategic, molecular evolution approach to systematically modulate designer excipients based on the cyclic imide chemical groups of an important (yet relatively insoluble) drug phenytoin. In these acrylamide- and methacrylate-containing polymers, a synthon approach was employed: one monomer served as a precipitation inhibitor for phenytoin recrystallization, while the comonomer provided hydrophilicity. Systems that maintained drug supersaturation in amorphous solid dispersions were identified with molecular-level understanding of noncovalent interactions using NOESY and DOSY NMR spectroscopy. Poly(N-isopropylacrylamide-co-N,N-dimethylacrylamide) (poly(NIPAm-co-DMA)) at 70 mol % NIPAm exhibited the highest drug solubilization, in which phenytoin associated with inhibiting NIPAm units only with lowered diffusivity in solution. In vitro dissolution tests of select spray-dried dispersions corroborated the screening trends between polymer chemical composition and solubilization performance, where the best NIPAm/DMA polymer elevated the mean area-under-the-dissolution-curve by 21 times its crystalline state at 10 wt % drug loading. When administered to rats for pharmacokinetic evaluation, the same leading poly(NIPAm-co-DMA) formulation tripled the oral bioavailability compared to a leading commercial excipient, HPMCAS, and translated to a remarkable 23-fold improvement over crystalline phenytoin. PMID:27800558

  4. High-power fused assemblies enabled by advances in fiber-processing technologies

    NASA Astrophysics Data System (ADS)

    Wiley, Robert; Clark, Brett

    2011-02-01

    The power handling capabilities of fiber lasers are limited by the technologies available to fabricate and assemble the key optical system components. Previous tools for the assembly, tapering, and fusion of fiber laser elements have had drawbacks with regard to temperature range, alignment capability, assembly flexibility and surface contamination. To provide expanded capabilities for fiber laser assembly, a wide-area electrical plasma heat source was used in conjunction with an optimized image analysis method and a flexible alignment system, integrated according to mechatronic principles. High-resolution imaging and vision-based measurement provided feedback to adjust assembly, fusion, and tapering process parameters. The system was used to perform assembly steps including dissimilar-fiber splicing, tapering, bundling, capillary bundling, and fusion of fibers to bulk optic devices up to several mm in diameter. A wide range of fiber types and diameters were tested, including extremely large diameters and photonic crystal fibers. The assemblies were evaluated for conformation to optical and mechanical design criteria, such as taper geometry and splice loss. The completed assemblies met the performance targets and exhibited reduced surface contamination compared to assemblies prepared on previously existing equipment. The imaging system and image analysis algorithms provided in situ fiber geometry measurement data that agreed well with external measurement. The ability to adjust operating parameters dynamically based on imaging was shown to provide substantial performance benefits, particularly in the tapering of fibers and bundles. The integrated design approach was shown to provide sufficient flexibility to perform all required operations with a minimum of reconfiguration.

  5. Timing of high-intensity pulses for myocardial cavitation-enabled therapy

    PubMed Central

    2014-01-01

    Background High-intensity ultrasound pulses intermittently triggered from an ECG signal can interact with circulating contrast agent microbubbles to produce myocardial cavitation microlesions of potential therapeutic value. In this study, the timing of therapy pulses relative to the ECG R wave was investigated to identify the optimal time point for tissue reduction therapy with regard to both the physiological cardiac response and microlesion production. Methods Rats were anesthetized, prepared for ultrasound, placed in a heated water bath, and treated with 1.5 MHz focused ultrasound pulses targeted to the left ventricular myocardium with an 8 MHz imaging transducer. Initially, the rats were treated for 1 min at each of six different time points in the ECG while monitoring blood pressure responses to assess cardiac functional effects. Next, groups of rats were treated at three different time points: end diastole, end systole, and mid-diastole to assess the impact of timing on microlesion creation. These rats were pretreated with Evans blue injections and were allowed to recover for 1 day until hearts were harvested for scoring of injured cardiomyocytes. Results The initial results showed a wide range of cardiac premature complexes in the ECG, which corresponded with blood pressure pulses for ultrasound pulses triggered during diastole. However, the microlesion experiment did not reveal any statistically significant variations in cardiomyocyte injury. Conclusion The end of systole (R + RR/3) was identified as an optimal trigger time point which produced identifiable ECG complexes and substantial cardiomyocyte injury but minimal cardiac functional disruption during treatment. PMID:25279221

  6. Strong Ion Regulatory Abilities Enable the Crab Xenograpsus testudinatus to Inhabit Highly Acidified Marine Vent Systems

    PubMed Central

    Hu, Marian Y.; Guh, Ying-Jey; Shao, Yi-Ta; Kuan, Pou-Long; Chen, Guan-Lin; Lee, Jay-Ron; Jeng, Ming-Shiou; Tseng, Yung-Che

    2016-01-01

    Hydrothermal vent organisms have evolved physiological adaptations to cope with extreme abiotic conditions including temperature and pH. To date, acid-base regulatory abilities of vent organisms are poorly investigated, although this physiological feature is essential for survival in low pH environments. We report the acid-base regulatory mechanisms of a hydrothermal vent crab, Xenograpsus testudinatus, endemic to highly acidic shallow-water vent habitats with average environment pH-values ranging between 5.4 and 6.6. Within a few hours, X. testudinatus restores extracellular pH (pHe) in response to environmental acidification of pH 6.5 (1.78 kPa pCO2) accompanied by an increase in blood HCO3- levels from 8.8 ± 0.3 to 31 ± 6 mM. Branchial Na+/K+-ATPase (NKA) and V-type H+-ATPase (VHA), the major ion pumps involved in branchial acid-base regulation, showed dynamic increases in response to acidified conditions on the mRNA, protein and activity level. Immunohistochemical analyses demonstrate the presence of NKA in basolateral membranes, whereas the VHA is predominantly localized in cytoplasmic vesicles of branchial epithelial- and pillar-cells. X. testudinatus is closely related to other strong osmo-regulating brachyurans, which is also reflected in the phylogeny of the NKA. Accordingly, our results suggest that the evolution of strong ion regulatory abilities in brachyuran crabs that allowed the occupation of ecological niches in euryhaline, freshwater, and terrestrial habitats are probably also linked to substantial acid-base regulatory abilities. This physiological trait allowed X. testudinatus to successfully inhabit one of the world's most acidic marine environments. PMID:26869933

  7. Highly Flexible Self-Assembled V2O5 Cathodes Enabled by Conducting Diblock Copolymers

    PubMed Central

    An, Hyosung; Mike, Jared; Smith, Kendall A.; Swank, Lisa; Lin, Yen-Hao; L. Pesek, Stacy; Verduzco, Rafael; Lutkenhaus, Jodie L.

    2015-01-01

    Mechanically robust battery electrodes are desired for applications in wearable devices, flexible displays, and structural energy and power. In this regard, the challenge is to balance mechanical and electrochemical properties in materials that are inherently brittle. Here, we demonstrate a unique water-based self-assembly approach that incorporates a diblock copolymer bearing electron- and ion-conducting blocks, poly(3-hexylthiophene)-block-poly(ethyleneoxide) (P3HT-b-PEO), with V2O5 to form a flexible, tough, carbon-free hybrid battery cathode. V2O5 is a promising lithium intercalation material, but it remains limited by its poor conductivity and mechanical properties. Our approach leads to a unique electrode structure consisting of interlocking V2O5 layers glued together with micellar aggregates of P3HT-b-PEO, which results in robust mechanical properties, far exceeding the those obtained from conventional fluoropolymer binders. Only 5 wt % polymer is required to triple the flexibility of V2O5, and electrodes comprised of 10 wt % polymer have unusually high toughness (293 kJ/m3) and specific energy (530 Wh/kg), both higher than reduced graphene oxide paper electrodes. Furthermore, addition of P3HT-b-PEO enhances lithium-ion diffusion, eliminates cracking during cycling, and boosts cyclability relative to V2O5 alone. These results highlight the importance of tradeoffs between mechanical and electrochemical performance, where polymer content can be used to tune both aspects. PMID:26391053

  8. Tales of scales: how to enable backup process tool qualification for high-end photomasks

    NASA Astrophysics Data System (ADS)

    Cantrell, G. R.; Bürgel, Christian; Sczyrba, Martin; Heumann, Jan; Meusemann, Stefan; Utzny, Clemens

    2012-06-01

    Strict reticle critical dimension (CD) control is needed to supply <= 20nm wafer technology nodes. In front end lithographic processes for example, precise temperature control in resist baking steps is considered paramount to limiting reticle CD error sources. Additionally, current density during writing and focus are continuously tracked in 50kV e-beam pattern generators (PG) in order to provide stable CD performance. Despite these strict controls (and many others), feedback compensation strategies are increasingly utilized in mask manufacturing to reach < 2nm 3σ CD uniformity (CDU). Such compensations require stable reticle CD signatures which can be problematic when alternate or backup process tools are employed. The AMTC has applied principle component analysis (PCA) to resist CD measurements of 50kV test reticles fabricated with chemically amplified resists (CAR) in order to quantify the resist CDU capabilities of front and backup lithographic process tools. PCA results elucidate significant resist CDU differences between similar lithographic process tools that are considered well matched via CDU 3σ comparisons. The utility of PCA relies on the statistical analysis of large data sets however, reticle CD sampling is typically sparse, on the 10-2 m or centimeter (cm) scale using conventional scanning electron microscopes (CD SEM). Higher CD spatial resolutions can be achieved using advanced inspection tools, which provide CD data on a substantially smaller length scale (10-4 m), thus yielding a considerably larger CD snapshot for front/backup process tool comparisons. Combining PCA analysis with high spatial resolution CD data provides novel insights into the opportunities for tool and process CD capabilities.

  9. Highly Flexible Self-Assembled V2O5 Cathodes Enabled by Conducting Diblock Copolymers

    DOE PAGES

    An, Hyosung; Mike, Jared; Smith, Kendall A.; Swank, Lisa; Lin, Yen-Hao; L. Pesek, Stacy; Verduzco, Rafael; Lutkenhaus, Jodie L.

    2015-09-22

    Mechanically robust battery electrodes are desired for applications in wearable devices, flexible displays, and structural energy and power. In this regard, the challenge is to balance mechanical and electrochemical properties in materials that are inherently brittle. Here, we demonstrate a unique water-based self-assembly approach that incorporates a diblock copolymer bearing electron- and ion-conducting blocks, poly(3-hexylthiophene)-block-poly(ethyleneoxide) (P3HT-b-PEO), with V2O5 to form a flexible, tough, carbon-free hybrid battery cathode. V2O5 is a promising lithium intercalation material, but it remains limited by its poor conductivity and mechanical properties. Our approach leads to a unique electrode structure consisting of interlocking V2O5 layers glued togethermore » with micellar aggregates of P3HT-b-PEO, which results in robust mechanical properties, far exceeding the those obtained from conventional fluoropolymer binders. Only 5 wt % polymer is required to triple the flexibility of V2O5, and electrodes comprised of 10 wt % polymer have unusually high toughness (293 kJ/m3) and specific energy (530 Wh/kg), both higher than reduced graphene oxide paper electrodes. Furthermore, addition of P3HT-b-PEO enhances lithium-ion diffusion, eliminates cracking during cycling, and boosts cyclability relative to V2O5 alone. These results highlight the importance of tradeoffs between mechanical and electrochemical performance, where polymer content can be used to tune both aspects.« less

  10. Highly Cross-Linked Epoxy Nanofiltration Membranes for the Separation of Organic Chemicals and Fish Oil Ethyl Esters.

    PubMed

    Gilmer, Chad M; Bowden, Ned B

    2016-09-14

    Membrane separations are highly desired for the chemical industry because they are inexpensive, avoid the use of heat, can be applied to the purification of a wide range of chemicals, and can be scaled to industrial levels. Separating chemicals with molecular weights between 100 and 300 g mol(-1) remains a significant challenge in the field of organic solvent nanofiltration (OSN) due to their similar sizes and rotational flexibility. In this work, we report the fabrication of poly(epoxy) membranes that show excellent selectivity of over 100:1 for chemicals in this range. The membranes are easily tuned to obtain different flux and selectivity by using interchangeable amine and epoxide monomers. These membranes were used to separate the important nutritional omega-3 fatty acid ethyl esters eicosapentaenoic ethyl ester (EPA-EE) and docosahexaenoic acid ethyl ester (DHA-EE) from each other, despite a small difference in molecular weight (26 g mol(-1)). This is the first example of a separation of EPA-EE and DHA-EE using a membrane process.

  11. Highly Cross-Linked Epoxy Nanofiltration Membranes for the Separation of Organic Chemicals and Fish Oil Ethyl Esters.

    PubMed

    Gilmer, Chad M; Bowden, Ned B

    2016-09-14

    Membrane separations are highly desired for the chemical industry because they are inexpensive, avoid the use of heat, can be applied to the purification of a wide range of chemicals, and can be scaled to industrial levels. Separating chemicals with molecular weights between 100 and 300 g mol(-1) remains a significant challenge in the field of organic solvent nanofiltration (OSN) due to their similar sizes and rotational flexibility. In this work, we report the fabrication of poly(epoxy) membranes that show excellent selectivity of over 100:1 for chemicals in this range. The membranes are easily tuned to obtain different flux and selectivity by using interchangeable amine and epoxide monomers. These membranes were used to separate the important nutritional omega-3 fatty acid ethyl esters eicosapentaenoic ethyl ester (EPA-EE) and docosahexaenoic acid ethyl ester (DHA-EE) from each other, despite a small difference in molecular weight (26 g mol(-1)). This is the first example of a separation of EPA-EE and DHA-EE using a membrane process. PMID:27552234

  12. Wear, delamination, and fatigue resistance of melt-annealed highly crosslinked UHMWPE cruciate-retaining knee inserts under activities of daily living.

    PubMed

    Popoola, Oludele O; Yao, Jian Q; Johnson, Todd S; Blanchard, Cheryl R

    2010-09-01

    The wear, delamination, and fatigue resistance of artificially aged gamma irradiation-sterilized conventional polyethylene (CPE) and gas-plasma-sterilized melt-annealed highly crosslinked polyethylene tibial inserts (HXPE) were compared. Six CPE and 12 HXPE (six irradiated at 58 kGy and six at 72 kGy) left knee inserts were wear tested for 5.5 million cycles (Mc) under loads and motions that mimic activities of daily living, such as walking, chair rise, stair ascent, and deep squatting. Another six HXPE (72 kGy) and six CPE inserts were also tested under conditions that could produce severe delamination for 8 Mc. Ten other knees (five 72 kGy HXPE and five CPE) were subjected to posterior edge loading fatigue testing for 5 Mc. The HXPE inserts had an average wear rate reduction of about 80% relative to their CPE counterparts during all activities. All of the CPE inserts delaminated and fractured during high cycle deep squat (152 degrees flexion) motions, while all the HXPE remained intact. None of the HXPE inserts delaminated after 8 Mc, while all of the CPE inserts developed delamination damage within 1.5-5.8 Mc of delamination testing. All CPE inserts developed subsurface cracks and delamination within 2.8 Mc during posterior edge loading fatigue studies, while none of the HXPE inserts showed cracking or delamination after 5 Mc. These results show that aged HXPE has higher wear and fatigue resistance than aged CPE, and offers potential long-term advantages for young active patients with sustained activities of daily living.

  13. Tailoring ultraresins based on the cross-linking of polyethylene imines. Comparative investigation of the chemical composition, the swelling, the mobility, the chemical accessibility, and the performance in solid-phase synthesis of very high loaded resins.

    PubMed

    Barth, Michael; Rademann, Jörg

    2004-01-01

    Ultraresins have been prepared from polyethyleneimines and cross-linking molecules and have been provided with various degrees of cross-linking. The total nitrogen loading and the loading with secondary and with tertiary amines have been determined in all products. Nitrogen loadings of the novel resins were up to 15 mmol/g, reactive secondary amines up to 13.8 mmol/g. In addition to the exceptionally high loading, the novel resins displayed efficient swelling volumes in polar and nonpolar solvents. The mobility of resin-bound species as determined by EPR-spectroscopy, depending on the amount of cross-linker, indicated good flexibility and reactivity of this resin type. The novel, high-loaded resins have been investigated subsequently in solid-phase synthesis. The Rink amide linker and two different hydroxy linkers (hydroxyacetamide, HMPB) have been attached to the resin. Despite the high loadings, the secondary amines were easily accessible and could be functionalized exhaustively. Reactivity of the linker-coupled resins was found to be closely related to the resin composition. Increased resin cross-linking led to reduced swelling, reduced mobility, and reduced reactivity in the synthesis of a medium-sized model peptide. As the result of the systematic investigation of structure-property relations in Ultraresins, a support material was identified that combined high reactivity and a mobility in the range of the extremely flexible Tentagel supports. In the optimized Ultraresin, >95% of all available secondary nitrogens could be coupled with Rink linker or with the small 2-hydroxyacetamide anchor, resulting in loadings from 2.7 to 6.8 mmol/g, respectively. A resin with an attached HMPB linker and spacer delivered analytically pure peptides in solid-phase synthesis, fully exploiting the exceptionally high loadings.

  14. Chitosan membranes for tissue engineering: comparison of different crosslinkers.

    PubMed

    Ruini, F; Tonda-Turo, C; Chiono, V; Ciardelli, G

    2015-11-03

    Chitosan (CS), a derivative of the naturally occurring biopolymer chitin, is an attractive material for biomedical applications thanks to its biocompatibility, biodegradability, antibacterial properties and ability to enhance cell adhesion and growth compared to other biopolymers. However, the physical and mechanical stability of CS based materials in aqueous solutions is limited and crosslinking agents are required to increase CS performances in a biological environment. In this work, the effect of three highly-biocompatible crosslinkers as genipin (GP), γ-glycidoxypropyltrimethoxysilane (GPTMS), dibasic sodium phosphate (DSP) and a combination of GPTMS and DSP (GPTMS_DSP) on CS physicochemical, thermal, morphological, mechanical properties, swelling and degradation behavior was investigated. Infrared spectroscopy and thermogravimetric analyses confirmed the chemical reaction between CS and the different crosslinkers. CS wettability was enhanced when CS was DSP ionically crosslinked showing contact angle values of about 65° and exhibiting a higher swelling behavior compared to covalently crosslinked films. Moreover, all the crosslinking methods analyzed improved the stability of CS in aqueous media, showed model molecule permeation in time and increased the mechanical properties when compared with non-crosslinked films. The possibility to tailor the final properties of CS scaffolds through crosslinking is a key strategy in applying CS in different biomedical and tissue engineering applications. The obtained results reveal that the optimization of the crosslinking mechanism provides CS membrane properties required in different biomedical applications.

  15. Shear-Thinning Supramolecular Hydrogels with Secondary Autonomous Covalent Crosslinking to Modulate Viscoelastic Properties In Vivo

    PubMed Central

    Rodell, Christopher B.; MacArthur, John W.; Dorsey, Shauna M.; Wade, Ryan J.; Wang, Leo L.; Woo, Y. Joseph

    2015-01-01

    Clinical percutaneous delivery of synthetically engineered hydrogels remains limited due to challenges posed by crosslinking kinetics – too fast leads to delivery failure, too slow limits material retention. To overcome this challenge, we exploit supramolecular assembly to localize hydrogels at the injection site and introduce subsequent covalent crosslinking to control final material properties. Supramolecular gels were designed through the separate pendant modifications of hyaluronic acid (HA) by the guest-host pair cyclodextrin and adamantane, enabling shear-thinning injection and high target site retention (>98%). Secondary covalent crosslinking occurred via addition of thiols and Michael-acceptors (i.e., methacrylates, acrylates, vinyl sulfones) on HA and increased hydrogel moduli (E=25.0±4.5kPa) and stability (>3.5 fold in vivo at 28 days). Application of the dual-crosslinking hydrogel to a myocardial infarct model showed improved outcomes relative to untreated and supramolecular hydrogel alone controls, demonstrating its potential in a range of applications where the precise delivery of hydrogels with tunable properties is desired. PMID:26526097

  16. High-utility conserved avian microsatellite markers enable parentage and population studies across a wide range of species

    PubMed Central

    2013-01-01

    Background Microsatellites are widely used for many genetic studies. In contrast to single nucleotide polymorphism (SNP) and genotyping-by-sequencing methods, they are readily typed in samples of low DNA quality/concentration (e.g. museum/non-invasive samples), and enable the quick, cheap identification of species, hybrids, clones and ploidy. Microsatellites also have the highest cross-species utility of all types of markers used for genotyping, but, despite this, when isolated from a single species, only a relatively small proportion will be of utility. Marker development of any type requires skill and time. The availability of sufficient “off-the-shelf” markers that are suitable for genotyping a wide range of species would not only save resources but also uniquely enable new comparisons of diversity among taxa at the same set of loci. No other marker types are capable of enabling this. We therefore developed a set of avian microsatellite markers with enhanced cross-species utility. Results We selected highly-conserved sequences with a high number of repeat units in both of two genetically distant species. Twenty-four primer sets were designed from homologous sequences that possessed at least eight repeat units in both the zebra finch (Taeniopygia guttata) and chicken (Gallus gallus). Each primer sequence was a complete match to zebra finch and, after accounting for degenerate bases, at least 86% similar to chicken. We assessed primer-set utility by genotyping individuals belonging to eight passerine and four non-passerine species. The majority of the new Conserved Avian Microsatellite (CAM) markers amplified in all 12 species tested (on average, 94% in passerines and 95% in non-passerines). This new marker set is of especially high utility in passerines, with a mean 68% of loci polymorphic per species, compared with 42% in non-passerine species. Conclusions When combined with previously described conserved loci, this new set of conserved markers will not only

  17. Bespoke contrast-matched diblock copolymer nanoparticles enable the rational design of highly transparent Pickering double emulsions

    NASA Astrophysics Data System (ADS)

    Rymaruk, Matthew J.; Thompson, Kate L.; Derry, Matthew J.; Warren, Nicholas J.; Ratcliffe, Liam P. D.; Williams, Clive N.; Brown, Steven L.; Armes, Steven P.

    2016-07-01

    We report the preparation of highly transparent oil-in-water Pickering emulsions using contrast-matched organic nanoparticles. This is achieved via addition of judicious amounts of either sucrose or glycerol to an aqueous dispersion of poly(glycerol monomethacrylate)56-poly(2,2,2-trifluoroethyl methacrylate)500 [PGMA-PTFEMA] diblock copolymer nanoparticles prior to high shear homogenization with an equal volume of n-dodecane. The resulting Pickering emulsions comprise polydisperse n-dodecane droplets of 20-100 μm diameter and exhibit up to 96% transmittance across the visible spectrum. In contrast, control experiments using non-contrast-matched poly(glycerol monomethacrylate)56-poly(benzyl methacrylate)300 [PGMA56-PBzMA300] diblock copolymer nanoparticles as a Pickering emulsifier only produced conventional highly turbid emulsions. Thus contrast-matching of the two immiscible phases is a necessary but not sufficient condition for the preparation of highly transparent Pickering emulsions: it is essential to use isorefractive nanoparticles in order to minimize light scattering. Furthermore, highly transparent oil-in-water-in-oil Pickering double emulsions can be obtained by homogenizing the contrast-matched oil-in-water Pickering emulsion prepared using the PGMA56-PTFEMA500 nanoparticles with a contrast-matched dispersion of hydrophobic poly(lauryl methacrylate)39-poly(2,2,2-trifluoroethyl methacrylate)800 [PLMA39-PTFEMA800] diblock copolymer nanoparticles in n-dodecane. Finally, we show that an isorefractive oil-in-water Pickering emulsion enables fluorescence spectroscopy to be used to monitor the transport of water-insoluble small molecules (pyrene and benzophenone) between n-dodecane droplets. Such transport is significantly less efficient than that observed for the equivalent isorefractive surfactant-stabilized emulsion. Conventional turbid emulsions do not enable such a comparison to be made because the intense light scattering leads to substantial spectral

  18. 2500 high-quality genomes reveal that the biogeochemical cycles of C, N, S and H are cross-linked by metabolic handoffs in the terrestrial subsurface

    NASA Astrophysics Data System (ADS)

    Anantharaman, K.; Brown, C. T.; Hug, L. A.; Sharon, I.; Castelle, C. J.; Shelton, A.; Bonet, B.; Probst, A. J.; Thomas, B. C.; Singh, A.; Wilkins, M.; Williams, K. H.; Tringe, S. G.; Beller, H. R.; Brodie, E.; Hubbard, S. S.; Banfield, J. F.

    2015-12-01

    Microorganisms drive the transformations of carbon compounds in the terrestrial subsurface, a key reservoir of carbon on earth, and impact other linked biogeochemical cycles. Our current knowledge of the microbial ecology in this environment is primarily based on 16S rRNA gene sequences that paint a biased picture of microbial community composition and provide no reliable information on microbial metabolism. Consequently, little is known about the identity and metabolic roles of the uncultivated microbial majority in the subsurface. In turn, this lack of understanding of the microbial processes that impact the turnover of carbon in the subsurface has restricted the scope and ability of biogeochemical models to capture key aspects of the carbon cycle. In this study, we used a culture-independent, genome-resolved metagenomic approach to decipher the metabolic capabilities of microorganisms in an aquifer adjacent to the Colorado River, near Rifle, CO, USA. We sequenced groundwater and sediment samples collected across fifteen different geochemical regimes. Sequence assembly, binning and manual curation resulted in the recovery of 2,542 high-quality genomes, 27 of which are complete. These genomes represent 1,300 non-redundant organisms comprising both abundant and rare community members. Phylogenetic analyses involving ribosomal proteins and 16S rRNA genes revealed the presence of up to 34 new phyla that were hitherto unknown. Less than 11% of all genomes belonged to the 4 most commonly represented phyla that constitute 93% of all currently available genomes. Genome-specific analyses of metabolic potential revealed the co-occurrence of important functional traits such as carbon fixation, nitrogen fixation and use of electron donors and electron acceptors. Finally, we predict that multiple organisms are often required to complete redox pathways through a complex network of metabolic handoffs that extensively cross-link subsurface biogeochemical cycles.

  19. Polybenzimidazole-crosslinked poly(vinylbenzyl chloride) with quaternary 1,4-diazabicyclo (2.2.2) octane groups as high-performance anion exchange membrane for fuel cells

    NASA Astrophysics Data System (ADS)

    Lu, Wangting; Zhang, Geng; Li, Jin; Hao, Jinkai; Wei, Feng; Li, Wenhui; Zhang, Jiying; Shao, Zhi-Gang; Yi, Baolian

    2015-11-01

    Development of anion exchange membrane (AEM) with high conductivity, good dimensional stability, desirable toughness and long life-time simultaneously is still a challenge for the practical application of AEM fuel cells. Herein, a novel AEM (denoted as PBI-c-PVBC/OH) is fabricated by applying polybenzimidazole (PBI) and 1,4-diazabicyclo (2.2.2) octane (DABCO) as the macromolecular crosslinker and quaternizing reagent for poly(vinylbenzyl chloride) (PVBC), respectively. With the aid of crosslinking by PBI, PBI-c-PVBC/OH exhibits good flexibility and strength both in dry and water-saturated state. Moreover, high hydroxide conductivity (>25 mS cm-1 at room temperature) and low swelling ratio (∼13%) is obtained, especially the swelling ratio nearly does not increase with temperature. The membrane is also advanced for the superior chemical stability in alkaline environment due to the stable polymer backbone and ionic conductive group (only one nitrogen atom in a DABCO molecule is quaternized). Furthermore, a peak power density of 230 mW cm-2 at 50 °C is obtained on the H2/O2 fuel cell using PBI-c-PVBC/OH, and the membrane presents high durability both in the constant current and continuous open circuit voltage testing. Therefore, it is considered that the PBI crosslinking together with DABCO quaternization can be regarded as a promising strategy in the development of AEM for fuel cells.

  20. Ultra-deep sequencing enables high-fidelity recovery of biodiversity for bulk arthropod samples without PCR amplification

    PubMed Central

    2013-01-01

    Background Next-generation-sequencing (NGS) technologies combined with a classic DNA barcoding approach have enabled fast and credible measurement for biodiversity of mixed environmental samples. However, the PCR amplification involved in nearly all existing NGS protocols inevitably introduces taxonomic biases. In the present study, we developed new Illumina pipelines without PCR amplifications to analyze terrestrial arthropod communities. Results Mitochondrial enrichment directly followed by Illumina shotgun sequencing, at an ultra-high sequence volume, enabled the recovery of Cytochrome c Oxidase subunit 1 (COI) barcode sequences, which allowed for the estimation of species composition at high fidelity for a terrestrial insect community. With 15.5 Gbp Illumina data, approximately 97% and 92% were detected out of the 37 input Operational Taxonomic Units (OTUs), whether the reference barcode library was used or not, respectively, while only 1 novel OTU was found for the latter. Additionally, relatively strong correlation between the sequencing volume and the total biomass was observed for species from the bulk sample, suggesting a potential solution to reveal relative abundance. Conclusions The ability of the new Illumina PCR-free pipeline for DNA metabarcoding to detect small arthropod specimens and its tendency to avoid most, if not all, false positives suggests its great potential in biodiversity-related surveillance, such as in biomonitoring programs. However, further improvement for mitochondrial enrichment is likely needed for the application of the new pipeline in analyzing arthropod communities at higher diversity. PMID:23587339

  1. Bespoke contrast-matched diblock copolymer nanoparticles enable the rational design of highly transparent Pickering double emulsions.

    PubMed

    Rymaruk, Matthew J; Thompson, Kate L; Derry, Matthew J; Warren, Nicholas J; Ratcliffe, Liam P D; Williams, Clive N; Brown, Steven L; Armes, Steven P

    2016-08-14

    We report the preparation of highly transparent oil-in-water Pickering emulsions using contrast-matched organic nanoparticles. This is achieved via addition of judicious amounts of either sucrose or glycerol to an aqueous dispersion of poly(glycerol monomethacrylate)56-poly(2,2,2-trifluoroethyl methacrylate)500 [PGMA-PTFEMA] diblock copolymer nanoparticles prior to high shear homogenization with an equal volume of n-dodecane. The resulting Pickering emulsions comprise polydisperse n-dodecane droplets of 20-100 μm diameter and exhibit up to 96% transmittance across the visible spectrum. In contrast, control experiments using non-contrast-matched poly(glycerol monomethacrylate)56-poly(benzyl methacrylate)300 [PGMA56-PBzMA300] diblock copolymer nanoparticles as a Pickering emulsifier only produced conventional highly turbid emulsions. Thus contrast-matching of the two immiscible phases is a necessary but not sufficient condition for the preparation of highly transparent Pickering emulsions: it is essential to use isorefractive nanoparticles in order to minimize light scattering. Furthermore, highly transparent oil-in-water-in-oil Pickering double emulsions can be obtained by homogenizing the contrast-matched oil-in-water Pickering emulsion prepared using the PGMA56-PTFEMA500 nanoparticles with a contrast-matched dispersion of hydrophobic poly(lauryl methacrylate)39-poly(2,2,2-trifluoroethyl methacrylate)800 [PLMA39-PTFEMA800] diblock copolymer nanoparticles in n-dodecane. Finally, we show that an isorefractive oil-in-water Pickering emulsion enables fluorescence spectroscopy to be used to monitor the transport of water-insoluble small molecules (pyrene and benzophenone) between n-dodecane droplets. Such transport is significantly less efficient than that observed for the equivalent isorefractive surfactant-stabilized emulsion. Conventional turbid emulsions do not enable such a comparison to be made because the intense light scattering leads to substantial spectral

  2. Bespoke contrast-matched diblock copolymer nanoparticles enable the rational design of highly transparent Pickering double emulsions.

    PubMed

    Rymaruk, Matthew J; Thompson, Kate L; Derry, Matthew J; Warren, Nicholas J; Ratcliffe, Liam P D; Williams, Clive N; Brown, Steven L; Armes, Steven P

    2016-08-14

    We report the preparation of highly transparent oil-in-water Pickering emulsions using contrast-matched organic nanoparticles. This is achieved via addition of judicious amounts of either sucrose or glycerol to an aqueous dispersion of poly(glycerol monomethacrylate)56-poly(2,2,2-trifluoroethyl methacrylate)500 [PGMA-PTFEMA] diblock copolymer nanoparticles prior to high shear homogenization with an equal volume of n-dodecane. The resulting Pickering emulsions comprise polydisperse n-dodecane droplets of 20-100 μm diameter and exhibit up to 96% transmittance across the visible spectrum. In contrast, control experiments using non-contrast-matched poly(glycerol monomethacrylate)56-poly(benzyl methacrylate)300 [PGMA56-PBzMA300] diblock copolymer nanoparticles as a Pickering emulsifier only produced conventional highly turbid emulsions. Thus contrast-matching of the two immiscible phases is a necessary but not sufficient condition for the preparation of highly transparent Pickering emulsions: it is essential to use isorefractive nanoparticles in order to minimize light scattering. Furthermore, highly transparent oil-in-water-in-oil Pickering double emulsions can be obtained by homogenizing the contrast-matched oil-in-water Pickering emulsion prepared using the PGMA56-PTFEMA500 nanoparticles with a contrast-matched dispersion of hydrophobic poly(lauryl methacrylate)39-poly(2,2,2-trifluoroethyl methacrylate)800 [PLMA39-PTFEMA800] diblock copolymer nanoparticles in n-dodecane. Finally, we show that an isorefractive oil-in-water Pickering emulsion enables fluorescence spectroscopy to be used to monitor the transport of water-insoluble small molecules (pyrene and benzophenone) between n-dodecane droplets. Such transport is significantly less efficient than that observed for the equivalent isorefractive surfactant-stabilized emulsion. Conventional turbid emulsions do not enable such a comparison to be made because the intense light scattering leads to substantial spectral

  3. Radiation induced estane polymer crosslinking

    SciTech Connect

    Fletcher, M.; Foster, P.

    1997-12-01

    The exposure of polymeric materials to radiation has been known to induce the effects of crosslinking and degradation. The crosslinking phenomena comes about when two long chain polymers become linked together by a primary bond that extends the chain and increases the viscosity, molecular weight and the elastic modules of the polymer. This process has been observed in relatively short periods of time with fairly high doses of radiation, on the order of several megarads/hour. This paper address low dose exposure over long periods of time to determine what the radiation effects are on the polymeric binder material in PBX 9501. An experimental sample of binder material without explosives will be placed into a thermal and radiation field produced from a W-48 put mod 0. Another sample will be placed in a thermal environment without the radiation. The following is the test plan that was submitted to the Pantex process. The data presented here will be from the first few weeks of exposure and this test will be continued over the next few years. Subsequent data will hopefully be presented in the next compatibility and aging conference.

  4. High-frame rate four dimensional optoacoustic tomography enables visualization of cardiovascular dynamics and mouse heart perfusion

    PubMed Central

    Deán-Ben, Xosé Luís; Ford, Steven James; Razansky, Daniel

    2015-01-01

    Functional imaging of mouse models of cardiac health and disease provides a major contribution to our fundamental understanding of the mammalian heart. However, imaging murine hearts presents significant challenges due to their small size and rapid heart rate. Here we demonstrate the feasibility of high-frame-rate, noninvasive optoacoustic imaging of the murine heart. The temporal resolution of 50 three-dimensional frames per second provides functional information at important phases of the cardiac cycle without the use of gating or other motion-reduction methods. Differentiation of the blood oxygenation state in the heart chambers was enabled by exploiting the wavelength dependence of optoacoustic signals. Real-time volumetric tracking of blood perfusion in the cardiac chambers was also evaluated using indocyanine green. Taken together, the newly-discovered capacities offer a unique tool set for in-vivo structural and functional imaging of the whole heart with high spatio-temporal resolution in all three dimensions. PMID:26130401

  5. Crosslinking biopolymers for biomedical applications.

    PubMed

    Reddy, Narendra; Reddy, Roopa; Jiang, Qiuran

    2015-06-01

    Biomaterials made from proteins, polysaccharides, and synthetic biopolymers are preferred but lack the mechanical properties and stability in aqueous environments necessary for medical applications. Crosslinking improves the properties of the biomaterials, but most crosslinkers either cause undesirable changes to the functionality of the biopolymers or result in cytotoxicity. Glutaraldehyde, the most widely used crosslinking agent, is difficult to handle and contradictory views have been presented on the cytotoxicity of glutaraldehyde-crosslinked materials. Recently, poly(carboxylic acids) that can crosslink in both dry and wet conditions have been shown to provide the desired improvements in tensile properties, increase in stability under aqueous conditions, and also promote cell attachment and proliferation. Green chemicals and newer crosslinking approaches are necessary to obtain biopolymeric materials with properties desired for medical applications.

  6. Influence of Cross-Linker Concentration on the Functionality of Carbodiimide Cross-Linked Gelatin Membranes for Retinal Sheet Carriers.

    PubMed

    Lai, Jui-Yang; Li, Ya-Ting

    2011-01-01

    Carbodiimide cross-linking can easily regulate the functionality of gelatin carriers used for retinal sheet delivery. This paper investigates the effect of cross-linker concentrations (0-0.4 mmol EDC/mg gelatin membrane (GM)) on the properties of the chemically-modified GMs. ATR-FT-IR and ninhydrin analyses results consistently indicated that the EDC cross-linking reaction approaches saturation at concentrations around 0.02 mmol EDC/mg GM. The thermal stability and resistance to water dissolution and collagenase digestion were significantly enhanced with increasing cross-linker concentration from 0.001 to 0.02 mmol EDC/mg GM. In addition, the chemical cross-linking did not affect the ability to form a tissue-encapsulating structure at 37°C. Irrespective of their cross-linking degree, the GMs had an appropriate degradation rate sufficient to allow tissue integration. It was noted that, although high cross-linker concentrations can be used to improve the delivery efficiency of gelatin samples, the treatment with 0.1-0.4 mmol EDC/mg GM may lead to poor biocompatibility. Results of Live/Dead and pro-inflammatory cytokine expression analyses showed that the exposure of ARPE-19 cultures to the test materials cross-linked with a concentration ≥0.1 mmol EDC/mg GM induces significant cytotoxicity and high levels of interleukin-1β and interleukin-6. However, the presence of EDC cross-linked gelatin membranes in the culture medium had no effect on the glutamate uptake capacity. It is concluded that among the cross-linked gelatin samples studied, 0.02 mmol EDC/mg GM is the best cross-linker concentration for preparation of retinal sheet delivery carriers.

  7. Wear performance of neat and vitamin E blended highly cross-linked PE under severe conditions: The combined effect of accelerated ageing and third body particles during wear test.

    PubMed

    Affatato, Saverio; De Mattia, Jonathan Salvatore; Bracco, Pierangiola; Pavoni, Eleonora; Taddei, Paola

    2016-12-01

    The objective of this study is to evaluate the effects of third-body particles on the in vitro wear behaviour of three different sets of polyethylene acetabular cups after prolonged testing in a hip simulator and accelerated ageing. Vitamin E-blended, cross-linked polyethylene (XLPE_VE), cross-linked polyethylene (XLPE) and conventional polyethylene (STD_PE) acetabular cups were simulator tested for two million cycles under severe conditions (i.e. by adding third-body particles to the bovine calf serum lubricant). Micro-Fourier Transform Infrared and micro-Raman spectroscopic analyses, differential scanning calorimetry, and crosslink density measurements were used to characterize the samples at a molecular level. The STD_PE cups had twice mass loss than the XLPE_VE components and four times than the XLPE samples; statistically significant differences were found between the mass losses of the three sets of cups. The observed wear trend was justified on the basis of the differences in cross-link density among the samples (XLPE>XLPE_VE>STD_PE). FTIR crystallinity profiles, bulk DSC crystallinity and surface micro-Raman crystallinity seemed to have a similar behaviour upon testing: all of them (as well as the all-trans and ortho-trans contents) revealed the most significant changes in XLPE and XLPE_VE samples. The more severe third-body wear testing conditions determined more noticeable changes in all spectroscopic markers with respect to previous tests. Unexpectedly, traces of bulk oxidation were found in both STD_PE (unirradiated) and XLPE (remelting-stabilized), which were expected to be stable to oxidation; on the contrary, XLPE_VE demonstrated a high oxidative stability in the present, highly demanding conditions.

  8. Mixing injector enables time-resolved crystallography with high hit rate at X-ray free electron lasers

    PubMed Central

    Calvey, George D.; Katz, Andrea M.; Schaffer, Chris B.; Pollack, Lois

    2016-01-01

    Knowledge of protein structure provides essential insight into function, enhancing our understanding of diseases and enabling new treatment development. X-ray crystallography has been used to solve the structures of more than 100 000 proteins; however, the vast majority represent long-lived states that do not capture the functional motions of these molecular machines. Reactions triggered by the addition of a ligand can be the most challenging to detect with crystallography because of the difficulty of synchronizing reactions to create detectable quantities of transient states. The development of X-ray free electron lasers (XFELs) and serial femtosecond crystallography (SFX) enables new approaches for solving protein structures following the rapid diffusion of ligands into micron sized protein crystals. Conformational changes occurring on millisecond timescales can be detected and time-resolved. Here, we describe a new XFEL injector which incorporates a microfluidic mixer to rapidly combine reactant and sample milliseconds before the sample reaches the X-ray beam. The mixing injector consists of bonded, concentric glass capillaries. The fabrication process, employing custom laser cut centering spacers and UV curable epoxy, ensures precise alignment of capillaries for repeatable, centered sample flow and dependable mixing. Crystal delivery capillaries are 50 or 75 μm in diameter and can contain an integrated filter depending on the demands of the experiment. Reaction times can be varied from submillisecond to several hundred milliseconds. The injector features rapid and uniform mixing, low sample dilution, and high hit rates. It is fully compatible with existing SFX beamlines.

  9. Mixing injector enables time-resolved crystallography with high hit rate at X-ray free electron lasers.

    PubMed

    Calvey, George D; Katz, Andrea M; Schaffer, Chris B; Pollack, Lois

    2016-09-01

    Knowledge of protein structure provides essential insight into function, enhancing our understanding of diseases and enabling new treatment development. X-ray crystallography has been used to solve the structures of more than 100 000 proteins; however, the vast majority represent long-lived states that do not capture the functional motions of these molecular machines. Reactions triggered by the addition of a ligand can be the most challenging to detect with crystallography because of the difficulty of synchronizing reactions to create detectable quantities of transient states. The development of X-ray free electron lasers (XFELs) and serial femtosecond crystallography (SFX) enables new approaches for solving protein structures following the rapid diffusion of ligands into micron sized protein crystals. Conformational changes occurring on millisecond timescales can be detected and time-resolved. Here, we describe a new XFEL injector which incorporates a microfluidic mixer to rapidly combine reactant and sample milliseconds before the sample reaches the X-ray beam. The mixing injector consists of bonded, concentric glass capillaries. The fabrication process, employing custom laser cut centering spacers and UV curable epoxy, ensures precise alignment of capillaries for repeatable, centered sample flow and dependable mixing. Crystal delivery capillaries are 50 or 75 μm in diameter and can contain an integrated filter depending on the demands of the experiment. Reaction times can be varied from submillisecond to several hundred milliseconds. The injector features rapid and uniform mixing, low sample dilution, and high hit rates. It is fully compatible with existing SFX beamlines.

  10. High activity enables life on a high-sugar diet: blood glucose regulation in nectar-feeding bats.

    PubMed

    Kelm, Detlev H; Simon, Ralph; Kuhlow, Doreen; Voigt, Christian C; Ristow, Michael

    2011-12-01

    High blood glucose levels caused by excessive sugar consumption are detrimental to mammalian health and life expectancy. Despite consuming vast quantities of sugar-rich floral nectar, nectar-feeding bats are long-lived, provoking the question of how they regulate blood glucose. We investigated blood glucose levels in nectar-feeding bats (Glossophaga soricina) in experiments in which we varied the amount of dietary sugar or flight time. Blood glucose levels increased with the quantity of glucose ingested and exceeded 25 mmol l(-1) blood in resting bats, which is among the highest values ever recorded in mammals fed sugar quantities similar to their natural diet. During normal feeding, blood glucose values decreased with increasing flight time, but only fell to expected values when bats spent 75 per cent of their time airborne. Either nectar-feeding bats have evolved mechanisms to avoid negative health effects of hyperglycaemia, or high activity is key to balancing blood glucose levels during foraging. We suggest that the coevolutionary specialization of bats towards a nectar diet was supported by the high activity and elevated metabolic rates of these bats. High activity may have conferred benefits to the bats in terms of behavioural interactions and foraging success, and is simultaneously likely to have increased their efficiency as plant pollinators.

  11. High activity enables life on a high-sugar diet: blood glucose regulation in nectar-feeding bats

    PubMed Central

    Kelm, Detlev H.; Simon, Ralph; Kuhlow, Doreen; Voigt, Christian C.; Ristow, Michael

    2011-01-01

    High blood glucose levels caused by excessive sugar consumption are detrimental to mammalian health and life expectancy. Despite consuming vast quantities of sugar-rich floral nectar, nectar-feeding bats are long-lived, provoking the question of how they regulate blood glucose. We investigated blood glucose levels in nectar-feeding bats (Glossophaga soricina) in experiments in which we varied the amount of dietary sugar or flight time. Blood glucose levels increased with the quantity of glucose ingested and exceeded 25 mmol l−1 blood in resting bats, which is among the highest values ever recorded in mammals fed sugar quantities similar to their natural diet. During normal feeding, blood glucose values decreased with increasing flight time, but only fell to expected values when bats spent 75 per cent of their time airborne. Either nectar-feeding bats have evolved mechanisms to avoid negative health effects of hyperglycaemia, or high activity is key to balancing blood glucose levels during foraging. We suggest that the coevolutionary specialization of bats towards a nectar diet was supported by the high activity and elevated metabolic rates of these bats. High activity may have conferred benefits to the bats in terms of behavioural interactions and foraging success, and is simultaneously likely to have increased their efficiency as plant pollinators. PMID:21490011

  12. Large Scale Chemical Cross-linking Mass Spectrometry Perspectives.

    PubMed

    Zybailov, Boris L; Glazko, Galina V; Jaiswal, Mihir; Raney, Kevin D

    2013-02-01

    The spectacular heterogeneity of a complex protein mixture from biological samples becomes even more difficult to tackle when one's attention is shifted towards different protein complex topologies, transient interactions, or localization of PPIs. Meticulous protein-by-protein affinity pull-downs and yeast-two-hybrid screens are the two approaches currently used to decipher proteome-wide interaction networks. Another method is to employ chemical cross-linking, which gives not only identities of interactors, but could also provide information on the sites of interactions and interaction interfaces. Despite significant advances in mass spectrometry instrumentation over the last decade, mapping Protein-Protein Interactions (PPIs) using chemical cross-linking remains time consuming and requires substantial expertise, even in the simplest of systems. While robust methodologies and software exist for the analysis of binary PPIs and also for the single protein structure refinement using cross-linking-derived constraints, undertaking a proteome-wide cross-linking study is highly complex. Difficulties include i) identifying cross-linkers of the right length and selectivity that could capture interactions of interest; ii) enrichment of the cross-linked species; iii) identification and validation of the cross-linked peptides and cross-linked sites. In this review we examine existing literature aimed at the large-scale protein cross-linking and discuss possible paths for improvement. We also discuss short-length cross-linkers of broad specificity such as formaldehyde and diazirine-based photo-cross-linkers. These cross-linkers could potentially capture many types of interactions, without strict requirement for a particular amino-acid to be present at a given protein-protein interface. How these shortlength, broad specificity cross-linkers be applied to proteome-wide studies? We will suggest specific advances in methodology, instrumentation and software that are needed to make

  13. The Use of Coded PCR Primers Enables High-Throughput Sequencing of Multiple Homolog Amplification Products by 454 Parallel Sequencing

    PubMed Central

    Bollback, Jonathan P.; Panitz, Frank; Bendixen, Christian; Nielsen, Rasmus; Willerslev, Eske

    2007-01-01

    Background The invention of the Genome Sequence 20™ DNA Sequencing System (454 parallel sequencing platform) has enabled the rapid and high-volume production of sequence data. Until now, however, individual emulsion PCR (emPCR) reactions and subsequent sequencing runs have been unable to combine template DNA from multiple individuals, as homologous sequences cannot be subsequently assigned to their original sources. Methodology We use conventional PCR with 5′-nucleotide tagged primers to generate homologous DNA amplification products from multiple specimens, followed by sequencing through the high-throughput Genome Sequence 20™ DNA Sequencing System (GS20, Roche/454 Life Sciences). Each DNA sequence is subsequently traced back to its individual source through 5′tag-analysis. Conclusions We demonstrate that this new approach enables the assignment of virtually all the generated DNA sequences to the correct source once sequencing anomalies are accounted for (miss-assignment rate<0.4%). Therefore, the method enables accurate sequencing and assignment of homologous DNA sequences from multiple sources in single high-throughput GS20 run. We observe a bias in the distribution of the differently tagged primers that is dependent on the 5′ nucleotide of the tag. In particular, primers 5′ labelled with a cytosine are heavily overrepresented among the final sequences, while those 5′ labelled with a thymine are strongly underrepresented. A weaker bias also exists with regards to the distribution of the sequences as sorted by the second nucleotide of the dinucleotide tags. As the results are based on a single GS20 run, the general applicability of the approach requires confirmation. However, our experiments demonstrate that 5′primer tagging is a useful method in which the sequencing power of the GS20 can be applied to PCR-based assays of multiple homologous PCR products. The new approach will be of value to a broad range of research areas, such as those of

  14. A nanonet-enabled Li ion battery cathode material with high power rate, high capacity, and long cycle lifetime.

    PubMed

    Zhou, Sa; Yang, Xiaogang; Lin, Yongjing; Xie, Jin; Wang, Dunwei

    2012-01-24

    The performance of advanced energy conversion and storage devices, including solar cells and batteries, is intimately connected to the electrode designs at the nanoscale. Consider a rechargeable Li ion battery, a prevalent energy storage technology, as an example. Among other factors, the electrode material design at the nanoscale is key to realizing the goal of measuring fast ionic diffusion and high electronic conductivity, the inherent properties that determine power rates, and good stability upon repeated charge and discharge, which is critical to the sustainable high capacities. Here we show that such a goal can be achieved by forming heteronanostructures on a radically new platform we discovered, TiSi(2) nanonets. In addition to the benefits of high surface area, good electrical conductivity, and superb mechanical strength offered by the nanonet, the design also takes advantage of how TiSi(2) reacts with O(2) upon heating. The resulting TiSi(2)/V(2)O(5) nanostructures exhibit a specific capacity of 350 Ah/kg, a power rate up to 14.5 kW/kg, and 78.7% capacity retention after 9800 cycles of charge and discharge. These figures indicate that a cathode material significantly better than V(2)O(5) of other morphologies is produced.

  15. The ALMA Phasing Project: New Frontiers in Ultra-High Resolution Astronomy Enabled by a Beamformed ALMA

    NASA Astrophysics Data System (ADS)

    Matthews, Lynn D.; Alef, W.; Anderson, J.; Barkats, D.; Crew, G. B.; Doeleman, S. S.; Fish, V. L.; Greenberg, J.; Hecht, M. H.; Hiriart, R.; Honma, M.; Impellizzeri, C.; Inoue, M.; Lacasse, R.; Lopez, B.; Mora-Klein, M.; Nagar, N.; Pankratius, V.; Pradel, N.; Rottmann, H.; Roy, A.; Ruszczyk, C.; Saez, A.; Shillue, B.; Treacy, R.; ALMA Phasing Project Team

    2014-01-01

    The Atacama Millimeter/submillimeter Array (ALMA) Phasing Project (APP) is an ongoing ALMA Development Project that will provide the means to coherently sum all of the individual ALMA antennas, allowing them to effectively function as a single aperture. This capability will allow ALMA to participate in global Very Long Baseline Interferometry (VLBI) networks operating in the millimeter and submillimeter, offering a dramatic improvement in sensitivity. This will in turn afford a wide range of new ultra-high angular resolution science applications. This poster will provide an overview of the APP design and implementation plan and highlight examples of new science enabled by a beamformed ALMA (including the study of black holes on Event Horizon scales, the detailed investigation of the launch and collimation of astrophysical jets, and astrometry of astrophysical masers with unprecedented precision). Commissioning and Science Verification of the APP is slated to begin in early 2014.

  16. Feasibility study of generating ultra-high harmonic radiation with a single stage echo-enabled harmonic generation scheme

    NASA Astrophysics Data System (ADS)

    Zhou, Kaishang; Feng, Chao; Wang, Dong

    2016-10-01

    The echo enabled harmonic generation (EEHG) scheme holds the ability for the generation of fully coherent soft x-ray free-electron laser (FEL) pulses directly from external UV seeding sources. In this paper, we study the feasibility of using a single stage EEHG to generate coherent radiation in the "water window" and beyond. Using the high-order operating modes of the EEHG scheme, intensive numerical simulations have been performed considering various three-dimensional effects. The simulation results demonstrated that coherent soft x-ray radiation at 150th harmonic (1.77 nm) of the seed can be produced by a single stage EEHG. The decreasing of the final bunching factor at the desired harmonic caused by intra beam scattering (IBS) effect has also been analyzed.

  17. Quantifying the Nucleation and Growth Kinetics of Microwave Nanochemistry Enabled by in Situ High-Energy X-ray Scattering.

    PubMed

    Liu, Qi; Gao, Min-Rui; Liu, Yuzi; Okasinski, John S; Ren, Yang; Sun, Yugang

    2016-01-13

    The fast reaction kinetics presented in the microwave synthesis of colloidal silver nanoparticles was quantitatively studied, for the first time, by integrating a microwave reactor with in situ X-ray diffraction at a high-energy synchrotron beamline. Comprehensive data analysis reveals two different types of reaction kinetics corresponding to the nucleation and growth of the Ag nanoparticles. The formation of seeds (nucleation) follows typical first-order reaction kinetics with activation energy of 20.34 kJ/mol, while the growth of seeds (growth) follows typical self-catalytic reaction kinetics. Varying the synthesis conditions indicates that the microwave colloidal chemistry is independent of concentration of surfactant. These discoveries reveal that the microwave synthesis of Ag nanoparticles proceeds with reaction kinetics significantly different from the synthesis present in conventional oil bath heating. The in situ X-ray diffraction technique reported in this work is promising to enable further understanding of crystalline nanomaterials formed through microwave synthesis.

  18. A highly parallel method for synthesizing DNA repeats enables the discovery of ‘smart’ protein polymers

    NASA Astrophysics Data System (ADS)

    Amiram, Miriam; Quiroz, Felipe Garcia; Callahan, Daniel J.; Chilkoti, Ashutosh

    2011-02-01

    Robust high-throughput synthesis methods are needed to expand the repertoire of repetitive protein-polymers for different applications. To address this need, we developed a new method, overlap extension rolling circle amplification (OERCA), for the highly parallel synthesis of genes encoding repetitive protein-polymers. OERCA involves a single PCR-type reaction for the rolling circle amplification of a circular DNA template and simultaneous overlap extension by thermal cycling. We characterized the variables that control OERCA and demonstrated its superiority over existing methods, its robustness, high-throughput and versatility by synthesizing variants of elastin-like polypeptides (ELPs) and protease-responsive polymers of glucagon-like peptide-1 analogues. Despite the GC-rich, highly repetitive sequences of ELPs, we synthesized remarkably large genes without recursive ligation. OERCA also enabled us to discover ‘smart’ biopolymers that exhibit fully reversible thermally responsive behaviour. This powerful strategy generates libraries of repetitive genes over a wide and tunable range of molecular weights in a ‘one-pot’ parallel format.

  19. Nano-sized structured layered positive electrode materials to enable high energy density and high rate capability lithium batteries

    DOEpatents

    Deng, Haixia; Belharouak, Ilias; Amine, Khalil

    2012-10-02

    Nano-sized structured dense and spherical layered positive active materials provide high energy density and high rate capability electrodes in lithium-ion batteries. Such materials are spherical second particles made from agglomerated primary particles that are Li.sub.1+.alpha.(Ni.sub.xCo.sub.yMn.sub.z).sub.1-tM.sub.tO.sub.2-dR.sub.d- , where M is selected from can be Al, Mg, Fe, Cu, Zn, Cr, Ag, Ca, Na, K, In, Ga, Ge, V, Mo, Nb, Si, Ti, Zr, or a mixture of any two or more thereof, R is selected from F, Cl, Br, I, H, S, N, or a mixture of any two or more thereof, and 0.ltoreq..alpha..ltoreq.0.50; 0

  20. Sensory processing within cockroach antenna enables rapid implementation of feedback control for high-speed running maneuvers.

    PubMed

    Mongeau, Jean-Michel; Sponberg, Simon N; Miller, John P; Full, Robert J

    2015-08-01

    Animals are remarkably stable during high-speed maneuvers. As the speed of locomotion increases, neural bandwidth and processing delays can limit the ability to achieve and maintain stable control. Processing the information of sensory stimuli into a control signal within the sensor itself could enable rapid implementation of whole-body feedback control during high-speed locomotion. Here, we show that processing in antennal afferents is sufficient to act as the control signal for a fast sensorimotor loop. American cockroaches Periplaneta americana use their antennae to mediate escape running by tracking vertical surfaces such as walls. A control theoretic model of wall following predicts that stable control is possible if the animal can compute wall position (P) and velocity, its derivative (D). Previous whole-nerve recordings from the antenna during simulated turning experiments demonstrated a population response consistent with P and D encoding, and suggested that the response was synchronized with the timing of a turn executed while wall following. Here, we record extracellularly from individual mechanoreceptors distributed along the antenna and show that these receptors encode D and have distinct latencies and filtering properties. The summed output of these receptors can be used as a control signal for rapid steering maneuvers. The D encoding within the antenna in addition to the temporal filtering properties and P dependence of the population of afferents support a sensory-encoding notion from control theory. Our findings support the notion that peripheral sensory processing can enable rapid implementation of whole-body feedback control during rapid running maneuvers.

  1. Utilization of highly robust and selective crosslinked polymeric ionic liquid-based sorbent coatings in direct-immersion solid-phase microextraction and high-performance liquid chromatography for determining polar organic pollutants in waters.

    PubMed

    Pacheco-Fernández, Idaira; Najafi, Ali; Pino, Verónica; Anderson, Jared L; Ayala, Juan H; Afonso, Ana M

    2016-09-01

    Several crosslinked polymeric ionic liquid (PIL)-based sorbent coatings of different nature were prepared by UV polymerization onto nitinol wires. They were evaluated in a direct-immersion solid-phase microextraction (DI-SPME) method in combination with high-performance liquid chromatography (HPLC) and diode array detection (DAD). The studied PIL coatings contained either vinyl alkyl or vinylbenzyl imidazolium-based (ViCnIm- or ViBCnIm-) IL monomers with different anions, as well as different dicationic IL crosslinkers. The analytical performance of these PIL-based SPME coatings was firstly evaluated for the extraction of a group of 10 different model analytes, including hydrocarbons and phenols, while exhaustively comparing the performance with commercial SPME fibers such as polydimethylsyloxane (PDMS), polyacrylate (PA) and polydimethylsiloxane/divinylbenzene (PDMS/DVB), and using all fibers under optimized conditions. Those fibers exhibiting a high selectivity for polar compounds were selected to carry out an analytical method for a group of 5 alkylphenols, including bisphenol-A (BPA) and nonylphenol (n-NP). Under optimum conditions, average relative recoveries of 108% and inter-day precision values (3 non-consecutive days) lower than 19% were obtained for a spiked level of 10µgL(-1). Correlations coefficients for the overall method ranged between 0.990 and 0.999, and limits of detection were down to 1µgL(-1). Tap water, river water, and bottled water were analyzed to evaluate matrix effects. Comparison with the PA fiber was also performed in terms of analytical performance. Partition coefficients (logKfs) of the alkylphenols to the SPME coating varied from 1.69 to 2.45 for the most efficient PIL-based fiber, and from 1.58 to 2.30 for the PA fiber. These results agree with those obtained by the normalized calibration slopes, pointing out the affinity of these PILs-based coatings.

  2. Utilization of highly robust and selective crosslinked polymeric ionic liquid-based sorbent coatings in direct-immersion solid-phase microextraction and high-performance liquid chromatography for determining polar organic pollutants in waters.

    PubMed

    Pacheco-Fernández, Idaira; Najafi, Ali; Pino, Verónica; Anderson, Jared L; Ayala, Juan H; Afonso, Ana M

    2016-09-01

    Several crosslinked polymeric ionic liquid (PIL)-based sorbent coatings of different nature were prepared by UV polymerization onto nitinol wires. They were evaluated in a direct-immersion solid-phase microextraction (DI-SPME) method in combination with high-performance liquid chromatography (HPLC) and diode array detection (DAD). The studied PIL coatings contained either vinyl alkyl or vinylbenzyl imidazolium-based (ViCnIm- or ViBCnIm-) IL monomers with different anions, as well as different dicationic IL crosslinkers. The analytical performance of these PIL-based SPME coatings was firstly evaluated for the extraction of a group of 10 different model analytes, including hydrocarbons and phenols, while exhaustively comparing the performance with commercial SPME fibers such as polydimethylsyloxane (PDMS), polyacrylate (PA) and polydimethylsiloxane/divinylbenzene (PDMS/DVB), and using all fibers under optimized conditions. Those fibers exhibiting a high selectivity for polar compounds were selected to carry out an analytical method for a group of 5 alkylphenols, including bisphenol-A (BPA) and nonylphenol (n-NP). Under optimum conditions, average relative recoveries of 108% and inter-day precision values (3 non-consecutive days) lower than 19% were obtained for a spiked level of 10µgL(-1). Correlations coefficients for the overall method ranged between 0.990 and 0.999, and limits of detection were down to 1µgL(-1). Tap water, river water, and bottled water were analyzed to evaluate matrix effects. Comparison with the PA fiber was also performed in terms of analytical performance. Partition coefficients (logKfs) of the alkylphenols to the SPME coating varied from 1.69 to 2.45 for the most efficient PIL-based fiber, and from 1.58 to 2.30 for the PA fiber. These results agree with those obtained by the normalized calibration slopes, pointing out the affinity of these PILs-based coatings. PMID:27343586

  3. Luminescence in crosslinked polyethylene at elevated temperatures

    NASA Astrophysics Data System (ADS)

    Bamji, S. S.; Bulinski, A. T.; Suzuki, H.; Matsuki, M.; Iwata, Z.

    1993-10-01

    Electrical treeing is often responsible for the breakdown of insulating materials used in power apparatus such as high-voltage transformers, cables, and capacitors. Insulation, such as crosslinked polyethylene (XLPE), used in underground high-voltage cables usually operates at temperatures above ambient. This paper describes the characteristics of luminescence, emitted prior to electrical tree inception, at a crosslinked polyethylene-semiconducting material (XLPE-semicon) interface held above room temperature. Use of a sensitive light detection system showed that XLPE subjected to elevated temperatures emits luminescence even without voltage application. This light was attributed to thermoluminescence which decreased with the decrease in the concentration of the crosslinking by-products present in the polymer. The spectra of thermoluminescence were only in the visible range. On the other hand, electroluminescence occurred when the XLPE-semicon interface was held above room temperature and subjected to high electric stress. This light did not depend on the concentration of the crosslinking by-products and the spectra of electroluminescence were in the visible and the ultraviolet ranges. It is proposed that XLPE-semicon interface held at elevated temperature and subjected to long-term voltage application initially emits both thermoluminescence and electroluminescence. As the crosslinking by-products exude out of the polymer, thermoluminescence decreases with time and ultimately ceases, but electroluminescence occurs as long as the voltage is applied to the polymer. Although the intensity of electroluminescence emitted at high temperature was lower than that emitted at ambient, sufficient ultraviolet radiation was emitted. The ultraviolet radiation could photodegrade the polymer and lead to electrical tree inception.

  4. High resolution light-sheet based high-throughput imaging cytometry system enables visualization of intra-cellular organelles

    NASA Astrophysics Data System (ADS)

    Regmi, Raju; Mohan, Kavya; Mondal, Partha Pratim

    2014-09-01

    Visualization of intracellular organelles is achieved using a newly developed high throughput imaging cytometry system. This system interrogates the microfluidic channel using a sheet of light rather than the existing point-based scanning techniques. The advantages of the developed system are many, including, single-shot scanning of specimens flowing through the microfluidic channel at flow rate ranging from micro- to nano- lit./min. Moreover, this opens-up in-vivo imaging of sub-cellular structures and simultaneous cell counting in an imaging cytometry system. We recorded a maximum count of 2400 cells/min at a flow-rate of 700 nl/min, and simultaneous visualization of fluorescently-labeled mitochondrial network in HeLa cells during flow. The developed imaging cytometry system may find immediate application in biotechnology, fluorescence microscopy and nano-medicine.

  5. Post-Polymerization Crosslinked Polyurethane Shape-Memory Polymers

    PubMed Central

    Hearon, K.; Gall, K.; Ware, T.; Maitland, D. J.; Bearinger, J. P.; Wilson, T. S.

    2011-01-01

    Novel urethane shape-memory polymers (SMPs) of significant industrial relevance have been synthesized and characterized. Chemically crosslinked SMPs have traditionally been made in a one-step polymerization of monomers and crosslinking agents. However, these new post-polymerization crosslinked SMPs can be processed into complex shapes by thermoplastic manufacturing methods and later crosslinked by heat exposure or by electron beam irradiation. Several series of linear, olefinic urethane polymers were made from 2-butene-1,4-diol, other saturated diols, and various aliphatic diisocyanates. These thermoplastics were melt-processed into desired geometries and thermally crosslinked at 200°C or radiation crosslinked at 50 kGy. The SMPs were characterized by solvent swelling and extraction, differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), tensile testing, and qualitative shape-recovery analysis. Swelling and DMA results provided concrete evidence of chemical crosslinking, and further characterization revealed that the urethanes had outstanding mechanical properties. Key properties include tailorable transitions between 25 and 80°C, tailorable rubbery moduli between 0.2 and 4.2 MPa, recoverable strains approaching 100%, failure strains of over 500% at Tg, and qualitative shape-recovery times of less than 12 seconds at body temperature (37°C). Because of its outstanding thermo-mechanical properties, one polyurethane was selected for implementation in the design of a complex medical device. These post-polymerization crosslinked urethane SMPs are an industrially relevant class of highly processable shape-memory materials. PMID:21572577

  6. Post-Polymerization Crosslinked Polyurethane Shape-Memory Polymers.

    PubMed

    Hearon, K; Gall, K; Ware, T; Maitland, D J; Bearinger, J P; Wilson, T S

    2011-07-01

    Novel urethane shape-memory polymers (SMPs) of significant industrial relevance have been synthesized and characterized. Chemically crosslinked SMPs have traditionally been made in a one-step polymerization of monomers and crosslinking agents. However, these new post-polymerization crosslinked SMPs can be processed into complex shapes by thermoplastic manufacturing methods and later crosslinked by heat exposure or by electron beam irradiation. Several series of linear, olefinic urethane polymers were made from 2-butene-1,4-diol, other saturated diols, and various aliphatic diisocyanates. These thermoplastics were melt-processed into desired geometries and thermally crosslinked at 200°C or radiation crosslinked at 50 kGy. The SMPs were characterized by solvent swelling and extraction, differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), tensile testing, and qualitative shape-recovery analysis. Swelling and DMA results provided concrete evidence of chemical crosslinking, and further characterization revealed that the urethanes had outstanding mechanical properties. Key properties include tailorable transitions between 25 and 80°C, tailorable rubbery moduli between 0.2 and 4.2 MPa, recoverable strains approaching 100%, failure strains of over 500% at T(g), and qualitative shape-recovery times of less than 12 seconds at body temperature (37°C). Because of its outstanding thermo-mechanical properties, one polyurethane was selected for implementation in the design of a complex medical device. These post-polymerization crosslinked urethane SMPs are an industrially relevant class of highly processable shape-memory materials.

  7. Ionic supramolecular bonds preserve mechanical properties and enable synergetic performance at high humidity in water-borne, self-assembled nacre-mimetics

    NASA Astrophysics Data System (ADS)

    Das, Paramita; Walther, Andreas

    2013-09-01

    Although tremendous effort has been focused on enhancing the mechanical properties of nacre-mimetic materials, conservation of high stiffness and strength against hydration-induced decay of mechanical properties at high humidity remains a fundamental challenge in such water-borne high-performance materials. Herein, we demonstrate that ionic supramolecular bonds, introduced by infiltration of divalent Cu2+ ions, allow efficient stabilization of the mechanical properties of self-assembled water-borne nacre-mimetics based on sustainable sodium carboxymethylcellulose (Na+CMC) and natural sodium montmorillonite nanoclay (Na+MTM) against high humidity (95% RH). The mechanical properties in the highly hydrated state (Young's modulus up to 13.5 GPa and tensile strength up to 125 MPa) are in fact comparable to a range of non-crosslinked nacre-mimetic materials in the dry state. Moreover, the Cu2+-treated nacre-inspired materials display synergetic mechanical properties as found in a simultaneous improvement of stiffness, strength and toughness, as compared to the pristine material. Significant inelastic deformation takes place considering the highly reinforced state. This contrasts the typical behaviour of tight, covalent crosslinks and is suggested to originate from a sacrificial, dynamic breakage and rebinding of transient supramolecular ionic bonds. Considering easy access to a large range of ionic interactions and alteration of counter-ion charge via external stimuli, we foresee responsive and adaptive mechanical properties in highly reinforced and stiff bio-inspired bulk nanocomposites and in other bio-inspired materials, e.g. nanocellulose papers and peptide-based materials.Although tremendous effort has been focused on enhancing the mechanical properties of nacre-mimetic materials, conservation of high stiffness and strength against hydration-induced decay of mechanical properties at high humidity remains a fundamental challenge in such water-borne high

  8. Traceless cross-linker for photocleavable bioconjugation.

    PubMed

    Wang, Rong; Yan, Funing; Qiu, Dengli; Jeong, Jae-Sun; Jin, Qiaoling; Kim, Tae-Young; Chen, Liaohai

    2012-04-18

    Photoresponsive bioconjugation empowers the development of novel methods for drug discovery, disease diagnosis, and high-throughput screening, among others. In this paper, we report on the characteristics of a traceless photocleavable cross-linker, di-6-(3-succinimidyl carbonyloxymethyl-4-nitro-phenoxy)-hexanoic acid disulfide diethanol ester (SCNE). The traceless feature and the biocompatibility of this photocleavable cross-linking reagent were corroborated. Consequently, we demonstrated its application in reversible phage particle immobilization that could provide a platform for direct single-phage screening. We also applied it in protein-photoprinting, where SCNE acts as a "photo-eraser" to remove the cross-linked protein molecules at a desired region in a simple, clean, and light-controllable fashion. We further demonstrated the two-tier atomic force microscopic (AFM) method that uses SCNE to carry out two subsequent AFM tasks in situ. The approach allows guided protein delivery and subsequent high-resolution imaging at the same local area, thus opening up the possibility of monitoring protein functions in live cells. The results imply that SCNE is a versatile cross-linker that can be used for a wide range of applications where photocleavage ensures clean and remote-controllable release of biological molecules from a substrate. PMID:22432929

  9. Dual-Beam Histotripsy: A Low-Frequency Pump Enabling a High-Frequency Probe for Precise Lesion Formation

    PubMed Central

    Lin, Kuang-Wei; Duryea, Alexander P.; Kim, Yohan; Hall, Timothy L.; Xu, Zhen; Cain, Charles A.

    2014-01-01

    Histotripsy produces tissue fractionation through dense energetic bubble clouds generated by short, high-pressure, ultrasound pulses. When using pulses shorter than 2 cycles, the generation of these energetic bubble clouds only depends on where the peak negative pressure (P–) exceeds an intrinsic threshold of a medium (26 – 30 MPa in soft tissue with high water content). This paper investigates a strategic method for precise lesion generation in which a low-frequency pump pulse is applied to enable a sub-threshold high-frequency probe pulse to exceed the intrinsic threshold. This pump-probe method of controlling a supra-threshold volume can be called “dual-beam histotripsy.” A 20-element dual-frequency (500 kHz and 3 MHz elements confocally aligned) array transducer was used to generate dual-beam histotripsy pulses in RBC phantoms and porcine hepatic tissue specimens. The results showed that, when sub-intrinsic-threshold pump (500 kHz) and probe (3 MHz) pulses were applied together, dense bubble clouds (and resulting lesions) were only generated when their peak negative pressures combined constructively to exceed the intrinsic threshold. The smallest reproducible lesion varied with the relative amplitude between the pump and probe pulses, and, with a higher proportion of the probe pulse, smaller lesions could be generated. When the propagation direction of the probe pulse relative to the pump pulse was altered, the shape of the produced lesion changed based on the region that exceeded intrinsic threshold. Since the low-frequency pump pulse is more immune to attenuation and aberrations, and the high-frequency probe pulse can provide precision in lesion formation, this dual-beam histotripsy approach would be very useful in situations where precise lesion formation is required through a highly attenuative and aberrative medium, such as transcranial therapy. This is particularly true if a small low-attenuation acoustic window is available for the high

  10. Dual-beam histotripsy: a low-frequency pump enabling a high-frequency probe for precise lesion formation.

    PubMed

    Lin, Kuang-Wei; Duryea, Alexander P; Kim, Yohan; Hall, Timothy L; Xu, Zhen; Cain, Charles A

    2014-02-01

    Histotripsy produces tissue fractionation through dense energetic bubble clouds generated by short, high-pressure, ultrasound pulses. When using pulses shorter than 2 cycles, the generation of these energetic bubble clouds only depends on where the peak negative pressure (P-) exceeds the intrinsic threshold of the medium (26 to 30 MPa in soft tissue with high water content). This paper investigates a strategic method for precise lesion generation in which a low-frequency pump pulse is applied to enable a sub-threshold high-frequency probe pulse to exceed the intrinsic threshold. This pump-probe method of controlling a supra-threshold volume can be called dual-beam histotripsy. A 20-element dual-frequency (500-kHz and 3-MHz elements confocally aligned) array transducer was used to generate dual-beam histotripsy pulses in red blood cell phantoms and porcine hepatic tissue specimens. The results showed that when sub-intrinsic-threshold pump (500-kHz) and probe (3-MHz) pulses were applied together, dense bubble clouds (and resulting lesions) were only generated when their peak negative pressures combined constructively to exceed the intrinsic threshold. The smallest reproducible lesion varied with the relative amplitude between the pump and probe pulses, and, with a higher proportion of the probe pulse, smaller lesions could be generated. When the propagation direction of the probe pulse relative to the pump pulse was altered, the shape of the produced lesion changed based on the region that exceeded intrinsic threshold. Because the low-frequency pump pulse is more immune to attenuation and aberrations, and the high-frequency probe pulse can provide precision in lesion formation, this dual-beam histotripsy approach would be very useful in situations in which precise lesion formation is required through a highly attenuative and aberrative medium, such as transcranial therapy. This is particularly true if a small low-attenuation acoustic window is available for the high

  11. Dual-beam histotripsy: a low-frequency pump enabling a high-frequency probe for precise lesion formation.

    PubMed

    Lin, Kuang-Wei; Duryea, Alexander P; Kim, Yohan; Hall, Timothy L; Xu, Zhen; Cain, Charles A

    2014-02-01

    Histotripsy produces tissue fractionation through dense energetic bubble clouds generated by short, high-pressure, ultrasound pulses. When using pulses shorter than 2 cycles, the generation of these energetic bubble clouds only depends on where the peak negative pressure (P-) exceeds the intrinsic threshold of the medium (26 to 30 MPa in soft tissue with high water content). This paper investigates a strategic method for precise lesion generation in which a low-frequency pump pulse is applied to enable a sub-threshold high-frequency probe pulse to exceed the intrinsic threshold. This pump-probe method of controlling a supra-threshold volume can be called dual-beam histotripsy. A 20-element dual-frequency (500-kHz and 3-MHz elements confocally aligned) array transducer was used to generate dual-beam histotripsy pulses in red blood cell phantoms and porcine hepatic tissue specimens. The results showed that when sub-intrinsic-threshold pump (500-kHz) and probe (3-MHz) pulses were applied together, dense bubble clouds (and resulting lesions) were only generated when their peak negative pressures combined constructively to exceed the intrinsic threshold. The smallest reproducible lesion varied with the relative amplitude between the pump and probe pulses, and, with a higher proportion of the probe pulse, smaller lesions could be generated. When the propagation direction of the probe pulse relative to the pump pulse was altered, the shape of the produced lesion changed based on the region that exceeded intrinsic threshold. Because the low-frequency pump pulse is more immune to attenuation and aberrations, and the high-frequency probe pulse can provide precision in lesion formation, this dual-beam histotripsy approach would be very useful in situations in which precise lesion formation is required through a highly attenuative and aberrative medium, such as transcranial therapy. This is particularly true if a small low-attenuation acoustic window is available for the high

  12. Characterization of Interstrand DNA-DNA Cross-Links Using the α-Hemolysin Protein Nanopore.

    PubMed

    Zhang, Xinyue; Price, Nathan E; Fang, Xi; Yang, Zhiyu; Gu, Li-Qun; Gates, Kent S

    2015-12-22

    Nanopore-based sensors have been studied extensively as potential tools for DNA sequencing, characterization of epigenetic modifications such as 5-methylcytosine, and detection of microRNA biomarkers. In the studies described here, the α-hemolysin protein nanopore embedded in a lipid bilayer was used for the detection and characterization of interstrand cross-links in duplex DNA. Interstrand cross-links are important lesions in medicinal chemistry and toxicology because they prevent the strand separation that is required for read-out of genetic information from DNA in cells. In addition, interstrand cross-links are used for the stabilization of duplex DNA in structural biology and materials science. Cross-linked DNA fragments produced unmistakable current signatures in the nanopore experiment. Some cross-linked substrates gave irreversible current blocks of >10 min, while others produced long current blocks (10-100 s) before the double-stranded DNA cross-link translocated through the α-hemolysin channel in a voltage-driven manner. The duration of the current block for the different cross-linked substrates examined here may be dictated by the stability of the duplex region left in the vestibule of the nanopore following partial unzipping of the cross-linked DNA. Construction of calibration curves measuring the frequency of cross-link blocking events (1/τon) as a function of cross-link concentration enabled quantitative determination of the amounts of cross-linked DNA present in samples. The unique current signatures generated by cross-linked DNA in the α-HL nanopore may enable the detection and characterization of DNA cross-links that are important in toxicology, medicine, and materials science.

  13. Transcriptome-based exon capture enables highly cost-effective comparative genomic data collection at moderate evolutionary scales

    PubMed Central

    2012-01-01

    Background To date, exon capture has largely been restricted to species with fully sequenced genomes, which has precluded its application to lineages that lack high quality genomic resources. We developed a novel strategy for designing array-based exon capture in chipmunks (Tamias) based on de novo transcriptome assemblies. We evaluated the performance of our approach across specimens from four chipmunk species. Results We selectively targeted 11,975 exons (~4 Mb) on custom capture arrays, and enriched over 99% of the targets in all libraries. The percentage of aligned reads was highly consistent (24.4-29.1%) across all specimens, including in multiplexing up to 20 barcoded individuals on a single array. Base coverage among specimens and within targets in each species library was uniform, and the performance of targets among independent exon captures was highly reproducible. There was no decrease in coverage among chipmunk species, which showed up to 1.5% sequence divergence in coding regions. We did observe a decline in capture performance of a subset of targets designed from a much more divergent ground squirrel genome (30 My), however, over 90% of the targets were also recovered. Final assemblies yielded over ten thousand orthologous loci (~3.6 Mb) with thousands of fixed and polymorphic SNPs among species identified. Conclusions Our study demonstrates the potential of a transcriptome-enabled, multiplexed, exon capture method to create thousands of informative markers for population genomic and phylogenetic studies in non-model species across the tree of life. PMID:22900609

  14. High-throughput sequencing enhanced phage display enables the identification of patient-specific epitope motifs in serum

    PubMed Central

    Christiansen, Anders; Kringelum, Jens V.; Hansen, Christian S.; Bøgh, Katrine L.; Sullivan, Eric; Patel, Jigar; Rigby, Neil M.; Eiwegger, Thomas; Szépfalusi, Zsolt; Masi, Federico de; Nielsen, Morten; Lund, Ole; Dufva, Martin

    2015-01-01

    Phage display is a prominent screening technique with a multitude of applications including therapeutic antibody development and mapping of antigen epitopes. In this study, phages were selected based on their interaction with patient serum and exhaustively characterised by high-throughput sequencing. A bioinformatics approach was developed in order to identify peptide motifs of interest based on clustering and contrasting to control samples. Comparison of patient and control samples confirmed a major issue in phage display, namely the selection of unspecific peptides. The potential of the bioinformatic approach was demonstrated by identifying epitopes of a prominent peanut allergen, Ara h 1, in sera from patients with severe peanut allergy. The identified epitopes were confirmed by high-density peptide micro-arrays. The present study demonstrates that high-throughput sequencing can empower phage display by (i) enabling the analysis of complex biological samples, (ii) circumventing the traditional laborious picking and functional testing of individual phage clones and (iii) reducing the number of selection rounds. PMID:26246327

  15. Fabrication of perforated isoporous membranes via a transfer-free strategy: enabling high-resolution separation of cells.

    PubMed

    Ou, Yang; Lv, Chang-Jiang; Yu, Wei; Mao, Zheng-Wei; Wan, Ling-Shu; Xu, Zhi-Kang

    2014-12-24

    Thin perforated membranes with ordered pores are ideal barriers for high-resolution and high-efficiency selective transport and separation of biological species. However, for self-assembled thin membranes with a thickness less than several micrometers, an additional step of transferring the membranes onto porous supports is generally required. In this article, we present a facile transfer-free strategy for fabrication of robust perforated composite membranes via the breath figure process, and for the first time, demonstrate the application of the membranes in high-resolution cell separation of yeasts and lactobacilli without external pressure, achieving almost 100% rejection of yeasts and more than 70% recovery of lactobacilli with excellent viability. The avoidance of the transfer step simplifies the fabrication procedure of composite membranes and greatly improves the membrane homogeneity. Moreover, the introduction of an elastic triblock copolymer increases the interfacial strength between the membrane and the support, and allows the preservation of composite membranes in a dry state. Such perforated ordered membranes can also be applied in other size-based separation systems, enabling new opportunities in bioseparation and biosensors. PMID:25421306

  16. Mixed-Source EGR for Enabling High Efficiency Clean Combustion Modes in a Light-Duty Diesel Engine

    SciTech Connect

    Cho, Kukwon; Han, Manbae; Wagner, Robert M; Sluder, Scott

    2008-01-01

    The source of exhaust gas recirculation (EGR), and consequently composition and temperature, has a significant effect on advanced combustion modes including stability, efficiency, and emissions. The effects of high-pressure loop EGR (HPL EGR) and low-pressure loop EGR (LPL EGR) on achieving high efficiency clean combustion (HECC) modes in a light-duty diesel engine were characterized in this study. High dilution operation is complicated in real-world situations due to inadequate control of mixture temperature and the slow response of LPL EGR systems. Mixed-source EGR (combination of HPL EGR and LPL EGR) was investigated as a reasonable approach for controlling mixture temperature. The potential of mixed-source EGR has been explored using LPL EGR as a 'base' for dilution rather than as a sole source. HPL EGR provides the 'trim' for controlling mixture temperature and has the potential for enabling precise control of dilution targets. This approach also has a benefit where LPL EGR does not provide sufficient dilution for achieving conditions appropriate for HECC operation. The balance of the required dilution could be achieved with HPL EGR mitigating the need for throttling or a LPL EGR pump. The results of this investigation revealed significant differences in engine-out emissions and performance for various EGR sources.

  17. Photo-induced cross-linking of unmodified proteins (PICUP) applied to amyloidogenic peptides.

    PubMed

    Rahimi, Farid; Maiti, Panchanan; Bitan, Gal

    2009-01-01

    The assembly of amyloidogenic proteins into toxic oligomers is a seminal event in the pathogenesis of protein misfolding diseases, including Alzheimer's, Parkinson's, and Huntington's diseases, hereditary amyotrophic lateral sclerosis, and type 2 diabetes. Owing to the metastable nature of these protein assemblies, it is difficult to assess their oligomer size distribution quantitatively using classical methods, such as electrophoresis, chromatography, fluorescence, or dynamic light scattering. Oligomers of amyloidogenic proteins exist as metastable mixtures, in which the oligomers dissociate into monomers and associate into larger assemblies simultaneously. PICUP stabilizes oligomer populations by covalent cross-linking and when combined with fractionation methods, such as sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) or size-exclusion chromatography (SEC), PICUP provides snapshots of the oligomer size distributions that existed before cross-linking. Hence, PICUP enables visualization and quantitative analysis of metastable protein populations and can be used to monitor assembly and decipher relationships between sequence modifications and oligomerization(1). Mechanistically, PICUP involves photo-oxidation of Ru(2+) in a tris(bipyridyl)Ru(II) complex (RuBpy) to Ru(3+) by irradiation with visible light in the presence of an electron acceptor. Ru(3+) is a strong one-electron oxidizer capable of abstracting an electron from a neighboring protein molecule, generating a protein radical(1,2). Radicals are unstable, highly-reactive species and therefore disappear rapidly through a variety of intra- and intermolecular reactions. A radical may utilize the high energy of an unpaired electron to react with another protein monomer forming a dimeric radical, which subsequently loses a hydrogen atom and forms a stable, covalently-linked dimer. The dimer may then react further through a similar mechanism with monomers or other dimers to form higher

  18. DNA Photolithography with Cinnamate Crosslinkers

    NASA Technical Reports Server (NTRS)

    Feng, Lang (Inventor); Chaikin, Paul Michael (Inventor)

    2016-01-01

    The present invention relates generally to cinnamate crosslinkers. Specifically, the present invention relates to gels, biochips, and functionalized surfaces useful as probes, in assays, in gels, and for drug delivery, and methods of making the same using a newly-discovered crosslinking configuration.

  19. Mixing injector enables time-resolved crystallography with high hit rate at X-ray free electron lasers

    PubMed Central

    Calvey, George D.; Katz, Andrea M.; Schaffer, Chris B.; Pollack, Lois

    2016-01-01

    Knowledge of protein structure provides essential insight into function, enhancing our understanding of diseases and enabling new treatment development. X-ray crystallography has been used to solve the structures of more than 100 000 proteins; however, the vast majority represent long-lived states that do not capture the functional motions of these molecular machines. Reactions triggered by the addition of a ligand can be the most challenging to detect with crystallography because of the difficulty of synchronizing reactions to create detectable quantities of transient states. The development of X-ray free electron lasers (XFELs) and serial femtosecond crystallography (SFX) enables new approaches for solving protein structures following the rapid diffusion of ligands into micron sized protein crystals. Conformational changes occurring on millisecond timescales can be detected and time-resolved. Here, we describe a new XFEL injector which incorporates a microfluidic mixer to rapidly combine reactant and sample milliseconds before the sample reaches the X-ray beam. The mixing injector consists of bonded, concentric glass capillaries. The fabrication process, employing custom laser cut centering spacers and UV curable epoxy, ensures precise alignment of capillaries for repeatable, centered sample flow and dependable mixing. Crystal delivery capillaries are 50 or 75 μm in diameter and can contain an integrated filter depending on the demands of the experiment. Reaction times can be varied from submillisecond to several hundred milliseconds. The injector features rapid and uniform mixing, low sample dilution, and high hit rates. It is fully compatible with existing SFX beamlines. PMID:27679802

  20. Mixing injector enables time-resolved crystallography with high hit rate at X-ray free electron lasers.

    PubMed

    Calvey, George D; Katz, Andrea M; Schaffer, Chris B; Pollack, Lois

    2016-09-01

    Knowledge of protein structure provides essential insight into function, enhancing our understanding of diseases and enabling new treatment development. X-ray crystallography has been used to solve the structures of more than 100 000 proteins; however, the vast majority represent long-lived states that do not capture the functional motions of these molecular machines. Reactions triggered by the addition of a ligand can be the most challenging to detect with crystallography because of the difficulty of synchronizing reactions to create detectable quantities of transient states. The development of X-ray free electron lasers (XFELs) and serial femtosecond crystallography (SFX) enables new approaches for solving protein structures following the rapid diffusion of ligands into micron sized protein crystals. Conformational changes occurring on millisecond timescales can be detected and time-resolved. Here, we describe a new XFEL injector which incorporates a microfluidic mixer to rapidly combine reactant and sample milliseconds before the sample reaches the X-ray beam. The mixing injector consists of bonded, concentric glass capillaries. The fabrication process, employing custom laser cut centering spacers and UV curable epoxy, ensures precise alignment of capillaries for repeatable, centered sample flow and dependable mixing. Crystal delivery capillaries are 50 or 75 μm in diameter and can contain an integrated filter depending on the demands of the experiment. Reaction times can be varied from submillisecond to several hundred milliseconds. The injector features rapid and uniform mixing, low sample dilution, and high hit rates. It is fully compatible with existing SFX beamlines. PMID:27679802

  1. Bespoke contrast-matched diblock copolymer nanoparticles enable the rational design of highly transparent Pickering double emulsions

    NASA Astrophysics Data System (ADS)

    Rymaruk, Matthew J.; Thompson, Kate L.; Derry, Matthew J.; Warren, Nicholas J.; Ratcliffe, Liam P. D.; Williams, Clive N.; Brown, Steven L.; Armes, Steven P.

    2016-07-01

    We report the preparation of highly transparent oil-in-water Pickering emulsions using contrast-matched organic nanoparticles. This is achieved via addition of judicious amounts of either sucrose or glycerol to an aqueous dispersion of poly(glycerol monomethacrylate)56-poly(2,2,2-trifluoroethyl methacrylate)500 [PGMA-PTFEMA] diblock copolymer nanoparticles prior to high shear homogenization with an equal volume of n-dodecane. The resulting Pickering emulsions comprise polydisperse n-dodecane droplets of 20-100 μm diameter and exhibit up to 96% transmittance across the visible spectrum. In contrast, control experiments using non-contrast-matched poly(glycerol monomethacrylate)56-poly(benzyl methacrylate)300 [PGMA56-PBzMA300] diblock copolymer nanoparticles as a Pickering emulsifier only produced conventional highly turbid emulsions. Thus contrast-matching of the two immiscible phases is a necessary but not sufficient condition for the preparation of highly transparent Pickering emulsions: it is essential to use isorefractive nanoparticles in order to minimize light scattering. Furthermore, highly transparent oil-in-water-in-oil Pickering double emulsions can be obtained by homogenizing the contrast-matched oil-in-water Pickering emulsion prepared using the PGMA56-PTFEMA500 nanoparticles with a contrast-matched dispersion of hydrophobic poly(lauryl methacrylate)39-poly(2,2,2-trifluoroethyl methacrylate)800 [PLMA39-PTFEMA800] diblock copolymer nanoparticles in n-dodecane. Finally, we show that an isorefractive oil-in-water Pickering emulsion enables fluorescence spectroscopy to be used to monitor the transport of water-insoluble small molecules (pyrene and benzophenone) between n-dodecane droplets. Such transport is significantly less efficient than that observed for the equivalent isorefractive surfactant-stabilized emulsion. Conventional turbid emulsions do not enable such a comparison to be made because the intense light scattering leads to substantial spectral

  2. Low-cost, highly transparent flexible low-e coating film to enable electrochromic windows with increased energy savings

    SciTech Connect

    Berland, Brian; Hollingsworth, Russell

    2015-03-31

    Five Quads of energy are lost through windows annually in the U.S. Low-e coatings are increasingly employed to reduce the wasted energy. Most commonly, the low-e coating is an oxide material applied directly to the glass at high temperature. With over 100,000,000 existing homes, a retrofit product is crucial to achieve widespread energy savings. Low-e films, i.e. coatings on polymeric substrates, are now also available to meet this need. However, the traditional oxide materials and process is incompatible with low temperature plastics. Alternate high performing low-e films typically incorporate materials that limit visible transmission to 35% or less. Further, the cost is high. The objective of this award was to develop a retrofit, integrated low-e/electrochromic window film to dramatically reduce energy lost through windows. While field testing of state-of-the-art electrochromic (EC) windows show the energy savings are maximized if a low-e coating is used in conjunction with the EC, available low-e films have a low visible transmission (~70% or less) that limits the achievable clear state and therefore, appearance and energy savings potential. Comprehensive energy savings models were completed at Lawrence Berkeley National Lab (LBNL). A parametric approach was used to project energy usage for windows with a large range of low-e properties across all U.S. climate zones, without limiting the study to materials that had already been produced commercially or made in a lab. The model enables projection of energy savings for low-e films as well as integrated low-e/EC products. This project developed a novel low-e film, optimized for compatibility with EC windows, using low temperature, high deposition rate processes for the growth of low-e coatings on plastic films by microwave plasma enhanced chemical vapor deposition. Silica films with good density and optical properties were demonstrated at deposition rates as high as 130Å/sec. A simple bi-layer low-e stack of

  3. Advanced Sulfur Cathode Enabled by Highly Crumpled Nitrogen-Doped Graphene Sheets for High-Energy-Density Lithium-Sulfur Batteries.

    PubMed

    Song, Jiangxuan; Yu, Zhaoxin; Gordin, Mikhail L; Wang, Donghai

    2016-02-10

    Herein, we report a synthesis of highly crumpled nitrogen-doped graphene sheets with ultrahigh pore volume (5.4 cm(3)/g) via a simple thermally induced expansion strategy in absence of any templates. The wrinkled graphene sheets are interwoven rather than stacked, enabling rich nitrogen-containing active sites. Benefiting from the unique pore structure and nitrogen-doping induced strong polysulfide adsorption ability, lithium-sulfur battery cells using these wrinkled graphene sheets as both sulfur host and interlayer achieved a high capacity of ∼1000 mAh/g and exceptional cycling stability even at high sulfur content (≥80 wt %) and sulfur loading (5 mg sulfur/cm(2)). The high specific capacity together with the high sulfur loading push the areal capacity of sulfur cathodes to ∼5 mAh/cm(2), which is outstanding compared to other recently developed sulfur cathodes and ideal for practical applications.

  4. Single-cell microarray enables high-throughput evaluation of DNA double-strand breaks and DNA repair inhibitors

    PubMed Central

    Weingeist, David M.; Ge, Jing; Wood, David K.; Mutamba, James T.; Huang, Qiuying; Rowland, Elizabeth A.; Yaffe, Michael B.; Floyd, Scott; Engelward, Bevin P.

    2013-01-01

    A key modality of non-surgical cancer management is DNA damaging therapy that causes DNA double-strand breaks that are preferentially toxic to rapidly dividing cancer cells. Double-strand break repair capacity is recognized as an important mechanism in drug resistance and is therefore a potential target for adjuvant chemotherapy. Additionally, spontaneous and environmentally induced DSBs are known to promote cancer, making DSB evaluation important as a tool in epidemiology, clinical evaluation and in the development of novel pharmaceuticals. Currently available assays to detect double-strand breaks are limited in throughput and specificity and offer minimal information concerning the kinetics of repair. Here, we present the CometChip, a 96-well platform that enables assessment of double-strand break levels and repair capacity of multiple cell types and conditions in parallel and integrates with standard high-throughput screening and analysis technologies. We demonstrate the ability to detect multiple genetic deficiencies in double-strand break repair and evaluate a set of clinically relevant chemical inhibitors of one of the major double-strand break repair pathways, non-homologous end-joining. While other high-throughput repair assays measure residual damage or indirect markers of damage, the CometChip detects physical double-strand breaks, providing direct measurement of damage induction and repair capacity, which may be useful in developing and implementing treatment strategies with reduced side effects. PMID:23422001

  5. Pump-free gradient-based micro-device enables quantitative and high-throughput bacterial growth inhibition analysis.

    PubMed

    Ran, Min; Wang, Ying; Wang, Sida; Luo, Chunxiong

    2015-08-01

    Antibiotic susceptibility testing is very important in antibiotic therapy. Traditional methods to determine antibiotic susceptibility include disk diffusion and broth dilution. However, these tests are always labor intensive, time-consuming, and need large amounts of reagents. In this paper, we demonstrated a novel pump-free micro-device that enables quantitative and high-throughput bacterial growth inhibition analysis. This device consists of a series of wells and diffusion-based antibiotic gradient channels. The wells serve as antibiotic sources and buffer sinks, and we could easily observe the bacterial growth in the gradient channels .The design of the multi-wells is adapted to the commercialized multi-channel pipette, which makes it very convenient for loading reagents into the wells. For each assay, only about 20 μL antibiotic solution is needed. As a demonstration, we used both fluorescence images and dark-field images to quantify the bacterial growth inhibition effect under different antibiotics. The quantitative data of bacterial growth inhibition under different antibiotics can be obtained within 3 to 4 h. Considering the simple operation process and the high-throughput and quantitative result this device can offer, it has great potential to be widely used in clinics and may be useful for the study of the kinetics of bacterial growth.

  6. High-Resolution Distance Dependence Study of Surface-Enhanced Raman Scattering Enabled by Atomic Layer Deposition.

    PubMed

    Masango, Sicelo S; Hackler, Ryan A; Large, Nicolas; Henry, Anne-Isabelle; McAnally, Michael O; Schatz, George C; Stair, Peter C; Van Duyne, Richard P

    2016-07-13

    We present a high-resolution distance dependence study of surface-enhanced Raman scattering (SERS) enabled by atomic layer deposition (ALD) at 55 and 100 °C. ALD is used to deposit monolayers of Al2O3 on bare silver film over nanospheres (AgFONs) and AgFONs functionalized with self-assembled monolayers. Operando SERS is used to measure the intensities of the Al-CH3 and C-H stretches from trimethylaluminum (TMA) as a function of distance from the AgFON surface. This study clearly demonstrates that SERS on AgFON substrates displays both a short- and long-range nanometer scale distance dependence. Excellent agreement is obtained between these experiments and theory that incorporates both short-range and long-range terms. This is a high-resolution operando SERS distance dependence study performed in one integrated experiment using ALD Al2O3 as the spacer layer and Raman label simultaneously. The long-range SERS distance dependence should make it possible to detect chemisorbed surface species located as far as ∼3 nm from the AgFON substrate and will provide new insight into the surface chemistry of ALD and catalytic reactions.

  7. Improved Selection of Internal Transcribed Spacer-Specific Primers Enables Quantitative, Ultra-High-Throughput Profiling of Fungal Communities

    PubMed Central

    Bokulich, Nicholas A.

    2013-01-01

    Ultra-high-throughput sequencing (HTS) of fungal communities has been restricted by short read lengths and primer amplification bias, slowing the adoption of newer sequencing technologies to fungal community profiling. To address these issues, we evaluated the performance of several common internal transcribed spacer (ITS) primers and designed a novel primer set and work flow for simultaneous quantification and species-level interrogation of fungal consortia. Primer comparison and validation were predicted in silico and by sequencing a “mock community” of mixed yeast species to explore the challenges of amplicon length and amplification bias for reconstructing defined yeast community structures. The amplicon size and distribution of this primer set are smaller than for all preexisting ITS primer sets, maximizing sequencing coverage of hypervariable ITS domains by very-short-amplicon, high-throughput sequencing platforms. This feature also enables the optional integration of quantitative PCR (qPCR) directly into the HTS preparatory work flow by substituting qPCR with these primers for standard PCR, yielding quantification of individual community members. The complete work flow described here, utilizing any of the qualified primer sets evaluated, can rapidly profile mixed fungal communities and capably reconstructed well-characterized beer and wine fermentation fungal communities. PMID:23377949

  8. Aqueous biphasic cancer cell migration assay enables robust, high-throughput screening of anti-cancer compounds.

    PubMed

    Lemmo, Stephanie; Nasrollahi, Samila; Tavana, Hossein

    2014-03-01

    Migration of tumor cells is a fundamental event implicated in metastatic progression of cancer. Therapeutic compounds with the ability to inhibit the motility of cancer cells are critical for preventing cancer metastasis. Achieving this goal requires new technologies that enable high-throughput drug screening against migration of cancer cells and expedite drug discovery. We report an easy-to-implement, robotically operated, cell migration microtechnology with the capability of simultaneous screening of multiple compounds. The technology utilizes a fully biocompatible polymeric aqueous two-phase system to pattern a monolayer of cells containing a cell-excluded gap that serves as the migration niche. We adapted this technology to a standard 96-well plate format and parametrically optimized it to generate highly consistent migration niches. The analysis of migration is done automatically using computerized schemes. We use statistical metrics and show the robustness of this assay for drug screening and its sensitivity to identify effects of different drug compounds on migration of cancer cells. This technology can be employed in core centers, research laboratories, and pharmaceutical industries to evaluate the efficacy of compounds against migration of various types of metastatic cancer cells prior to expensive animal tests and thus, streamline anti-migratory drug screening.

  9. High-Resolution Distance Dependence Study of Surface-Enhanced Raman Scattering Enabled by Atomic Layer Deposition.

    PubMed

    Masango, Sicelo S; Hackler, Ryan A; Large, Nicolas; Henry, Anne-Isabelle; McAnally, Michael O; Schatz, George C; Stair, Peter C; Van Duyne, Richard P

    2016-07-13

    We present a high-resolution distance dependence study of surface-enhanced Raman scattering (SERS) enabled by atomic layer deposition (ALD) at 55 and 100 °C. ALD is used to deposit monolayers of Al2O3 on bare silver film over nanospheres (AgFONs) and AgFONs functionalized with self-assembled monolayers. Operando SERS is used to measure the intensities of the Al-CH3 and C-H stretches from trimethylaluminum (TMA) as a function of distance from the AgFON surface. This study clearly demonstrates that SERS on AgFON substrates displays both a short- and long-range nanometer scale distance dependence. Excellent agreement is obtained between these experiments and theory that incorporates both short-range and long-range terms. This is a high-resolution operando SERS distance dependence study performed in one integrated experiment using ALD Al2O3 as the spacer layer and Raman label simultaneously. The long-range SERS distance dependence should make it possible to detect chemisorbed surface species located as far as ∼3 nm from the AgFON substrate and will provide new insight into the surface chemistry of ALD and catalytic reactions. PMID:27243108

  10. The Subaru Coronagraphic Extreme Adaptive Optics System: Enabling High-Contrast Imaging on Solar-System Scales

    NASA Astrophysics Data System (ADS)

    Jovanovic, N.; Martinache, F.; Guyon, O.; Clergeon, C.; Singh, G.; Kudo, T.; Garrel, V.; Newman, K.; Doughty, D.; Lozi, J.; Males, J.; Minowa, Y.; Hayano, Y.; Takato, N.; Morino, J.; Kuhn, J.; Serabyn, E.; Norris, B.; Tuthill, P.; Schworer, G.; Stewart, P.; Close, L.; Huby, E.; Perrin, G.; Lacour, S.; Gauchet, L.; Vievard, S.; Murakami, N.; Oshiyama, F.; Baba, N.; Matsuo, T.; Nishikawa, J.; Tamura, M.; Lai, O.; Marchis, F.; Duchene, G.; Kotani, T.; Woillez, J.

    2015-09-01

    The Subaru Coronagraphic Extreme Adaptive Optics (SCExAO) instrument is a multipurpose high-contrast imaging platform designed for the discovery and detailed characterization of exoplanetary systems and serves as a testbed for high-contrast imaging technologies for ELTs. It is a multiband instrument which makes use of light from 600 to 2500 nm, allowing for coronagraphic direct exoplanet imaging of the inner 3λ/D from the stellar host. Wavefront sensing and control are key to the operation of SCExAO. A partial correction of low-order modes is provided by Subaru's facility adaptive optics system with the final correction, including high-order modes, implemented downstream by a combination of a visible pyramid wavefront sensor and a 2000-element deformable mirror. The well-corrected NIR (y-K bands) wavefronts can then be injected into any of the available coronagraphs, including but not limited to the phase-induced amplitude apodization and the vector vortex coronagraphs, both of which offer an inner working angle as low as 1λ/D. Noncommon path, low-order aberrations are sensed with a coronagraphic low-order wavefront sensor in the infrared (IR). Low noise, high frame rate NIR detectors allow for active speckle nulling and coherent differential imaging, while the HAWAII 2RG detector in the HiCIAO imager and/or the CHARIS integral field spectrograph (from mid-2016) can take deeper exposures and/or perform angular, spectral, and polarimetric differential imaging. Science in the visible is provided by two interferometric modules: VAMPIRES and FIRST, which enable subdiffraction limited imaging in the visible region with polarimetric and spectroscopic capabilities respectively. We describe the instrument in detail and present preliminary results both on-sky and in the laboratory.

  11. A Study into the Collision-induced Dissociation (CID) Behavior of Cross-Linked Peptides*

    PubMed Central

    Giese, Sven H.; Fischer, Lutz; Rappsilber, Juri

    2016-01-01

    Cross-linking/mass spectrometry resolves protein–protein interactions or protein folds by help of distance constraints. Cross-linkers with specific properties such as isotope-labeled or collision-induced dissociation (CID)-cleavable cross-linkers are in frequent use to simplify the identification of cross-linked peptides. Here, we analyzed the mass spectrometric behavior of 910 unique cross-linked peptides in high-resolution MS1 and MS2 from published data and validate the observation by a ninefold larger set from currently unpublished data to explore if detailed understanding of their fragmentation behavior would allow computational delivery of information that otherwise would be obtained via isotope labels or CID cleavage of cross-linkers. Isotope-labeled cross-linkers reveal cross-linked and linear fragments in fragmentation spectra. We show that fragment mass and charge alone provide this information, alleviating the need for isotope-labeling for this purpose. Isotope-labeled cross-linkers also indicate cross-linker-containing, albeit not specifically cross-linked, peptides in MS1. We observed that acquisition can be guided to better than twofold enrich cross-linked peptides with minimal losses based on peptide mass and charge alone. By help of CID-cleavable cross-linkers, individual spectra with only linear fragments can be recorded for each peptide in a cross-link. We show that cross-linked fragments of ordinary cross-linked peptides can be linearized computationally and that a simplified subspectrum can be extracted that is enriched in information on one of the two linked peptides. This allows identifying candidates for this peptide in a simplified database search as we propose in a search strategy here. We conclude that the specific behavior of cross-linked peptides in mass spectrometers can be exploited to relax the requirements on cross-linkers. PMID:26719564

  12. Distributed Analysis of Hip Implants Using Six National and Regional Registries: Comparing Metal-on-Metal with Metal-on-Highly Cross-Linked Polyethylene Bearings in Cementless Total Hip Arthroplasty in Young Patients

    PubMed Central

    Furnes, Ove; Paxton, Elizabeth; Cafri, Guy; Graves, Stephen; Bordini, Barbara; Comfort, Thomas; Rivas, Moises Coll; Banerjee, Samprit; Sedrakyan, Art

    2014-01-01

    Background: The regulation of medical devices has attracted controversy recently because of problems related to metal-on-metal hip implants. There is growing evidence that metal-on-metal implants fail early and cause local and systemic complications. However, the failure associated with metal-on-metal head size is not consistently documented and needs to be communicated to patients and surgeons. The purpose of this study is to compare implant survival of metal on metal with that of metal on highly cross-linked polyethylene. Methods: Using a distributed health data network, primary total hip arthroplasties were identified from six national and regional total joint arthroplasty registries (2001 to 2010). Inclusion criteria were patient age of forty-five to sixty-four years, cementless total hip arthroplasties, primary osteoarthritis diagnosis, and exclusion of the well-known outlier implant ASR (articular surface replacement). The primary outcome was revision for any reason. A meta-analysis of survival probabilities was performed with use of a fixed-effects model. Metal-on-metal implants with a large head size of >36 mm were compared with metal-on-highly cross-linked polyethylene implants. Results: Metal-on-metal implants with a large head size of >36 mm were used in 5172 hips and metal-on-highly cross-linked polyethylene implants were used in 14,372 hips. Metal-on-metal total hip replacements with a large head size of >36 mm had an increased risk of revision compared with metal-on-highly cross-linked polyethylene total hip replacements with more than two years of follow-up, with no difference during the first two years after implantation. The results of the hazard ratios (and 95% confidence intervals) from the multivariable model at various durations of follow-up were 0.95 (0.74 to 1.23) at zero to two years (p = 0.698), 1.42 (1.16 to 1.75) at more than two years to four years (p = 0.001), 1.78 (1.45 to 2.19) at more than four years to six years (p < 0.001), and 2

  13. Motion-Correction Enabled Ultra-High Resolution In-Vivo 7T-MRI of the Brain

    PubMed Central

    Federau, Christian

    2016-01-01

    Objectives To demonstrate the image quality that can be obtained for multiple contrasts using ultra-high resolution MRI (highest nominal resolution: 350 μm isotropic) at 7T using appropriate motion-correction. Materials and Methods An MRI-based fat-excitation motion navigator (which requires no additional hardware) was incorporated into T1-weighted (MP2RAGE, 350 μm nominal isotropic resolution, total scan time 124 mins over 2 sessions. The MP2RAGE also provides quantitative T1-maps), 3D-TSE (380 μm nominal isotropic resolution, total scan time 58 mins) and T2*-weighted protocols (3D-GRE, 380 μm nominal isotropic resolution, total scan time 42 mins) on a 7T MR system. Images from each contrast are presented from a single healthy adult male volunteer (34 years) for direct comparison. The subject provided written consent in accordance with the local review board. Results Images of various brain structures are revealed at unprecedented quality for in-vivo MRI. The presented images permit, for example, to delimit the internal structure of the basal ganglia and thalamus. The single digitationes of the hippocampus are visible, and the gyrus dentatus can be visualized. Intracortical contrast was also observed in the neocortex, including the stria of Gennari of the primary visual cortex. Conclusions Appropriate motion-correction allows MRI scans to be performed with extended scan times enabling exceptionally high resolution scans with high image quality, with the use of a 7T scanner allowing large brain coverage for 350–380 μm isotropic voxels with total scan times for each contrast ranging from 42 to 124 minutes. PMID:27159492

  14. Photoprecursor Approach Enables Preparation of Well-Performing Bulk-Heterojunction Layers Comprising a Highly Aggregating Molecular Semiconductor.

    PubMed

    Suzuki, Mitsuharu; Yamaguchi, Yuji; Takahashi, Kohei; Takahira, Katsuya; Koganezawa, Tomoyuki; Masuo, Sadahiro; Nakayama, Ken-ichi; Yamada, Hiroko

    2016-04-01

    Active-layer morphology critically affects the performance of organic photovoltaic cells, and thus its optimization is a key toward the achievement of high-efficiency devices. However, the optimization of active-layer morphology is sometimes challenging because of the intrinsic properties of materials such as strong self-aggregating nature or low miscibility. This study postulates that the "photoprecursor approach" can serve as an effective means to prepare well-performing bulk-heterojunction (BHJ) layers containing highly aggregating molecular semiconductors. In the photoprecursor approach, a photoreactive precursor compound is solution-deposited and then converted in situ to a semiconducting material. This study employs 2,6-di(2-thienyl)anthracene (DTA) and [6,6]-phenyl-C71-butyric acid methyl ester as p- and n-type materials, respectively, in which DTA is generated by the photoprecursor approach from the corresponding α-diketone-type derivative DTADK. When only chloroform is used as a cast solvent, the photovoltaic performance of the resulting BHJ films is severely limited because of unfavorable film morphology. The addition of a high-boiling-point cosolvent, o-dichlorobenzene (o-DCB), to the cast solution leads to significant improvement such that the resulting active layers afford up to approximately 5 times higher power conversion efficiencies. The film structure is investigated by two-dimensional grazing-incident wide-angle X-ray diffraction, atomic force microscopy, and fluorescence microspectroscopy to demonstrate that the use of o-DCB leads to improvement in film crystallinity and increase in charge-carrier generation efficiency. The change in film structure is assumed to originate from dynamic molecular motion enabled by the existence of solvent during the in situ photoreaction. The unique features of the photoprecursor approach will be beneficial in extending the material and processing scopes for the development of organic thin-film devices. PMID

  15. Reactive electrospinning and biodegradation of cross-linked methacrylated polycarbonate nanofibers.

    PubMed

    Wu, Ruizhi; Zhang, Jian-Feng; Fan, Yuwei; Stoute, Diana; Lallier, Thomas; Xu, Xiaoming

    2011-06-01

    The objectives of this study were to fabricate cross-linked biodegradable polycarbonate nanofibers and to investigate their biodegradability by different enzymes. Poly(2,3-dihydroxycarbonate) was synthesized from naturally occurring l-tartaric acid. The hydroxyl groups on the functional polycarbonate were converted to methacrylate groups to enable the polymer to cross-link under UV irradiation. Smooth cross-linked methacrylated polycarbonate nanofibers (300-1800 nm) were fabricated by a reactive electrospinning process with in situ UV radiation from a mixed solution of linear methacrylated polycarbonate (MPC) and poly(ethylene oxide) (PEO) (MPC:PEO = 9:1) in methanol/chloroform (50/50). These cross-linked nanofibers have shown excellent solvent resistance and their solubility decreases with increasing degree of cross-linking. The thermal properties of linear and cross-linked polycarbonate nanofibers were investigated by differential scanning calorimetry and thermogravimetric analysis. The cross-linked polycarbonate nanofibers show no melting point below 200 °C and their decomposition temperature increases with increasing cross-linking degree. Their biodegradation products by five different enzymes were analyzed using liquid chromatography-mass spectrometry (LC-MS). The biodegradability of the polycarbonate nanofibers decreases with increasing cross-linking degree. These nanofibers were found to support human fibroblast survival and to promote cell attachment. This study demonstrates that cross-linked biodegradable polycarbonate nanofibers with different chemical properties and biodegradability can be fabricated using the novel reactive electrospinning technology to meet the needs of different biomedical applications.

  16. Chitosan-based membranes with different ionic crosslinking density for pharmaceutical and industrial applications.

    PubMed

    Gierszewska, Magdalena; Ostrowska-Czubenko, Jadwiga

    2016-11-20

    Chitosan membranes (Ch), ionically crosslinked with pentasodium tripolyphosphate (TPP), were prepared using chitosan of medium and high molecular weight of similar degree of deacetylation and different crosslinking conditions. An effect of synthesis conditions (pH of crosslinking TPP solution equal to 5.5 and 9.0) on molecular and supermolecular structure and on crosslinking density of Ch/TPP membranes was confirmed using Fourier transform infrared spectroscopy (FTIR), wide-angle X-ray diffraction (WAXD) method and energy dispersive X-ray (EDX) spectrometry. Atomic-force microscopy (AFM) and contact angle measurements indicated some differences in membrane roughness and hydrophilicity. The state of water in non-crosslinked and ionically crosslinked Ch membranes containing different amount of water was investigated by low temperature differential scanning calorimetry (DSC) measurements. DSC analysis confirmed presence of freezing and non-freezing water in non-crosslinked and ionically crosslinked membranes. The amount of non-freezing water generally decreased after Ch crosslinking and was affected by crosslinking conditions and crosslinking density. Molecular weight of Ch had only slight influence on all characterized properties of ionically crosslinked membranes.

  17. Chitosan-based membranes with different ionic crosslinking density for pharmaceutical and industrial applications.

    PubMed

    Gierszewska, Magdalena; Ostrowska-Czubenko, Jadwiga

    2016-11-20

    Chitosan membranes (Ch), ionically crosslinked with pentasodium tripolyphosphate (TPP), were prepared using chitosan of medium and high molecular weight of similar degree of deacetylation and different crosslinking conditions. An effect of synthesis conditions (pH of crosslinking TPP solution equal to 5.5 and 9.0) on molecular and supermolecular structure and on crosslinking density of Ch/TPP membranes was confirmed using Fourier transform infrared spectroscopy (FTIR), wide-angle X-ray diffraction (WAXD) method and energy dispersive X-ray (EDX) spectrometry. Atomic-force microscopy (AFM) and contact angle measurements indicated some differences in membrane roughness and hydrophilicity. The state of water in non-crosslinked and ionically crosslinked Ch membranes containing different amount of water was investigated by low temperature differential scanning calorimetry (DSC) measurements. DSC analysis confirmed presence of freezing and non-freezing water in non-crosslinked and ionically crosslinked membranes. The amount of non-freezing water generally decreased after Ch crosslinking and was affected by crosslinking conditions and crosslinking density. Molecular weight of Ch had only slight influence on all characterized properties of ionically crosslinked membranes. PMID:27561522

  18. Facile synthesis of core-shell/hollow anisotropic particles via control of cross-linking during one-pot dispersion polymerization.

    PubMed

    Liu, Yanan; Ma, Yuhong; Liu, Lianying; Yang, Wantai

    2015-05-01

    Preparation of anisotropic particles based on seed phase separation involves multiple processes, and asymmetrical structures and surfaces cannot be produced when anisotropic shapes emerge. In conventional one-pot dispersion polymerization (Dis.P) using cross-linker, only spherical particles are prepared due to rapid and high cross-linking. Herein, monodisperse snowman-like particles with core-shell/hollow structures and partially rough surface were synthesized straightforward by a modified one-pot Dis.P, in which ethylene glycol and water (6/4, vol.) were used as medium, and ammonium persulfate (APS) aqueous solution, vinyl acetate (VA) and/or acrylic acid (AA), divinylbenzene (DVB) and styrene (St) were added at 6h. The cross-linking of growing particles was confined to exterior (forming cross-linked shell), and gel contents were low, leading to phase separation. Asymmetrical morphologies, structures, sizes and surface roughness were flexibly tuned by varying amounts of APS, VA and/or AA, water and DVB, and DVB adding speed. At low APS contents or high DVB amounts, the inhomogeneous cross-linking of head enabled its phase to separate, producing elongated head. With addition of VA and AA, phase separations inside head and body were induced, generating hollow structure. Adding DVB very slowly, nonlinear growth of third compartment occurred, forming bowed head. PMID:25626132

  19. A parallel algorithm for error correction in high-throughput short-read data on CUDA-enabled graphics hardware.

    PubMed

    Shi, Haixiang; Schmidt, Bertil; Liu, Weiguo; Müller-Wittig, Wolfgang

    2010-04-01

    Emerging DNA sequencing technologies open up exciting new opportunities for genome sequencing by generating read data with a massive throughput. However, produced reads are significantly shorter and more error-prone compared to the traditional Sanger shotgun sequencing method. This poses challenges for de novo DNA fragment assembly algorithms in terms of both accuracy (to deal with short, error-prone reads) and scalability (to deal with very large input data sets). In this article, we present a scalable parallel algorithm for correcting sequencing errors in high-throughput short-read data so that error-free reads can be available before DNA fragment assembly, which is of high importance to many graph-based short-read assembly tools. The algorithm is based on spectral alignment and uses the Compute Unified Device Architecture (CUDA) programming model. To gain efficiency we are taking advantage of the CUDA texture memory using a space-efficient Bloom filter data structure for spectrum membership queries. We have tested the runtime and accuracy of our algorithm using real and simulated Illumina data for different read lengths, error rates, input sizes, and algorithmic parameters. Using a CUDA-enabled mass-produced GPU (available for less than US$400 at any local computer outlet), this results in speedups of 12-84 times for the parallelized error correction, and speedups of 3-63 times for both sequential preprocessing and parallelized error correction compared to the publicly available Euler-SR program. Our implementation is freely available for download from http://cuda-ec.sourceforge.net .

  20. Nitrile crosslinked polyphenyl-quinoxaline/graphite fiber composites

    NASA Technical Reports Server (NTRS)

    Alston, W. B.

    1976-01-01

    Studies were performed to reduce the 600 F thermoplasticity of polyphenylquinoxaline (PPQ) matrix resins by introducing crosslinking by the reaction of terminal nitrile groups. Seven solvents and solvent mixtures were studied as the crosslinking catalysts and used to fabricate crosslinked PPQ/HMS graphite fiber composites. The room temperature and 600 F composite mechanical properties after short time and prolonged 600 F air exposure and the 600 F composite weight loss were determined and compared to those properties of high molecular weight, linear PPQ/HMS graphite fiber composites.

  1. Toward High Performance Integrated Semiconductor Micro and Nano Lasers Enabled by Transparent Conducting Materials: from Thick Structure to Thin Film

    NASA Astrophysics Data System (ADS)

    Ou, Fang

    Integrated semiconductor lasers working at the wavelength around 1.3 microm and 1.55 microm are of great interest for the research of photonic integrated circuit (PIC) since they are the crucial components for optical communications and many other applications. To satisfy the requirement of the next generation optical communication and computing systems, integrated semiconductor lasers are expected to have high device performance like very low lasing threshold, high output powers, high speed and possibility of being integrated with electronics. This dissertation focuses on the design and realization of InP based high performance electrically pumped integrated semiconductor lasers. In the dissertation, we first design the tall structure based electrically pumped integrated micro-lasers. Those lasers are capable of giving >10 mW output power with a moderate low threshold current density (0.5--5 kA/cm 2). Besides, a new enhanced radiation loss based coupler design is demonstrated to realize single directional output for curvilinear cavities. Second, the thin film structure based integrated semiconductor laser designs are proposed. Both structures use the side conduction geometry to enable the electrical injection into the thin film laser cavity. The performance enhancement of the thin film structure based lasers is analyzed compared to the tall structure. Third, we investigate the TCO materials. CdO deposited by PLD and In 2O3 deposited by IAD are studied from aspects of their physical, optical and electrical properties. Those materials can give a wide range of tunability in their conductivity (1--5000 S/cm) and optical transparency (loss 200--5000 cm-1), which is of great interest in realizing novel nanophotonic devices. In addition, the electrical contact properties of those materials to InP are also studied. Experiment result shows that both CdO and In2O3 can achieve good ohmic contact to n-InP with contact resistance as low as 10-6O·cm 2. At last, we investigate

  2. Chemical crosslinking of the subunits of HIV-1 reverse transcriptase.

    PubMed Central

    Debyser, Z.; De Clercq, E.

    1996-01-01

    The reverse transcriptase (RT) of the human immunodeficiency virus type 1 (HIV-1) is composed of two subunits of 66 and 51 kDa in a 1 to 1 ratio. Because dimerization is a prerequisite for enzymatic activity, interference with the dimerization process could constitute an alternative antiviral strategy for RT inhibition. Here we describe an in vitro assay for the study of the dimerization state of HIV-1 reverse transcriptase based on chemical crosslinking of the subunits with dimethylsuberimidate. Crosslinking results in the formation of covalent bonds between the subunits, so that the crosslinked species can be resolved by denaturing gel electrophoresis. Crosslinked RT species with molecular weight greater than that of the dimeric form accumulate during a 1-15-min time course. Initial evidence suggests that those high molecular weight species represent trimers and tetramers and may be the result of intramolecular crosslinking of the subunits of a higher-order RT oligomer. A peptide that corresponds to part of the tryptophan repeat motif in the connection domain of HIV-1 RT inhibits crosslink formation as well as enzymatic activity. The crosslinking assay thus allows the investigation of the effect of inhibitors on the dimerization of HIV-1 RT. PMID:8745406

  3. Poly(arlyene ether sulfone) based semi-interpenetrating polymer network membranes containing cross-linked poly(vinyl phosphonic acid) chains for fuel cell applications at high temperature and low humidity conditions

    NASA Astrophysics Data System (ADS)

    Kim, Kihyun; Heo, Pilwon; Ko, Taeyun; Kim, Ki-hyun; Kim, Sung-Kon; Pak, Chanho; Lee, Jong-Chan

    2015-10-01

    Semi-interpenetrating polymer network (semi-IPN) membranes are prepared by in-situ casting and thermal-initiated radical polymerization of vinyl phosphonic acid (VPA) and bis(2-(methacryloyloxy)ethyl) phosphate (BMAEP) in N,N-dimethylacetamide solutions of sulfonated poly(arylene ether sulfone) (SPAES). The incorporation of VPA units into the SPAES membranes improves proton conductivity especially at high temperature and low humidity conditions. In addition the cross-linker, BMAEP, prevents the decrease of the mechanical and chemical stabilities by the aliphatic linear poly(vinyl phosphonic acid) chains in the semi-IPN membranes, and furthermore the phosphonic acid group in BMAEP can prevent the decrease of the proton conductivity by the formation of cross-linked structures. Therefore, the resulting semi-IPN membranes show high proton conductivities up to 15 mS cm-1 at 120 °C and 40% RH. The fuel cell performance (187 mW cm-2 at 120 °C and 40% RH) of membrane-electrode assembly (MEA) from the semi-IPN membrane is found to be superior to that (145 mW cm-2 at 120 °C and 40% RH) of MEA from the SPAES membrane. The durability test result at the operating conditions indicates that the semi-IPN membrane is electrochemically very stable maintaining the low hydrogen cross-over and high power densities.

  4. Interfacial Bioorthogonal Cross-Linking

    PubMed Central

    2015-01-01

    Described herein is interfacial bioorthogonal cross-linking, the use of bioorthogonal chemistry to create and pattern biomaterials through diffusion-controlled gelation at the liquid-gel interface. The basis is a rapid (k2 284000 M–1 s–1) reaction between strained trans-cyclooctene (TCO) and tetrazine (Tz) derivatives. Syringe delivery of Tz-functionalized hyaluronic acid (HA-Tz) to a bath of bis-TCO cross-linker instantly creates microspheres with a cross-linked shell through which bis-TCO diffuses freely to introduce further cross-linking at the interface. Tags can be introduced with 3D resolution without external triggers or templates. Water-filled hydrogel channels were prepared by simply reversing the order of addition. Prostate cancer cells encapsulated in the microspheres have 99% viability, proliferate readily, and form aggregated clusters. This process is projected to be useful in the fabrication of cell-instructive matrices for in vitro tissue models. PMID:25177528

  5. Solubility Partner IF2 Domain I Enables High Yield Synthesis of Transducible Transcription Factors in E. coli

    PubMed Central

    Yang, William C.; Welsh, John P.; Lee, Jieun; Cooke, John P.; Swartz, James

    2011-01-01

    Since the discovery that somatic cells could be reprogrammed back to a pluripotent state through the viral expression of a certain set of transcription factors, there has been great interest in reprogramming using a safer and more clinically relevant protein-based approach. However, the search for an efficient reprogramming approach utilizing the transcription factors in protein form requires a significant amount of protein material. Milligram quantities of transcription factors are challenging to obtain due to low yields and poor solubility. In this work, we describe enhanced production of the pluripotency transcription factors Oct4, Sox2, Klf4, Nanog, and Lin28 after fusing them to a solubility partner, IF2 Domain I (IF2D1). We expressed and purified milligram quantities of the fusion proteins. Though the transcription factor passenger proteins became insoluble after removal of the IF2D1, the un-cleaved Oct4, Sox2, Klf4, Nanog fusion proteins exhibited specific binding to their consensus DNA sequences. However, when we administered the un-cleaved IF2D1-Oct4-R9 and IF2D1-Sox2-R9 to fibroblasts and measured their ability to influence transcriptional activity, we found that they were not fully bioactive; IF2D1-Oct4-R9 and IF2D1-Sox2-R9 influenced only a subset of their downstream gene targets. Thus, while the IF2D1 solubility partner enabled soluble production of the fusion protein at high levels, it did not yield fully bioactive transcription factors. PMID:21757009

  6. Xanthine oxidase-catalyzed crosslinking of cell membrane proteins.

    PubMed

    Girotti, A W; Thomas, J P; Jordan, J E

    1986-12-01

    Isolated erythrocyte membranes exposed to protease-free xanthine oxidase plus xanthine and ferric iron undergo lipid peroxidation and protein crosslinking (appearance of high molecular weight aggregates on sodium dodecyl sulfate (SDS) gel electrophoresis). Spectrin is more susceptible to crosslinking than the other polypeptides. Thiol-reducible bonds (disulfides) as well as nonreducible bonds are generated, the former type relatively rapidly (detected within 10-20 min) and the latter type more slowly (usually detected after 1 h). Reducible crosslinking is inhibited by catalase, but not by superoxide dismutase, desferrioxamine, butylated hydroxyltoluene, and mannitol; whereas nonreducible crosslinking, like free radical lipid peroxidation, is inhibited by all of these agents except mannitol. Zinc(II) also inhibits lipid peroxidation, but stimulates disulfide bond formation to the virtual exclusion of all other crosslinking. Our results indicate that disulfide formation is dependent on H2O2, but not O2- or iron. However, O2-, H2O2, and iron are all required for lipid peroxidation and nondisulfide crosslinking, suggesting the intermediacy of OH generated via the iron-catalyzed Haber-Weiss reaction. The possible role of malonaldehyde (MDA, a by-product of lipid peroxidation) in the latter type of crosslinking was examined. Solubilized samples of xanthine/xanthine oxidase-treated membranes showed a strong visible fluorescence (emission maximum 450 nm; excitation 390 nm). This resembled the fluorescence of membranes treated with authentic MDA, which forms conjugated imine linkages between amino groups. Fluorescence scanning of SDS gels from MDA-treated membranes showed a strong signal coincident with crosslinked proteins and also one in the low molecular weight, nonprotein region, suggestive of aminolipid conjugates. Similar scanning on xanthine/xanthine oxidase-reacted membranes indicated that all fluorescence is associated with the lipid fraction. Thus, nonreducible

  7. Investigation of Phycobilisome Subunit Interaction Interfaces by Coupled Cross-linking and Mass Spectrometry*

    PubMed Central

    Tal, Ofir; Trabelcy, Beny; Gerchman, Yoram; Adir, Noam

    2014-01-01

    The phycobilisome (PBS) is an extremely large light-harvesting complex, common in cyanobacteria and red algae, composed of rods and core substructures. These substructures are assembled from chromophore-bearing phycocyanin and allophycocyanin subunits, nonpigmented linker proteins and in some cases additional subunits. To date, despite the determination of crystal structures of isolated PBS components, critical questions regarding the interaction and energy flow between rods and core are still unresolved. Additionally, the arrangement of minor PBS components located inside the core cylinders is unknown. Different models of the general architecture of the PBS have been proposed, based on low resolution images from electron microscopy or high resolution crystal structures of isolated components. This work presents a model of the assembly of the rods onto the core arrangement and for the positions of inner core components, based on cross-linking and mass spectrometry analysis of isolated, functional intact Thermosynechococcus vulcanus PBS, as well as functional cross-linked adducts. The experimental results were utilized to predict potential docking interactions of different protein pairs. Combining modeling and cross-linking results, we identify specific interactions within the PBS subcomponents that enable us to suggest possible functional interactions between the chromophores of the rods and the core and improve our understanding of the assembly, structure, and function of PBS. PMID:25296757

  8. Carboxyl-modified poly(vinyl alcohol)-crosslinked chitosan hydrogel films for potential wound dressing.

    PubMed

    Zhang, Di; Zhou, Wei; Wei, Bing; Wang, Xin; Tang, Rupei; Nie, Jiemin; Wang, Jun

    2015-07-10

    The objective of this study was to develop a novel carboxyl-modified poly(vinyl alcohol)-crosslinked chitosan hydrogel films for potential wound dressing. To prepare the crosslinked hydrogels, poly(vinyl alcohol) (PVA) was grafted with succinate acid to yield carboxyl-modified poly(vinyl alcohol) (PVA-COOH). Hydrogel films based on PVA-COOH and chitosan (CS) at different concentrations were crosslinked through the formation of amide linkages. The mechanical properties of these crosslinked hydrogel films in dry and swollen state were greatly improved with high swelling ratio. Water vapor and oxygen permeability evaluations indicated that crosslinked hydrogel films could maintain a moist environment over wound bed. Biocompatibility test showed the crosslinked hydrogels had no cytotoxicity and hemolytic potential. Gentamicin sulfate-loaded crosslinked hydrogel films showed sustained drug release profile, and could effectively suppress bacterial proliferation and protect wound from infection.

  9. DC conduction and breakdown characteristics of Al2O3/cross-linked polyethylene nanocomposites for high voltage direct current transmission cable insulation

    NASA Astrophysics Data System (ADS)

    Park, Yong-Jun; Kwon, Jung-Hun; Sim, Jae-Yong; Hwang, Ju-Na; Seo, Cheong-Won; Kim, Ji-Ho; Lim, Kee-Joe

    2014-08-01

    We have discussed a cross-linked polyethylene (XLPE) nanocomposite insulating material that is able to DC voltage applications. Nanocomposites, which are composed in polymer matrix mixed with nano-fillers, have received considerable attention because of their potential benefits as dielectrics. The nano-sized alumina oxide (Al2O3)/XLPE nanocomposite was prepared, and three kinds of test, such as DC breakdown, DC polarity reversal breakdown, and volume resistivity were performed. By the addition of nano-sized Al2O3 filler, both the DC breakdown strength and the volume resistivity of XLPE were increased. A little homogeneous space charge was observed in Al2O3/XLPE nanocomposite material in the vicinity of electrode through the polarity reversal breakdown test. From these results, it is thought that the addition of Al2O3 nano-filler is effective for the improvement of DC electrical insulating properties of XLPE.

  10. Development of the High-Order Decoupled Direct Method in Three Dimensions for Particulate Matter: Enabling Advanced Sensitivity Analysis in Air Quality Models

    EPA Science Inventory

    The high-order decoupled direct method in three dimensions for particular matter (HDDM-3D/PM) has been implemented in the Community Multiscale Air Quality (CMAQ) model to enable advanced sensitivity analysis. The major effort of this work is to develop high-order DDM sensitivity...

  11. Spectroscopic characterization of collagen cross-links in bone

    NASA Technical Reports Server (NTRS)

    Paschalis, E. P.; Verdelis, K.; Doty, S. B.; Boskey, A. L.; Mendelsohn, R.; Yamauchi, M.

    2001-01-01

    Collagen is the most abundant protein of the organic matrix in mineralizing tissues. One of its most critical properties is its cross-linking pattern. The intermolecular cross-linking provides the fibrillar matrices with mechanical properties such as tensile strength and viscoelasticity. In this study, Fourier transform infrared (FTIR) spectroscopy and FTIR imaging (FTIRI) analyses were performed in a series of biochemically characterized samples including purified collagen cross-linked peptides, demineralized bovine bone collagen from animals of different ages, collagen from vitamin B6-deficient chick homogenized bone and their age- and sex-matched controls, and histologically stained thin sections from normal human iliac crest biopsy specimens. One region of the FTIR spectrum of particular interest (the amide I spectral region) was resolved into its underlying components. Of these components, the relative percent area ratio of two subbands at approximately 1660 cm(-1) and approximately 1690 cm(-1) was related to collagen cross-links that are abundant in mineralized tissues (i.e., pyridinoline [Pyr] and dehydrodihydroxylysinonorleucine [deH-DHLNL]). This study shows that it is feasible to monitor Pyr and DHLNL collagen cross-links spatial distribution in mineralized tissues. The spectroscopic parameter established in this study may be used in FTIRI analyses, thus enabling the calculation of relative Pyr/DHLNL amounts in thin (approximately 5 microm) calcified tissue sections with a spatial resolution of approximately 7 microm.

  12. Evaluating Dimethyldiethoxysilane for use in Polyurethane Crosslinked Silica Aerogels

    NASA Technical Reports Server (NTRS)

    Randall, Jason P.; Meador, Mary Ann B.; Jana, Sadhan C.

    2008-01-01

    Silica aerogels are highly porous materials which exhibit exceptionally low density and thermal conductivity. Their "pearl necklace" nanostructure, however, is inherently weak; most silica aerogels are brittle and fragile. The strength of aerogels can be improved by employing an additional crosslinking step using isocyanates. In this work, dimethyldiethoxysilane (DMDES) is evaluated for use in the silane backbone of polyurethane crosslinked aerogels. Approximately half of the resulting aerogels exhibited a core/shell morphology of hard crosslinked aerogel surrounding a softer, uncrosslinked center. Solid state NMR and scanning electron microscopy results indicate the DMDES incorporated itself as a conformal coating around the outside of the secondary silica particles, in much the same manner as isocyanate crosslinking. Response surface curves were generated from compression data, indicating levels of reinforcement comparable to that in previous literature, despite the core/shell morphology.

  13. Laser crosslink configurations for RF satellite communications systems

    NASA Astrophysics Data System (ADS)

    Sebacher, K. S.; Lambert, S. G.; Pautler, J. A.; Carter, J. P.

    Predictions of future satellite communications traffic indicate that an increased capacity for satellite communications systems is required. Crosslinks between satellites provide improvements in communications throughput for these systems. Crosslinks also increase system flexibility and remove the dependence of world-wide information flow on relay ground stations located outside the continental United States. Laser crosslinks provide the additional advantage of eliminating susceptibility to space-based or ground-based jammers. Laser terminals are also smaller and require smaller antennas than an RF terminal. This paper describes the advantages of adding laser crosslinks to RF satellite communications systems. Characteristics of the required RF/optical interfaces on-board the satellites are addessed. Terminal configurations that provide reliable, accurate laser communications at high data rates are described.

  14. The colibactin warhead crosslinks DNA

    NASA Astrophysics Data System (ADS)

    Vizcaino, Maria I.; Crawford, Jason M.

    2015-05-01

    Members of the human microbiota are increasingly being correlated to human health and disease states, but the majority of the underlying microbial metabolites that regulate host-microbe interactions remain largely unexplored. Select strains of Escherichia coli present in the human colon have been linked to the initiation of inflammation-induced colorectal cancer through an unknown small-molecule-mediated process. The responsible non-ribosomal peptide-polyketide hybrid pathway encodes ‘colibactin’, which belongs to a largely uncharacterized family of small molecules. Genotoxic small molecules from this pathway that are capable of initiating cancer formation have remained elusive due to their high instability. Guided by metabolomic analyses, here we employ a combination of NMR spectroscopy and bioinformatics-guided isotopic labelling studies to characterize the colibactin warhead, an unprecedented substituted spirobicyclic structure. The warhead crosslinks duplex DNA in vitro, providing direct experimental evidence for colibactin's DNA-damaging activity. The data support unexpected models for both colibactin biosynthesis and its mode of action.

  15. Epoxy Crosslinked Silica Aerogels (X-Aerogels)

    NASA Technical Reports Server (NTRS)

    fabrizio, Eve; Ilhan, Faysal; Meador, Mary Ann; Johnston, Chris; Leventis, Nicholas

    2004-01-01

    NASA is interested in the development of strong lightweight materials for the dual role of thermal insulator and structural component for space vehicles; freeing more weight for useful payloads. Aerogels are very-low density materials (0.010 to 0.5 g/cc) that, due to high porosity (meso- and microporosity), can be, depending on the chemical nature of the network, ideal thermal insulators (thermal conductivity approx. 15 mW/mK). However, aerogels are extremely fragile. For practical application of aerogels, one must increase strength without compromising the physical properties attributed to low density. This has been achieved by templated growth of an epoxy polymer layer that crosslinks the "pearl necklace" network of nanoparticles: the framework of a typical silica aerogel. The requirement for conformal accumulation of the epoxy crosslinker is reaction both with the surface of silica and with itself. After cross-linking, the strength of a typical aerogel monolith increases by a factor of 200, in the expense of only a 2-fold increase in density. Strength is increased further by coupling residual unreacted epoxides with diamine.

  16. Bioorthogonally cross-linked hydrogel network with precisely controlled disintegration time over a broad range.

    PubMed

    Xu, Jianwen; Feng, Ellva; Song, Jie

    2014-03-19

    Hydrogels with predictable degradation are highly desired for biomedical applications where timely disintegration of the hydrogel (e.g., drug delivery, guided tissue regeneration) is required. However, precisely controlling hydrogel degradation over a broad range in a predictable manner is challenging due to limited intrinsic variability in the degradation rate of liable bonds and difficulties in modeling degradation kinetics for complex polymer networks. More often than not, empirical tuning of the degradation profile results in undesired changes in other properties. Here we report a simple but versatile hydrogel platform that allows us to formulate hydrogels with predictable disintegration time from 2 to >250 days yet comparable macroscopic physical properties. This platform is based on a well-defined network formed by two pairs of four-armed polyethylene glycol macromers terminated with azide and dibenzocyclooctyl groups, respectively, via labile or stable linkages. The high-fidelity bioorthogonal reaction between the symmetric hydrophilic macromers enables robust cross-linking in water, phosphate-buffered saline, and cell culture medium to afford tough hydrogels capable of withstanding >90% compressive strain. Strategic placement of labile ester linkages near the cross-linking site within this superhydrophilic network, accomplished by adjustments of the ratio of the macromers used, enables broad tuning of the disintegration rates precisely matching with the theoretical predictions based on first-order linkage cleavage kinetics. This platform can be exploited for applications where a precise degradation rate is targeted.

  17. Robust Cross-Linked Stereocomplexes and C60 Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization.

    PubMed

    Vidal, Fernando; Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene Y-X

    2016-08-01

    The successful synthesis of highly syndiotactic polar vinyl polymers bearing the reactive pendant vinyl group on each repeat unit, which is enabled by perfectly chemoselective and highly syndiospecific coordination polymerization of divinyl polar monomers developed through this work, has allowed the construction of robust cross-linked supramolecular stereocomplexes and C60 inclusion complexes. The metal-mediated coordination polymerization of three representative polar divinyl monomers, including vinyl methacrylate (VMA), allyl methacrylate (AMA), and N,N-diallyl acrylamide (DAA) by Cs-ligated zirconocenium ester enolate catalysts under ambient conditions exhibits complete chemoselectivity and high stereoselectivity, thus producing the corresponding vinyl-functionalized polymers with high (92% rr) to quantitative (>99% rr) syndiotacticity. A combined experimental (synthetic, kinetic, and mechanistic) and theoretical (DFT) investigation has yielded a unimetallic, enantiomorphic-site-controlled propagation mechanism. Postfunctionalization of the obtained syndiotactic vinyl-functionalized polymers via the thiol-ene click and photocuring reactions readily produced the corresponding thiolated polymers and flexible cross-linked thin-film materials, respectively. Complexation of such syndiotactic vinyl-functionalized polymers with isotactic poly(methyl methacrylate) and fullerene C60 generates supramolecular crystalline helical stereocomplexes and inclusion complexes, respectively. Cross-linking of such complexes affords robust cross-linked stereocomplexes that are solvent-resistant and also exhibit considerably enhanced thermal and mechanical properties compared with the un-cross-linked stereocomplexes. PMID:27388024

  18. Cross-linking multiwall carbon nanotubes using PFPA to build robust, flexible and highly aligned large-scale sheets and yarns.

    PubMed

    Inoue, Yoku; Nakamura, Kazumichi; Miyasaka, Yuta; Nakano, Takayuki; Kletetschka, Gunther

    2016-03-18

    Multi-walled carbon nanotube (CNT) structures, including unidirectionally aligned sheets and spun yarns, were fabricated by direct dry-spinning methods from spinnable CNT arrays. We improved the mechanical properties of the CNT structures. CNTs were tailored in sheets and yarns using perfluorophenyl azide (PFPA) as a binding agent. The azide group of PFPA bonds to graphene crystal surfaces under UV radiation exposed for 1 h. For the CNT sheet, Young's modulus increased from 1.6 to 32.9 GPa and tensile strength increased from 35.9 MPa to 144.5 MPa. For the CNT yarns Young's modulus increased from 29.5 to 78.0 GPa and tensile strength increased from 639.1 to 675.6 MPa. With this treatment, the CNT sheets became more robust and more flexible materials. Since cross-linking of CNTs by PFPA is a simple and rapid process, it is suitable for fabrication of enhanced CNT materials. PMID:26871413

  19. Cross-linking multiwall carbon nanotubes using PFPA to build robust, flexible and highly aligned large-scale sheets and yarns

    NASA Astrophysics Data System (ADS)

    Inoue, Yoku; Nakamura, Kazumichi; Miyasaka, Yuta; Nakano, Takayuki; Kletetschka, Gunther

    2016-03-01

    Multi-walled carbon nanotube (CNT) structures, including unidirectionally aligned sheets and spun yarns, were fabricated by direct dry-spinning methods from spinnable CNT arrays. We improved the mechanical properties of the CNT structures. CNTs were tailored in sheets and yarns using perfluorophenyl azide (PFPA) as a binding agent. The azide group of PFPA bonds to graphene crystal surfaces under UV radiation exposed for 1 h. For the CNT sheet, Young’s modulus increased from 1.6 to 32.9 GPa and tensile strength increased from 35.9 MPa to 144.5 MPa. For the CNT yarns Young’s modulus increased from 29.5 to 78.0 GPa and tensile strength increased from 639.1 to 675.6 MPa. With this treatment, the CNT sheets became more robust and more flexible materials. Since cross-linking of CNTs by PFPA is a simple and rapid process, it is suitable for fabrication of enhanced CNT materials.